WO2018181511A1 - Method for delaminating adhesive sheet - Google Patents
Method for delaminating adhesive sheet Download PDFInfo
- Publication number
- WO2018181511A1 WO2018181511A1 PCT/JP2018/012838 JP2018012838W WO2018181511A1 WO 2018181511 A1 WO2018181511 A1 WO 2018181511A1 JP 2018012838 W JP2018012838 W JP 2018012838W WO 2018181511 A1 WO2018181511 A1 WO 2018181511A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- adhesive sheet
- adhesive layer
- meth
- Prior art date
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/683—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
Definitions
- the present invention relates to a pressure-sensitive adhesive sheet peeling method capable of reducing the adhesive strength at a desired timing and easily peeling the adherend.
- an adhesive sheet may be used to temporarily fix a processing target such as an electronic member such as a semiconductor wafer or a display device constituent member (electronic member / optical member).
- a pressure-sensitive adhesive sheet can reduce the pressure-sensitive adhesive force of the pressure-sensitive adhesive sheet at a desired timing by a method such as applying energy, thereby facilitating the separation of the object to be processed (the adherend).
- it is subjected to a desired processing step in a state where an adherend such as an electronic member or an optical member is fixed to the adhesive sheet.
- An object of the present invention is to provide a peeling method between an adhesive sheet and an adherend that can reduce the adhesive force at a desired timing by a novel action mechanism.
- this invention is a peeling method of the adhesive sheet which peels an adhesive sheet provided with an adhesive layer at least, and the to-be-adhered body stuck on the adhesive surface of the said adhesive layer,
- the said adhesive layer is
- the pressure-sensitive adhesive layer has an air chamber inside, and at least the pressure-sensitive adhesive sheet to which the adherend is adhered is subjected to a decompression treatment for expanding the gas in the air chamber, whereby the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer is increased.
- the pressure-sensitive adhesive sheet peeling method is provided, wherein the pressure-sensitive adhesive sheet and the adherend are peeled off (Invention 1).
- the “sheet” in the present invention includes the concept of “tape”.
- the adhesive force can be reduced at a desired timing by a novel action mechanism of expanding the gas in the air chamber by a decompression process. Peeling of the sheet and the adherend can be facilitated.
- the pressure reduction treatment is made lower than the atmospheric pressure of the environment in which the adhesive sheet is adhered to the adherend (Invention 2).
- the adhesive composition which forms the said adhesive layer may not have active energy ray curability and thermosetting (invention 3), and this invention (invention) In 3), it is preferable that the pressure-sensitive adhesive composition contains a (meth) acrylic acid ester polymer (Invention 4).
- the adhesive composition which forms the said adhesive layer may have active energy ray curability or thermosetting (invention 5), and in this invention (invention 5)
- the active energy ray-curable pressure-sensitive adhesive composition preferably contains a (meth) acrylic acid ester polymer having an active energy ray-curable group in the side chain (Invention 6).
- the said pressure reduction process may be performed (invention 7), and the said pressure reduction After the treatment, the pressure-sensitive adhesive layer may be cured by irradiating the pressure-sensitive adhesive layer with energy rays (Invention 8).
- the pressure-sensitive adhesive sheet is preferably used for temporarily fixing the adherend (Invention 9).
- the adherend is an electronic member or an optical member. It may be a member (Invention 10).
- this invention is a manufacturing method of the workpiece obtained by processing a workpiece
- a manufacturing method is provided (Invention 11).
- the adhesive force can be reduced at a desired timing by a novel action mechanism, and the peeling between the pressure-sensitive adhesive sheet and the adherend is facilitated. be able to.
- the peeling method of the adhesive sheet which concerns on this embodiment is a method of peeling an adhesive sheet provided with an adhesive layer at least, and the to-be-adhered body stuck on the adhesive surface of the said adhesive layer.
- the pressure-sensitive adhesive layer has an air chamber inside, and in the present embodiment, at least the pressure-sensitive adhesive sheet to which the adherend is adhered is subjected to a decompression process for expanding the gas in the air chamber. The adhesive strength of the pressure-sensitive adhesive layer is reduced, and the pressure-sensitive adhesive sheet and the adherend are easily separated.
- FIG. 1 is a sectional view of an adhesive sheet used in one embodiment of the present invention.
- the pressure-sensitive adhesive sheet 1 according to this embodiment includes a pressure-sensitive adhesive layer 2, and the pressure-sensitive adhesive layer 2 has an air chamber 3 inside.
- the pressure-sensitive adhesive sheet 1 according to the present embodiment is a surface opposite to the pressure-sensitive adhesive surface P (the surface in contact with the adherend, the upper surface in FIG. 1) in the pressure-sensitive adhesive layer (the lower surface in FIG. 1).
- a substrate 4 may be further provided.
- the pressure-sensitive adhesive sheet 1 according to this embodiment can be used for temporarily fixing an electronic member or an optical member, for example.
- the case where it is used for temporarily fixing a semiconductor wafer will be mainly described.
- the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition that does not have active energy ray curability and thermosetting (hereinafter sometimes referred to as “non-curable” in the present specification). It may be a pressure-sensitive adhesive layer, or may be a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition having active energy ray curability or thermosetting. When the pressure-sensitive adhesive layer is composed of multiple layers, a combination of a non-curable pressure-sensitive adhesive layer and a curable pressure-sensitive adhesive layer may be used.
- Non-curable pressure-sensitive adhesive compositions examples include acrylic pressure-sensitive adhesive compositions, rubber-based pressure-sensitive adhesive compositions, silicone-based pressure-sensitive adhesive compositions, and urethane-based pressure-sensitive adhesives. Examples thereof include a composition, a polyester-based pressure-sensitive adhesive composition, a polyvinyl ether-based pressure-sensitive adhesive composition, and among them, an acrylic pressure-sensitive adhesive composition is preferable.
- an acrylic adhesive composition what contains a conventionally well-known (meth) acrylic acid ester polymer can be used. In the present specification, the term “polymer” includes the concept of “copolymer”.
- the (meth) acrylic acid ester polymer (A) contained in the acrylic pressure-sensitive adhesive composition may be a homopolymer formed from one type of (meth) acrylic acid ester monomer, or a plurality of types of ( The copolymer may be a copolymer formed from a (meth) acrylate monomer, or a copolymer formed from one or more types of (meth) acrylate monomers and monomers other than (meth) acrylate monomers. It may be a polymer. Moreover, a (meth) acrylic acid ester polymer (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
- Specific types of the compound that becomes the (meth) acrylic acid ester monomer are not particularly limited, and specific examples include (meth) acrylic acid, (meth) acrylic acid ester, and derivatives thereof (acrylonitrile, itaconic acid, and the like).
- Specific examples of (meth) acrylic acid esters include chain skeletons such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
- (meth) acrylate Having Dorokishi group (meth) acrylate; glycidyl (meth) acrylate, (meth) acrylates having reactive functional groups other than hydroxy group, such as N- methylaminoethyl (meth) acrylate.
- monomers other than (meth) acrylic acid ester monomers include olefins such as ethylene and norbornene, vinyl acetate, and styrene.
- the (meth) acrylic acid ester monomer is an alkyl (meth) acrylate, the alkyl group preferably has 1 to 18 carbon atoms.
- (meth) acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms.
- the (meth) acrylic acid ester polymer (A) is directly contained in the pressure-sensitive adhesive composition.
- at least a part thereof may be contained as a crosslinked product by performing a crosslinking reaction with a crosslinking agent.
- the (meth) acrylic acid ester polymer (A) preferably has a reactive functional group that reacts with the crosslinking agent.
- the type of the reactive functional group is not particularly limited, and may be appropriately determined based on the type of the crosslinking agent.
- examples of the reactive functional group of the (meth) acrylic acid ester polymer (A) include a hydroxy group, a carboxyl group, and an amino group. These highly reactive hydroxy groups are preferred.
- examples of the reactive functional group of the (meth) acrylic acid ester polymer (A) include a carboxyl group, an amino group, an amide group, etc. These highly reactive carboxyl groups are preferred.
- the method for introducing the reactive functional group into the (meth) acrylic acid ester polymer (A) is not particularly limited.
- the (meth) acrylic acid ester polymer (A) using a monomer having a reactive functional group is used.
- a constitutional unit based on a monomer having a reactive functional group is contained in the polymer skeleton.
- a carboxyl group is introduced into the (meth) acrylic acid ester polymer (A)
- a (meth) acrylic acid ester polymer (A) is formed using a monomer having a carboxyl group such as (meth) acrylic acid. do it.
- the (meth) acrylic acid ester polymer (A) When the (meth) acrylic acid ester polymer (A) has a reactive functional group, it accounts for the total mass of the (meth) acrylic acid ester polymer (A) from the viewpoint of making the degree of crosslinking a good range.
- the proportion of the mass of the structural portion derived from the monomer having a reactive functional group is preferably about 1 to 20% by mass, and more preferably 2 to 10% by mass.
- the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A) is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,500,000 from the viewpoint of film forming properties at the time of coating. preferable.
- the weight average molecular weights of the (meth) acrylic acid ester polymer (A) and the (meth) acrylic acid ester polymers (B1) and (B3) described later are gel permeation chromatography (GPC). It is a value in terms of standard polystyrene measured by the method, and details of the measuring method are shown in the examples described later.
- the glass transition temperature Tg of the (meth) acrylic acid ester polymer (A) is preferably in the range of ⁇ 70 ° C. to 30 ° C., more preferably in the range of ⁇ 60 ° C. to 20 ° C.
- the glass transition temperature can be calculated from the Fox equation.
- the active energy ray-curable pressure-sensitive adhesive composition has an active energy ray-curable compound (B2) and an active energy ray-curable group introduced into the side chain ( It is preferable that at least one of the (meth) acrylic acid ester polymer (B3) is contained.
- the active energy ray-curable pressure-sensitive adhesive composition is composed of the active energy ray-curable compound (B2) and the (meth) acrylic acid ester polymer (B3) in which an active energy ray-curable group is introduced into the side chain.
- the active energy ray-curable pressure-sensitive adhesive composition may further contain a (meth) acrylic acid ester polymer (B1) having no active energy ray curability.
- (1-2-1) (Meth) acrylic acid ester polymer having no active energy ray curability (B1)
- the adhesive composition which forms the adhesive layer in this embodiment contains the (meth) acrylic acid ester polymer (B1) which does not have active energy ray curability
- the said (meth) acrylic acid ester polymer (B1) ) May be contained in the pressure-sensitive adhesive composition as it is, or at least a part thereof may be contained as a crosslinked product by performing a crosslinking reaction with a crosslinking agent described later.
- (meth) acrylic acid ester polymer (B1) the same thing as the (meth) acrylic acid ester polymer (A) mentioned above regarding the non-curable adhesive composition can be used.
- the active energy ray curable compound (B2) is a compound having an active energy ray curable group and polymerized when irradiated with active energy rays such as ultraviolet rays and electron beams.
- the active energy ray-curable group possessed by the active energy ray-curable compound (B2) is, for example, a group containing an active energy ray-curable carbon-carbon double bond, and specifically includes a (meth) acryloyl group, vinyl Examples include groups.
- Examples of the active energy ray-curable compound (B2) are not particularly limited as long as the active energy ray-curable group has the above-mentioned active energy ray-curable group.
- low molecular weight compounds monofunctional and polyfunctional monomers and Oligomer
- Specific examples of the low molecular weight active energy ray-curable compound (B2) include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol monohydroxypenta.
- the active energy ray-curable compound (B2) usually has a molecular weight of 100 to 30,000, preferably about 300 to 10,000.
- the content of the active energy ray-curable compound (B2) in the active energy ray-curable adhesive composition and the content ratio with other components are not particularly limited, but the active energy ray-curable adhesive composition is active energy.
- the active energy ray-curable adhesive composition is active energy.
- the active energy ray curable compound (B2) is the above (meth) acrylic acid.
- the amount is preferably 10 to 400 parts by mass, more preferably about 30 to 350 parts by mass with respect to 100 parts by mass of the ester polymer (B1).
- the active energy ray-curable compound (B2) when it contains the active energy ray-curable compound (B2) and the (meth) acrylic acid ester polymer (B3) in which an active energy ray-curable group is introduced in the side chain described later, )
- the content of the active energy ray-curable compound (B2) is preferably in the above range with respect to 100 parts by mass of the acrylic ester polymer (B3).
- the active energy ray-curable pressure-sensitive adhesive composition has the active energy ray-curable compound (B2), the (meth) acrylic acid ester polymer (B1), and the active energy ray-curable group introduced into the side chain.
- the total amount of the (meth) acrylic acid ester polymer (B1) and the (meth) acrylic acid ester polymer (B3) is 100 parts by mass.
- the content of the active energy ray-curable compound (B2) is preferably in the above range.
- (1-2-3) (Meth) acrylic acid ester polymer (B3) having an active energy ray-curable group introduced in the side chain
- the active energy ray-curable pressure-sensitive adhesive composition in the present embodiment contains a (meth) acrylic acid ester polymer (B3) having an active energy ray-curable group introduced in the side chain, such (meth) acrylic acid ester
- the polymer (B3) may be contained in the pressure-sensitive adhesive composition as it is, or at least a part thereof may be contained as a crosslinked product by performing a crosslinking reaction with a crosslinking agent described later.
- the main skeleton of the (meth) acrylic acid ester polymer (B3) in which the active energy ray-curable group is introduced into the side chain is not particularly limited, and is the same as that of the aforementioned (meth) acrylic acid ester polymer (B1). Are illustrated.
- the active energy ray-curable group introduced into the side chain of the (meth) acrylate polymer (B3) is, for example, a group containing an active energy ray-curable carbon-carbon double bond.
- a meth) acryloyl group etc. can be illustrated.
- the active energy ray-curable group may be bonded to the (meth) acrylic acid ester polymer (B3) via an alkylene group, an alkyleneoxy group, a polyalkyleneoxy group, or the like.
- the (meth) acrylic acid ester polymer (B3) in which an active energy ray-curable group is introduced into the side chain contains, for example, a functional group such as a hydroxy group, a carboxyl group, an amino group, a substituted amino group, and an epoxy group.
- a (meth) acrylic acid ester polymer is reacted with a substituent that reacts with the functional group and a curable group-containing compound having 1 to 5 active energy ray-curable carbon-carbon double bonds per molecule. Obtained.
- Such a (meth) acrylic acid ester polymer includes a (meth) acrylic acid ester monomer or a derivative thereof having a functional group such as a hydroxy group, a carboxyl group, an amino group, a substituted amino group, and an epoxy group, and the component (B1) described above. It can be obtained by copolymerizing with a monomer that constitutes.
- curable group-containing compound examples include (meth) acryloyloxyethyl isocyanate, meta-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, (meth) acryloyl isocyanate, allyl isocyanate, glycidyl (meth) acrylate, (meth) Acrylic acid etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types.
- the active energy ray hardening group was introduce
- the kind of the reactive functional group is not particularly limited, and the (meth) acrylic acid ester polymer (B1) described above (and the (meth) acrylic acid ester polymer (A) described above with respect to the non-curable pressure-sensitive adhesive composition) and The same thing can be illustrated.
- the weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (B3) having an active energy ray-curable group introduced in the side chain is preferably 100,000 to 2,000,000, and 300,000 to 1,500,000. More preferably.
- the glass transition temperature (Tg) of the (meth) acrylic acid ester polymer (B3) is preferably in the range of ⁇ 70 to 30 ° C., more preferably in the range of ⁇ 60 to 20 ° C.
- the glass transition temperature (Tg) of the (meth) acrylic acid ester polymer (B3) refers to that of the (meth) acrylic acid ester polymer before being reacted with the curable group-containing compound.
- thermosetting pressure-sensitive adhesive composition examples include those containing an epoxy resin, a phenol resin, and the like.
- the adhesive composition forming the adhesive layer in this embodiment may contain a crosslinking agent capable of reacting with the polymer contained in the above-mentioned adhesive composition.
- the pressure-sensitive adhesive layer in this embodiment comprises a polymer ((meth) acrylic acid ester polymer (A), (B1), (B3), etc.) contained in the pressure-sensitive adhesive composition and a crosslinking agent. Contains a cross-linked product obtained by a cross-linking reaction.
- crosslinking agent examples include polyimine compounds such as polyisocyanate compounds, epoxy compounds, metal chelate compounds, and aziridine compounds, melamine resins, urea resins, dialdehydes, methylol polymers, metal alkoxides, metal salts, and the like. 1 type can be used individually or in combination of 2 or more types. Among these, an epoxy compound or a polyisocyanate compound is preferable because it is easy to control the crosslinking reaction.
- a polyisocyanate compound is a compound having two or more isocyanate groups per molecule.
- aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like
- epoxy compound examples include 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, ethylene glycol diglycidyl ether. 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidylaniline, diglycidylamine and the like.
- the content of the crosslinking agent in the pressure-sensitive adhesive composition that forms the pressure-sensitive adhesive layer is the polymer contained in the pressure-sensitive adhesive composition (for example, (meth) acrylic acid ester polymers (A), (B1) and (B3)). Is preferably 0.01 to 50 parts by mass, more preferably 0.02 to 10 parts by mass, and more preferably 0.03 to 5 parts by mass with respect to 100 parts by mass of the total amount of Part is more preferable, and 0.08 to 0.5 part by mass is particularly preferable.
- the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer in the present embodiment contains a crosslinking agent
- an appropriate crosslinking accelerator may be contained depending on the type of the crosslinking agent.
- the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer in the present embodiment includes, in addition to the above components, a photopolymerization initiator, a photosensitizer, a crosslinking accelerator, a dye, a pigment, and the like. You may contain various additives, such as a coloring material, a flame retardant, a filler, a heat conductive agent, a tackifier, a plasticizer, and an antistatic agent.
- the pressure-sensitive adhesive composition when the pressure-sensitive adhesive composition has active energy ray curability that is cured by active energy rays such as ultraviolet rays, the pressure-sensitive adhesive composition preferably contains a photopolymerization initiator.
- photopolymerization initiators examples include photoinitiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, and peroxide compounds, and photosensitizers such as amines and quinones.
- 1-hydroxycyclohexyl phenyl ketone benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, ⁇ -chloranthraquinone 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like, and these can be used alone or in combination of two or more.
- ultraviolet rays When ultraviolet rays are used as energy rays, the irradiation time and irradiation amount can be reduced by blending a photopolymerization initiator.
- an adhesive layer has an air chamber in the inside.
- the gas in the air chamber expands due to the decompression process to be described later, whereby a pressure in the direction in which the air chamber expands is applied to the air chamber, and as a result, the adhesive force of the adhesive sheet decreases.
- the gas contained in the air chamber is not particularly limited, but may be, for example, air or an inert gas such as nitrogen, carbon dioxide, or argon.
- the shape of the air chamber is typically substantially spherical from the viewpoint of ease of formation, but is not limited thereto.
- the average diameter of the air chamber is not particularly limited, but is preferably, for example, 0.1 to 500 ⁇ m, more preferably 1 to 100 ⁇ m, and particularly preferably 10 to 50 ⁇ m.
- the volume ratio of the air chamber in the pressure-sensitive adhesive layer is, for example, preferably 0.5 to 20.0%, more preferably 1.0 to 10.0%, and more preferably 1.5 to 5%. Particularly preferred is 0.0%.
- the pressure-sensitive adhesive sheet can easily maintain a desired adhesive force before decompression, and the adherend can be more securely fixed. After pressure reduction, the effect of reducing the adhesive force due to the expansion of the gas in the air chamber becomes more excellent, and the adhesive sheet and the adherend are more easily separated.
- the average diameter of the air chamber is, for example, photographed the pressure-sensitive adhesive layer with a digital microscope or a scanning electron microscope (SEM), and the air chamber having a diameter of 0.1 ⁇ m or more, preferably about 10 or more air chambers, It can obtain
- the average diameter is calculated in terms of a spherical air chamber having an equivalent volume.
- the volume ratio of the air chambers in the pressure-sensitive adhesive layer is obtained by photographing the pressure-sensitive adhesive layer with a digital microscope or SEM and measuring the area ratio of the air chamber portion in the predetermined range, preferably about five or more photographed images. From the result of measuring the area ratio of the air chamber portions, the volume ratio of the air chamber can be obtained.
- the method for forming the air chamber in the pressure-sensitive adhesive layer is not particularly limited, and a known method can be appropriately employed.
- a method in which the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer is vigorously stirred and a gas such as air is intentionally mixed a method in which gas is injected (bubbled) into the pressure-sensitive adhesive composition, a hollow filler (a gas in the interior) And the like, and a method of forming an air chamber by foaming after forming a pressure-sensitive adhesive layer by blending a thermal foaming agent or the like into the pressure-sensitive adhesive composition.
- a surfactant may be added to the pressure-sensitive adhesive composition from the viewpoint of easy formation of the air chamber by mixing and injection of gas and the stability of the formed air chamber.
- surfactants include ionic surfactants, hydrocarbon surfactants, silicone surfactants, and fluorine surfactants.
- the thickness of the pressure-sensitive adhesive layer in this embodiment is preferably 5 to 100 ⁇ m, particularly preferably 10 to 50 ⁇ m, and 15 to 30 ⁇ m. More preferably. It is preferable that the pressure-sensitive adhesive layer has a thickness of 5 ⁇ m or more because more space can be secured during decompression. It is preferable for the thickness of the pressure-sensitive adhesive layer to be 100 ⁇ m or less because the film thickness accuracy during application can be ensured.
- the adhesive strength of the adhesive sheet is preferably 0.5 to 50 N / 25 mm, more preferably 2 to 40 N / 25 mm, and particularly preferably 5 to 30 N / 25 mm. .
- the adherend can be reliably fixed. For example, it is very useful for temporarily fixing the adherend in the processing step of the adherend.
- the adhesive force here does not perform the pressure reduction process mentioned later (When the adhesive composition has active energy ray curable property or thermosetting property, irradiation and heating of the active energy ray are not further performed).
- a silicon mirror wafer is used as an adherend, and the adhesive sheet is bonded to the mirror surface, and the adhesive strength (N / 25 mm) measured by the 180 ° peeling method according to JIS Z0237: 2009 is used.
- the adhesive strength reduction rate of the adhesive sheet is preferably 5% or more, more preferably 10% or more, and particularly preferably 30% or more. When the adhesive strength of the adhesive sheet is within the above range, in this embodiment, the adhesive sheet and the adherend are more easily separated.
- the adhesive force decreasing rate here is before performing the pressure reduction process mentioned later (When the adhesive composition has active energy ray curable or thermosetting, after irradiation or heating of active energy rays)
- the adhesive strength is measured as described above, and is calculated by the following formula based on the obtained value.
- Adhesive strength reduction rate (%) (adhesive strength before decompression ⁇ adhesive strength after decompression) / (adhesive strength after decompression) ⁇ 100
- the irradiation or heating of the active energy ray when the pressure-sensitive adhesive composition has active energy ray curable property or thermosetting property may be before or after the decompression treatment, Even in this case, the adhesive strength reduction rate is calculated by the above formula.
- the lower limit of the stress relaxation rate of the pressure-sensitive adhesive layer is preferably 30% or more, particularly preferably 45% or more, and 60% or more. Is more preferable.
- the upper limit of the stress relaxation rate of the pressure-sensitive adhesive layer is preferably 100% or less, particularly preferably 90% or less, and further preferably 80% or less.
- the stress relaxation rate of the pressure-sensitive adhesive layer here is not subjected to a decompression treatment described later (if the pressure-sensitive adhesive composition has active energy ray curable or thermosetting properties, irradiation or heating with active energy rays is further performed.
- the stress relaxation rate after being stretched by 300% in a tensile test and held for 300 seconds. Specifically, the tensile test was performed at a speed of 200 mm / min with an adhesive formed into a thickness of 500 ⁇ m, a width of 15 mm, and a length of 55 mm (of which the measurement range is 25 mm) in an environment of 23 ° C. and 50% RH. It is assumed that the stretching is performed by 300%.
- the lower limit of the breaking elongation of the pressure-sensitive adhesive layer is preferably 200% or more, particularly preferably 500% or more, and preferably 1000% or more. Is more preferable.
- the upper limit of the elongation at break of the pressure-sensitive adhesive layer is preferably 5000% or less, particularly preferably 4000% or less, and further preferably 3000% or less.
- the pressure-sensitive adhesive layer was measured as a single pressure-sensitive adhesive layer without a substrate or the like, and specifically, molded into a thickness of 500 ⁇ m, a width of 15 mm, and a length of 55 mm (of which the measurement range is 25 mm). The obtained adhesive is stretched at a speed of 200 mm / min in an environment of 23 ° C. and 50% RH.
- the lower limit of the gel fraction of the pressure-sensitive adhesive layer is preferably 1% or more, particularly preferably 2% or more, and 3% or more. Is more preferable.
- the upper limit of the gel fraction of the pressure-sensitive adhesive layer is preferably 80% or less, particularly preferably 70% or less, and further preferably 60% or less.
- the lower limit of the gel fraction of the pressure-sensitive adhesive layer is 1% or more, stability as a pressure-sensitive adhesive sheet can be ensured by reaction between the pressure-sensitive adhesives due to crosslinking.
- the upper limit of the gel fraction of the pressure-sensitive adhesive layer is 80% or less, it is easy to impart tack to the pressure-sensitive adhesive sheet, and good temporary fixability can be obtained.
- the gel fraction of an adhesive layer here is not performing the pressure reduction process mentioned later (When an adhesive composition has active energy ray sclerosis
- the pressure-sensitive adhesive sheet according to this embodiment may include a base material in addition to the pressure-sensitive adhesive layer.
- the base material is not particularly limited as long as the pressure-sensitive adhesive sheet can appropriately function in a desired process such as an adherend processing process.
- a paper base material, a resin film or sheet, a paper base The base material etc. which laminated the material with resin are mentioned, According to the use of the adhesive sheet of 1 aspect of this embodiment, it can select suitably.
- the film is composed of a resin-based material as a main material because of its advantage against the pressure reduction effect.
- Such films include ethylene-copolymer films such as ethylene-vinyl acetate copolymer films, ethylene- (meth) acrylic acid copolymer films, and ethylene- (meth) acrylic acid ester copolymer films; low density Polyethylene film such as polyethylene (LDPE) film, linear low density polyethylene (LLDPE) film, high density polyethylene (HDPE) film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, ethylene-norbornene copolymer film, Polyolefin film such as norbornene resin film; Polyvinyl chloride film such as polyvinyl chloride film and vinyl chloride copolymer film; Polyethylene terephthalate film, Polybutylene tele Polyester film of tallate films; polyurethane film; polyimide film; polystyrene films; polycarbonate films; and fluorine resin film. Further, modified films such as these crosslinked films and ionomer films are also used
- the film constituting the base material preferably includes at least one of an ethylene copolymer film and a polyolefin film. It is easy to control the mechanical characteristics of an ethylene copolymer film in a wide range by changing the copolymerization ratio. For this reason, the base material provided with the ethylene-based copolymer film easily satisfies the mechanical properties required as the base material of the pressure-sensitive adhesive sheet according to this embodiment. Moreover, since the ethylene copolymer film has relatively high adhesion to the pressure-sensitive adhesive layer, peeling at the interface between the base material and the pressure-sensitive adhesive layer hardly occurs when used as a pressure-sensitive adhesive sheet.
- the base material used in the present embodiment contains various additives such as pigments, dyes, flame retardants, plasticizers, antistatic agents, lubricants, fillers, etc., in the film mainly composed of the above-mentioned resin-based material. May be.
- the pigment include titanium dioxide and carbon black.
- the filler include organic materials such as melamine resin, inorganic materials such as fumed silica, and metal materials such as nickel particles. The content of such an additive is not particularly limited, but should be within a range where the substrate exhibits a desired function and does not lose smoothness and flexibility.
- the substrate is preferably permeable to ultraviolet rays.
- the base material has the transparency of an electron beam.
- the adherend has energy ray permeability and the energy beam is irradiated from the adherend side, the substrate does not need to have energy ray permeability.
- a component having one or more kinds selected from the group consisting of a carboxyl group and its ions and salts is provided on the surface of the substrate on the side of the pressure-sensitive adhesive layer (hereinafter also referred to as “substrate-coated surface”). Is preferably present.
- substrate-coated surface a component having one or more kinds selected from the group consisting of a carboxyl group and its ions and salts.
- the base material itself is an ethylene- (meth) acrylic acid copolymer film, an ionomer resin film, etc., and the resin constituting the base material is selected from the group consisting of carboxyl groups, ions and salts thereof. Or you may have 2 or more types.
- the substrate is, for example, a polyolefin film, and the substrate-adhered surface side is subjected to corona treatment or a primer layer is provided. May be.
- Various coating films may be provided on the surface of the substrate opposite to the substrate deposition surface.
- the thickness of the substrate is not limited as long as the pressure-sensitive adhesive sheet can function properly in a desired process, but it is preferably 5 to 1000 ⁇ m, more preferably 10 to 500 ⁇ m, and still more preferably 12 to 12 from the viewpoint of handleability and economy.
- the thickness is 250 ⁇ m, more preferably 15 to 150 ⁇ m.
- the release sheet is laminated on the adhesive surface of the adhesive layer for the purpose of protecting the adhesive layer until the adhesive layer is applied to the adherend. It may be.
- the configuration of the release sheet is arbitrary, and examples include a release film of a plastic film with a release agent.
- Specific examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene.
- the release agent silicone-based, fluorine-based, long-chain alkyl-based, and the like can be used, and among these, a silicone-based material that is inexpensive and provides stable performance is preferable.
- the thickness of the release sheet is not particularly limited, but is usually about 20 to 250 ⁇ m.
- the manufacturing method of an adhesive sheet is a method which can form the adhesive layer formed from the above-mentioned adhesive composition, and can form an air chamber inside an adhesive layer. If there is, the detailed method is not particularly limited.
- a method for producing a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer it is only necessary that a pressure-sensitive adhesive layer formed from the above-mentioned pressure-sensitive adhesive composition can be laminated on one surface of the base material.
- a coating composition containing the above-mentioned pressure-sensitive adhesive composition and optionally further containing a solvent or a dispersion medium is prepared.
- the coating composition may be vigorously stirred and a gas such as air may be intentionally mixed, or a gas may be injected (bubbled) into the coating composition.
- a gas such as air
- a gas may be injected (bubbled) into the coating composition.
- the coating composition thus obtained is applied on one surface of the substrate by a die coater, curtain coater, spray coater, slit coater, knife coater, etc. to form a coating film, and the coating film
- a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer and a substrate can be formed.
- the release sheet in this laminate may be peeled off as a process material, or the adhesive layer may be protected until being attached to an adherend such as an electronic member or an optical member.
- the properties of the coating composition are not particularly limited as long as it can be applied, and may contain a component for forming the pressure-sensitive adhesive layer as a solute or a dispersoid.
- the coating composition contains a thermal foaming agent
- the thermal foaming agent is foamed by changing the drying conditions (temperature, time, etc.) or by separately providing a heat treatment.
- a chamber may be formed.
- the coating composition contains a cross-linking agent, (meth) acrylic acid in the coating film can be obtained by changing the drying conditions (temperature, time, etc.) or by separately providing a heat treatment.
- crosslinking refers to a reaction performed before sticking the pressure-sensitive adhesive sheet to the adherend, and before sticking to the adherend is, for example, the pressure-sensitive adhesive described above. A step of forming a layer may be mentioned. Therefore, “crosslinking” of the pressure-sensitive adhesive is clearly distinguished from “curing” described later.
- a coating film is formed on the release surface of the above-described release sheet to form a coating film, which is dried to form a laminate composed of the pressure-sensitive adhesive layer and the release sheet.
- a laminate of the pressure-sensitive adhesive sheet and the release sheet may be obtained by forming a body and attaching the surface of the pressure-sensitive adhesive layer of the laminate opposite to the surface on the release sheet side to the substrate.
- the release sheet in this laminate may be peeled off as a process material, or the adhesive layer may be protected until being attached to an adherend such as an electronic member or an optical member.
- the composition for coating on the release surface of the aforementioned release sheet Is applied to form a coating film, which is dried to form a laminate composed of a pressure-sensitive adhesive layer and a release sheet, and the surface on the side opposite to the release sheet side of the pressure-sensitive adhesive layer of this laminate is It can affix on the peeling surface of this release sheet, and can obtain the laminated body which consists of a release sheet / adhesive sheet / release sheet.
- the release sheet in this laminate may be peeled off as a process material, or the adhesive layer may be protected until being attached to an adherend such as an electronic member or an optical member.
- Examples of the workpiece W to be subjected to the peeling method according to this embodiment include electronic members such as a semiconductor wafer, a semiconductor package, a multilayer substrate, a ceramic green sheet laminate, a batch sealing module; a liquid crystal display member, and an organic EL display member. And optical members such as an optical filter, a polarizing plate, and a retardation plate.
- the attachment of the workpiece W and the pressure-sensitive adhesive sheet 1 may be performed under atmospheric pressure, or may be performed in a chamber in which the atmospheric pressure is controlled by the pressure control device 10 described later.
- the atmospheric pressure in which the sticking process is performed or the atmospheric pressure in the chamber corresponds to the pressure of the gas in the air chamber 3 in the subsequent process, and the sticking process is performed after appropriately adjusting the atmospheric pressure. It becomes easy to control the amount of gas expansion in the decompression process.
- work W stuck on the adhesive sheet 1 by the sticking process can be attached
- processing steps include a back grinding process, a circuit forming process, a dicing process, a die sort process, and the like if the work W is a semiconductor wafer, and a laminating process and a transfer process if the work W is a display device component. Etc.
- the workpiece W is processed into a workpiece W ′.
- the adhesive sheet 1 is peeled from the workpiece W as described later after the processing step of the workpiece W, it can be said that it is used for temporarily fixing the workpiece W during the processing step.
- the adhesive sheet 1 in a state where the workpiece W ′ is adhered is placed in the chamber of the pressure control device 10 (FIG. 2C).
- the pressure-sensitive adhesive sheet 1 in a state where the workpiece W ′ is adhered is placed so that the workpiece W ′ is on the lower side of the pressure-sensitive adhesive sheet 1. It is preferable to place in the chamber.
- the workpiece W ′ can be expanded when the air chamber 3 can be expanded in the decompression process. It may be placed in the chamber so that is on the upper side of the adhesive sheet 1.
- the pressure reduction treatment is preferably lower than the atmospheric pressure of the pasting environment, more preferably lower so that the atmospheric pressure in the chamber has a difference of 10 kPa or more than the atmospheric pressure of the pasting environment.
- the difference is more preferably 30 kPa or more, still more preferably 50 kPa or more, further preferably 80 kPa or more, and particularly preferably 90 kPa or more.
- the lower limit value of the pressure in the chamber is not particularly limited, but is usually 10 ⁇ 7 Pa or more, preferably 10 ⁇ 5 Pa or more, more preferably 10 ⁇ 1 Pa or more, and even more, from a technical viewpoint.
- it is 10 Pa or more, More preferably, it is 100 Pa or more, Especially preferably, it is 1000 Pa or more.
- the pressure-sensitive adhesive layer 2 is relatively soft as a result of the decompression process, a convex portion is formed on a part of the pressure-sensitive adhesive surface P following the expansion of the air chamber 3 as shown in FIG. Arise.
- the plurality of air chambers 3 may communicate with each other to form a larger air chamber 3. It is preferable to form a larger air chamber 3 because the expansion effect due to the reduced pressure becomes more remarkable.
- the air chamber 3 in the vicinity of the adhesive surface P expands, it may be exposed on the adhesive surface P, and the portion that was the air chamber 3 may become a concave portion of the adhesive surface P. As a result, irregularities are formed on the adhesive surface P.
- the adhesive area between the pressure-sensitive adhesive layer 2 and the workpiece W ′ decreases, and the adhesive force of the pressure-sensitive adhesive sheet 1 to the workpiece W ′ decreases.
- the adhesive layer 2 peels a part or all from the workpiece W 'from the location (FIG. 2 ( e)).
- the pressure-sensitive adhesive layer 2 when the pressure-sensitive adhesive layer 2 is relatively hard, the processed product of the pressure-sensitive adhesive sheet 1 with almost no expansion of the air chamber 3 and deformation of the pressure-sensitive adhesive surface P as shown in FIG. In some cases, the adhesive strength to W ′ decreases, and the adhesive layer 2 peels from the workpiece W ′ as shown in FIG. This is considered to be because the force that pushes up the base material in the longitudinal direction of the adhesive is prioritized over the expansion of the adhesive because the adhesive is relatively hard.
- the pressure-sensitive adhesive sheet 1 and the workpiece W ′ can be easily peeled off by decreasing the adhesive force of the pressure-sensitive adhesive layer 2 to the workpiece W ′.
- the pressure-sensitive adhesive sheet 1 and the workpiece W ′ can be peeled as they are in the state shown in FIG. 2E.
- the pressure-sensitive adhesive sheet 1 is placed in the chamber so that the workpiece W ′ is on the upper side of the pressure-sensitive adhesive sheet 1.
- the pressure-sensitive adhesive sheet 1 and the workpiece W ′ are peeled off by the weight of the workpiece W ′. You can also.
- the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer 2 has active energy ray curable or thermosetting property, the active energy ray irradiation or after the above-described processing step and before or after the decompression treatment. It is preferable to cure the pressure-sensitive adhesive layer 2 by heating.
- the pressure-sensitive adhesive layer 2 is cured before the pressure reduction treatment, the pressure-sensitive adhesive layer 2 is relatively hard at the stage of the pressure reduction treatment. The pressure-sensitive adhesive layer 2, the workpiece W ′, and the adhesive force can be reduced with almost no unevenness formation.
- the pressure-sensitive adhesive layer 2 when the pressure-sensitive adhesive layer 2 is cured after the pressure reduction treatment, the pressure-sensitive adhesive layer 2 is relatively soft at the stage of the pressure reduction treatment, so that the expansion of the air chamber 3 and the formation of irregularities on the pressure-sensitive adhesive surface P (FIG. 2D) ), The pressure-sensitive adhesive force can be further reduced by curing the pressure-sensitive adhesive layer 2, and the pressure-sensitive adhesive layer 2 and the workpiece W ′ can be easily separated from each other.
- “curing” of the pressure-sensitive adhesive refers to a reaction performed after the pressure-sensitive adhesive sheet 1 is adhered to an adherend (work W, workpiece W ′). Therefore, for example, it is clearly distinguished from the above-mentioned “crosslinking” of the pressure-sensitive adhesive.
- examples of the active energy ray for curing the pressure-sensitive adhesive composition include ionizing radiation, that is, ultraviolet rays, X-rays, and electron beams. Among these, ultraviolet rays that are relatively easy to introduce irradiation equipment are preferable.
- near ultraviolet rays including ultraviolet rays having a wavelength of about 200 to 380 nm may be used for ease of handling.
- the amount of light may be appropriately selected according to the type of active energy ray-curable group possessed by the active energy ray-curable pressure-sensitive adhesive composition and the thickness of the pressure-sensitive adhesive layer 2, and is usually about 50 to 1500 mJ / cm 2 . 200 to 1000 mJ / cm 2 is preferable, and 300 to 800 mJ / cm 2 is more preferable.
- the ultraviolet illumination is usually 50 ⁇ 1500mW / cm 2 or so, preferably 200 ⁇ 1000mW / cm 2, more preferably 300 ⁇ 800mW / cm 2.
- the ultraviolet light source is not particularly limited, and for example, an electrodeless lamp, a high-pressure mercury lamp, a metal halide lamp, a UV-LED, or the like is used.
- the acceleration voltage is appropriately selected according to the type of active energy ray-curable group possessed by the active energy ray-curable adhesive composition and the thickness of the adhesive layer 2. Usually, the acceleration voltage is preferably about 10 to 1000 kV.
- the irradiation dose may be set within a range where the active energy ray-curable pressure-sensitive adhesive composition is appropriately cured, and is usually selected within a range of 10 to 1000 krad.
- the electron beam source is not particularly limited.
- various electron beam accelerators such as a cockcroft Walton type, a bandegraph type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type may be used. it can.
- these active energy rays may be irradiated from the surface opposite to the pressure-sensitive adhesive surface P (the surface on which the workpiece W ′ is adhered) in the pressure-sensitive adhesive sheet 1. preferable.
- the pressure-sensitive adhesive composition has thermosetting properties
- a heating means for curing the pressure-sensitive adhesive composition for example, an appropriate means such as a hot plate, a hot air dryer, or a near infrared lamp can be adopted. It can.
- the heating conditions are appropriately set depending on the heating temperature required for the thermosetting of the pressure-sensitive adhesive layer 2, the desired peelability, the heat resistance of the workpiece W and the workpiece W ', the heating means, and the like.
- As general heating conditions for example, when a hot plate is used, a temperature of 80 to 250 ° C., a heating time of 5 seconds to 60 seconds, and the like are exemplified.
- the pressure-sensitive adhesive layer 2 of the pressure-sensitive adhesive sheet 1 has an air chamber 3 therein, and a decompression process for expanding the gas in the air chamber 3, The adhesive force to the adherend of the adhesive sheet 1 is reduced.
- the adhesive force can be reduced at a desired timing by a novel mechanism of expanding the gas by the decompression process, thereby facilitating the peeling between the adhesive sheet and the adherend. Can do.
- the adhesive force of the pressure-sensitive adhesive layer 2 is reduced using only active energy ray curable or thermosetting, the selection of materials is limited because the curing reaction (that is, chemical reaction) is sufficiently advanced. End up.
- the adhesive force can be reduced by the expansion of the gas due to the decompression process, so that the active energy ray curable property or thermosetting property is not used at all or only partially used. Therefore, the freedom degree of the material which comprises the adhesive layer 2 can be made large.
- the adhesive strength of the adhesive layer 2 decreases.
- thermosetting property is not used at all or only partially used. Even if a heating process is included in the workpiece, the workpiece W can be sufficiently temporarily fixed.
- another layer may be interposed between the base material 4 and the pressure-sensitive adhesive layer 2 in the pressure-sensitive adhesive sheet 1.
- the pressure-sensitive adhesive sheet may be a double-sided pressure-sensitive adhesive sheet comprising only a pressure-sensitive adhesive layer without a base material.
- a method of peeling a double-sided pressure-sensitive adhesive sheet having a first pressure-sensitive adhesive surface and a second pressure-sensitive adhesive surface, and a first adherend adhered to the first pressure-sensitive adhesive surface can do.
- a second adherend may be attached to the second adhesive surface.
- an air chamber is formed inside the pressure-sensitive adhesive layer.
- the gas in the air chamber expands, and the first adherend
- the first adherend and the pressure-sensitive adhesive sheet can be peeled off.
- the pressure-sensitive adhesive prepared in (1) above was applied to the release-treated surface of a release sheet (product of Lintec Co., Ltd., product name “SP-PET381031”, thickness 38 ⁇ m, polyethylene terephthalate film laminated with a silicone release agent). 1) was applied with an applicator and dried at 100 ° C. for 1 minute to form an adhesive layer. The thickness of the pressure-sensitive adhesive layer after drying was 25 ⁇ m. A polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name “Lumirror T-60”, thickness 50 ⁇ m) is bonded to the obtained pressure-sensitive adhesive layer, and then, under conditions of 23 ° C. and relative humidity 50%. This was seasoned for 7 days and used as an adhesive sheet.
- a release sheet product of Lintec Co., Ltd., product name “SP-PET381031”, thickness 38 ⁇ m, polyethylene terephthalate film laminated with a silicone release agent.
- the obtained adhesive sheet it observed with the digital microscope from the base material side, and measured the average diameter and volume ratio of the air chamber in an adhesive layer.
- the average diameter of the air chamber was 21 ⁇ m.
- the volume ratio of the air chamber which occupies for an adhesive layer was 2.1%.
- Composition comprising 100 parts by mass (solid content) of the above-mentioned energy beam curable acrylic ester copolymer and energy beam curable acrylate polyfunctional monomer and oligomer as an energy beam polymerizable group-containing oligomer (Nippon Kayaku Co., Ltd.) 80 parts by mass (solid name) manufactured by company, product name “KAYARAD NKR-001” and energy ray curable urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., product name “UV-3210EA”, mass average molecular weight: 9000 , Glass transition temperature: ⁇ 27 ° C.) 20 parts by mass (solid content), isocyanate-based crosslinking agent (product name “Coronate L” manufactured by Tosoh Corporation), 0.1 part by mass (solid content), and photopolymerization initiator 1-Hydroxy-cyclohexyl-phenyl-ketone (Ciba Specialty Chemicals) Mixed product name
- a pressure-sensitive adhesive sheet was produced in the same manner as in Production Example 1 except that the obtained pressure-sensitive adhesive (2) was used in place of the pressure-sensitive adhesive (1).
- the average diameter and volume ratio of the air chamber were measured in the same manner as the adhesive sheet of Production Example 1.
- the average diameter of the air chamber was 18 ⁇ m.
- the volume ratio of the air chamber which occupies for an adhesive layer was 1.6%.
- polystyrene equivalent weight average molecular weight is a standard polystyrene equivalent value measured (GPC measurement) under the following conditions using a gel permeation chromatograph (manufactured by Tosoh Corporation, product name “HLC-8020”).
- the ultraviolet irradiation conditions are an illuminance of 700 mW / cm 2 and a light amount of 700 mJ / cm 2 in a wavelength range of 200 to 380 nm.
- the illuminance and light amount are determined by an illuminance / light meter (product name “UV Power Pack II” manufactured by EIT). Used to measure illuminance and light intensity.
- Example 3 The pressure-sensitive adhesive sheet obtained in Production Example 2 was cut into a size of 25 mm in length and 300 mm in width, and then a glass plate (manufactured by Nippon Sheet Glass Co., Ltd., soda lime glass) in an environment of 23 ° C. and 50% RH (relative humidity). , Length 150 mm ⁇ width 70 mm ⁇ thickness 2 mm) and allowed to stand for 24 hours in the same environment. After standing, leave it in a quartz glass chamber and use a decompressor connected to the chamber with a hose to reduce the atmospheric pressure in the chamber to 2 kPa and hold it for 10 seconds while irradiating with ultraviolet rays.
- a decompressor connected to the chamber with a hose to reduce the atmospheric pressure in the chamber to 2 kPa and hold it for 10 seconds while irradiating with ultraviolet rays.
- Adhesive strength reduction rate (%) (adhesive strength before decompression ⁇ adhesive strength after decompression) / (adhesive strength before decompression) ⁇ 100
- Adhesive strength reduction rate (%) (adhesive strength before decompression ⁇ adhesive strength after decompression) / (adhesive strength before decompression) ⁇ 100
- the adhesive force after UV curing is used instead of the adhesive force before decompression in the above formula
- the adhesive force after decompression and UV curing is used instead of the adhesive force after decompression, and the same formula as above.
- the adhesive strength reduction rate was calculated.
- Example 4 the adhesive strength after UV curing is used instead of the adhesive strength before decompression in the above formula, and the adhesive strength after UV curing and after decompression is used instead of the adhesive strength after decompression, and the same formula as above.
- the adhesive strength reduction rate was calculated. The results are shown in Table 1.
- ⁇ Stress relaxation rate> In each production example, the substrate was changed to a heavy release sheet (product name “SP-PET 382050”, thickness 38 ⁇ m, polyethylene terephthalate film laminated with a silicone release agent) manufactured by Lintec Corporation, and dried. A substrate-less double-sided pressure-sensitive adhesive sheet sandwiched between two release sheets was prepared in the same manner as described in the production examples except that the pressure-sensitive adhesive layer was applied to have a thickness of 500 ⁇ m.
- SP-PET 382050 thickness 38 ⁇ m, polyethylene terephthalate film laminated with a silicone release agent
- the substrate-less double-sided pressure-sensitive adhesive sheet was allowed to stand in an atmosphere of 23 ° C. and 50% RH for 2 weeks, and then a sample having a width of 15 mm ⁇ 55 mm was cut out from the pressure-sensitive adhesive sheet in which a plurality of the pressure-sensitive adhesive layers were laminated.
- the release sheet laminated on the surface layer was peeled off, and the sample was set in a universal tensile testing machine (manufactured by Shimadzu Corporation, Autograph AG-10kNIS) so that the sample measurement range was 15 mm wide ⁇ 25 mm long. Then, in an environment of 23 ° C.
- the base material-less pressure-sensitive adhesive sheet used for the measurement of the stress relaxation rate was cut into a size of 80 mm ⁇ 80 mm, and the pressure-sensitive adhesive layer from which the release sheet was removed was wrapped in a polyester mesh (number of meshes: 200 mesh / inch), The mass of only the adhesive was weighed with a precision balance. The mass at this time is M1.
- the pressure-sensitive adhesive sample was immersed in an ethyl acetate solvent at room temperature (23 ° C.) for 24 hours. Thereafter, the pressure-sensitive adhesive was taken out and air-dried for 24 hours in an environment of a temperature of 23 ° C. and 50% RH, and further dried in an oven at 80 ° C. for 12 hours. The mass of only the pressure-sensitive adhesive after drying was weighed with a precision balance. The mass at this time is M2.
- the gel fraction (%) is represented by (M2 / M1) ⁇ 100.
- the measurement results are shown in Table 1.
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Abstract
The present invention pertains to an adhesive sheet 1 delamination method for delaminating the adhesive sheet 1 provided with at least an adhesive layer 2 and delaminating attaching bodies W, W' attached to the adhesive surface P of the adhesive layer 2, wherein the method is characterized in that: the adhesive layer 2 has an air chamber 3 therein; and a depressurizing process for expanding a gas inside the air chamber 3 is performed on the adhesive sheet 1, to which at least the attaching bodies W, W' are attached, to thereby reduce the adhesion of the adhesive layer 2 and delaminate the adhesive sheet 1 and the attaching bodies W, W'. Through this method, the adhesion can be reduced at a desired timing by means of a novel acting mechanism.
Description
本発明は、所望のタイミングで粘着力を低下させることができ、被着体の剥離が容易な粘着シートの剥離方法に関するものである。
The present invention relates to a pressure-sensitive adhesive sheet peeling method capable of reducing the adhesive strength at a desired timing and easily peeling the adherend.
半導体チップや表示装置などの製造工程においては、半導体ウェハ等の電子部材や表示装置構成部材（電子部材・光学部材）といった加工対象を仮固定するために粘着シートが用いられることがある。かかる粘着シートは、エネルギーを加える等の方法により、所望のタイミングで粘着シートの粘着力を低下させることができるものであり、これにより加工対象（被着体）の剥離が容易となる。前述した製造工程においては、例えば、電子部材や光学部材等の被着体を粘着シートに固定した状態で、所望の加工工程に付される。
In the manufacturing process of a semiconductor chip, a display device, etc., an adhesive sheet may be used to temporarily fix a processing target such as an electronic member such as a semiconductor wafer or a display device constituent member (electronic member / optical member). Such a pressure-sensitive adhesive sheet can reduce the pressure-sensitive adhesive force of the pressure-sensitive adhesive sheet at a desired timing by a method such as applying energy, thereby facilitating the separation of the object to be processed (the adherend). In the manufacturing process described above, for example, it is subjected to a desired processing step in a state where an adherend such as an electronic member or an optical member is fixed to the adhesive sheet.
かかる粘着シートの粘着力を低下させる方法として、活性エネルギー線硬化型粘着剤を用いて粘着剤層を形成し、活性エネルギー線を照射することで粘着剤層を硬化させて粘着力を低下させる方法（例えば、特許文献１参照）、熱膨張性粒子を粘着剤層に含有させ、加熱により熱膨張性粒子を膨張させて粘着剤層の粘着力を低下させる方法（例えば、特許文献２参照）などが提案されている。
As a method of reducing the adhesive strength of such an adhesive sheet, a method of forming an adhesive layer using an active energy ray-curable adhesive and curing the adhesive layer by irradiating active energy rays to reduce the adhesive strength (For example, refer to Patent Document 1), a method in which thermally expandable particles are contained in an adhesive layer, and the thermally expandable particles are expanded by heating to reduce the adhesive force of the adhesive layer (for example, refer to Patent Document 2). Has been proposed.
本発明は、新規な作用機構により、所望のタイミングで粘着力を低下させることのできる、粘着シートと被着体との剥離方法を提供することを目的とする。
An object of the present invention is to provide a peeling method between an adhesive sheet and an adherend that can reduce the adhesive force at a desired timing by a novel action mechanism.
第１に本発明は、少なくとも粘着剤層を備える粘着シートと、前記粘着剤層の粘着面に貼着された被着体とを剥離する粘着シートの剥離方法であって、前記粘着剤層は、内部に気室を有しており、少なくとも前記被着体が貼着された前記粘着シートに対し、前記気室中の気体を膨張させる減圧処理を行うことにより、前記粘着剤層の粘着力を低下させ、前記粘着シートと前記被着体とを剥離することを特徴とする粘着シートの剥離方法を提供する（発明１）。
1st this invention is a peeling method of the adhesive sheet which peels an adhesive sheet provided with an adhesive layer at least, and the to-be-adhered body stuck on the adhesive surface of the said adhesive layer, Comprising: The said adhesive layer is The pressure-sensitive adhesive layer has an air chamber inside, and at least the pressure-sensitive adhesive sheet to which the adherend is adhered is subjected to a decompression treatment for expanding the gas in the air chamber, whereby the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer is increased. The pressure-sensitive adhesive sheet peeling method is provided, wherein the pressure-sensitive adhesive sheet and the adherend are peeled off (Invention 1).
なお、本発明における「シート」には、「テープ」の概念も含まれるものとする。
The “sheet” in the present invention includes the concept of “tape”.
本発明に係る粘着シートと被着体との剥離方法によれば、減圧処理により前記気室内の気体を膨張させるという新規な作用機構により、所望のタイミングで粘着力を低下させることができ、粘着シートと被着体との剥離を容易にすることができる。
According to the peeling method between the pressure-sensitive adhesive sheet and the adherend according to the present invention, the adhesive force can be reduced at a desired timing by a novel action mechanism of expanding the gas in the air chamber by a decompression process. Peeling of the sheet and the adherend can be facilitated.
上記発明（発明１）において、前記減圧処理は、前記粘着シートを前記被着体に貼着した環境の雰囲気圧力よりも低くすることが好ましい（発明２）。
In the above invention (Invention 1), it is preferable that the pressure reduction treatment is made lower than the atmospheric pressure of the environment in which the adhesive sheet is adhered to the adherend (Invention 2).
上記発明（発明１，２）において、前記粘着剤層を形成する粘着剤組成物は、活性エネルギー線硬化性および熱硬化性を有さないものであってよく（発明３）、かかる発明（発明３）において、前記粘着剤組成物は（メタ）アクリル酸エステル重合体を含有することが好ましい（発明４）。
In the said invention (invention 1 and 2), the adhesive composition which forms the said adhesive layer may not have active energy ray curability and thermosetting (invention 3), and this invention (invention) In 3), it is preferable that the pressure-sensitive adhesive composition contains a (meth) acrylic acid ester polymer (Invention 4).
上記発明（発明１，２）において、前記粘着剤層を形成する粘着剤組成物は活性エネルギー線硬化性または熱硬化性を有するものであってよく（発明５）、かかる発明（発明５）において、前記活性エネルギー線硬化型粘着剤組成物は、側鎖に活性エネルギー線硬化性基を有する（メタ）アクリル酸エステル重合体を含有することが好ましい（発明６）。
In the said invention (invention 1 and 2), the adhesive composition which forms the said adhesive layer may have active energy ray curability or thermosetting (invention 5), and in this invention (invention 5) The active energy ray-curable pressure-sensitive adhesive composition preferably contains a (meth) acrylic acid ester polymer having an active energy ray-curable group in the side chain (Invention 6).
上記発明（発明５，６）においては、前記粘着剤層に対しエネルギー線を照射して前記粘着剤層を硬化させたのち、前記減圧処理を行ってもよく（発明７）、また、前記減圧処理を行ったのち、前記粘着剤層に対しエネルギー線を照射して前記粘着剤層を硬化させてもよい（発明８）。
In the said invention (invention 5 and 6), after irradiating an energy ray with respect to the said adhesive layer and hardening the said adhesive layer, the said pressure reduction process may be performed (invention 7), and the said pressure reduction After the treatment, the pressure-sensitive adhesive layer may be cured by irradiating the pressure-sensitive adhesive layer with energy rays (Invention 8).
上記発明（発明１～８）において、前記粘着シートは、前記被着体の仮固定に用いられることが好ましく（発明９）、かかる発明（発明９）において、前記被着体は電子部材または光学部材であってもよい（発明１０）。
In the above inventions (Inventions 1 to 8), the pressure-sensitive adhesive sheet is preferably used for temporarily fixing the adherend (Invention 9). In the invention (Invention 9), the adherend is an electronic member or an optical member. It may be a member (Invention 10).
第２に本発明は、ワークを加工して得られる加工物の製造方法であって、ワークと、少なくとも粘着剤層を備え、前記粘着剤層の内部に複数の独立した気室を有する粘着シートとを貼着する貼着工程と、前記粘着シートに貼着された前記ワークを加工して加工物とする加工工程と、少なくとも前記加工物が貼着された前記粘着シートを減圧環境に置いて前記気室中の気体を膨張させる減圧処理を行うことにより、前記粘着剤層の粘着力を低下させ、前記加工物と前記粘着シートとを剥離する剥離工程とを備えることを特徴とする加工物の製造方法を提供する（発明１１）。
2ndly, this invention is a manufacturing method of the workpiece obtained by processing a workpiece | work, Comprising: A workpiece | work and an adhesive sheet which have an independent air chamber inside the said adhesive layer provided at least with an adhesive layer An adhesion step for adhering and a processing step for processing the workpiece adhered to the pressure-sensitive adhesive sheet into a processed product, and placing the pressure-sensitive adhesive sheet to which at least the processed material is adhered in a reduced pressure environment. A workpiece having a peeling step of reducing the adhesive force of the pressure-sensitive adhesive layer by performing a decompression process for expanding the gas in the air chamber and peeling the workpiece and the pressure-sensitive adhesive sheet. A manufacturing method is provided (Invention 11).
本発明に係る粘着シートと被着体との剥離方法によれば、新規な作用機構により、所望のタイミングで粘着力を低下させることができ、粘着シートと被着体との剥離を容易にすることができる。
According to the peeling method between the pressure-sensitive adhesive sheet and the adherend according to the present invention, the adhesive force can be reduced at a desired timing by a novel action mechanism, and the peeling between the pressure-sensitive adhesive sheet and the adherend is facilitated. be able to.
以下、本発明の実施形態について説明する。
本実施形態に係る粘着シートの剥離方法は、少なくとも粘着剤層を備える粘着シートと、当該粘着剤層の粘着面に貼着された被着体とを剥離する方法である。
かかる粘着剤層は、内部に気室を有しており、本実施形態においては、少なくとも被着体が貼着された粘着シートに対し、気室中の気体を膨張させる減圧処理を行うことにより、粘着剤層の粘着力を低下させ、粘着シートと被着体との剥離を容易にする。 Hereinafter, embodiments of the present invention will be described.
The peeling method of the adhesive sheet which concerns on this embodiment is a method of peeling an adhesive sheet provided with an adhesive layer at least, and the to-be-adhered body stuck on the adhesive surface of the said adhesive layer.
The pressure-sensitive adhesive layer has an air chamber inside, and in the present embodiment, at least the pressure-sensitive adhesive sheet to which the adherend is adhered is subjected to a decompression process for expanding the gas in the air chamber. The adhesive strength of the pressure-sensitive adhesive layer is reduced, and the pressure-sensitive adhesive sheet and the adherend are easily separated.
本実施形態に係る粘着シートの剥離方法は、少なくとも粘着剤層を備える粘着シートと、当該粘着剤層の粘着面に貼着された被着体とを剥離する方法である。
かかる粘着剤層は、内部に気室を有しており、本実施形態においては、少なくとも被着体が貼着された粘着シートに対し、気室中の気体を膨張させる減圧処理を行うことにより、粘着剤層の粘着力を低下させ、粘着シートと被着体との剥離を容易にする。 Hereinafter, embodiments of the present invention will be described.
The peeling method of the adhesive sheet which concerns on this embodiment is a method of peeling an adhesive sheet provided with an adhesive layer at least, and the to-be-adhered body stuck on the adhesive surface of the said adhesive layer.
The pressure-sensitive adhesive layer has an air chamber inside, and in the present embodiment, at least the pressure-sensitive adhesive sheet to which the adherend is adhered is subjected to a decompression process for expanding the gas in the air chamber. The adhesive strength of the pressure-sensitive adhesive layer is reduced, and the pressure-sensitive adhesive sheet and the adherend are easily separated.
〔粘着シート〕
図１は本発明の一実施形態にて用いる粘着シートの断面図である。本実施形態に係る粘着シート１は、粘着剤層２を備えて構成され、粘着剤層２は、内部に気室３を有する。また、本実施形態に係る粘着シート１は、粘着剤層における粘着面Ｐ（被着体と接触する面，図１における上側の面）とは反対側の面（図１における下側の面）に、さらに基材４を備えてもよい。本実施形態に係る粘着シート１は、例えば、電子部材や光学部材を仮固定するために用いることができる。以下、半導体ウェハを仮固定するために用いられる場合を中心に説明する。 [Adhesive sheet]
FIG. 1 is a sectional view of an adhesive sheet used in one embodiment of the present invention. The pressure-sensitiveadhesive sheet 1 according to this embodiment includes a pressure-sensitive adhesive layer 2, and the pressure-sensitive adhesive layer 2 has an air chamber 3 inside. In addition, the pressure-sensitive adhesive sheet 1 according to the present embodiment is a surface opposite to the pressure-sensitive adhesive surface P (the surface in contact with the adherend, the upper surface in FIG. 1) in the pressure-sensitive adhesive layer (the lower surface in FIG. 1). In addition, a substrate 4 may be further provided. The pressure-sensitive adhesive sheet 1 according to this embodiment can be used for temporarily fixing an electronic member or an optical member, for example. Hereinafter, the case where it is used for temporarily fixing a semiconductor wafer will be mainly described.
図１は本発明の一実施形態にて用いる粘着シートの断面図である。本実施形態に係る粘着シート１は、粘着剤層２を備えて構成され、粘着剤層２は、内部に気室３を有する。また、本実施形態に係る粘着シート１は、粘着剤層における粘着面Ｐ（被着体と接触する面，図１における上側の面）とは反対側の面（図１における下側の面）に、さらに基材４を備えてもよい。本実施形態に係る粘着シート１は、例えば、電子部材や光学部材を仮固定するために用いることができる。以下、半導体ウェハを仮固定するために用いられる場合を中心に説明する。 [Adhesive sheet]
FIG. 1 is a sectional view of an adhesive sheet used in one embodiment of the present invention. The pressure-sensitive
（１）粘着剤層
粘着剤層は、活性エネルギー線硬化性および熱硬化性を有しない（以下、本明細書において「非硬化性」ということがある。）の粘着剤組成物から形成される粘着剤層であってもよいし、活性エネルギー線硬化性または熱硬化性を有する粘着剤組成物から形成される粘着剤層であってもよい。また、粘着剤層が多層からなる場合には、非硬化性の粘着剤層と硬化性の粘着剤層とを組み合わせたものであってもよい。 (1) Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition that does not have active energy ray curability and thermosetting (hereinafter sometimes referred to as “non-curable” in the present specification). It may be a pressure-sensitive adhesive layer, or may be a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition having active energy ray curability or thermosetting. When the pressure-sensitive adhesive layer is composed of multiple layers, a combination of a non-curable pressure-sensitive adhesive layer and a curable pressure-sensitive adhesive layer may be used.
粘着剤層は、活性エネルギー線硬化性および熱硬化性を有しない（以下、本明細書において「非硬化性」ということがある。）の粘着剤組成物から形成される粘着剤層であってもよいし、活性エネルギー線硬化性または熱硬化性を有する粘着剤組成物から形成される粘着剤層であってもよい。また、粘着剤層が多層からなる場合には、非硬化性の粘着剤層と硬化性の粘着剤層とを組み合わせたものであってもよい。 (1) Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition that does not have active energy ray curability and thermosetting (hereinafter sometimes referred to as “non-curable” in the present specification). It may be a pressure-sensitive adhesive layer, or may be a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition having active energy ray curability or thermosetting. When the pressure-sensitive adhesive layer is composed of multiple layers, a combination of a non-curable pressure-sensitive adhesive layer and a curable pressure-sensitive adhesive layer may be used.
（１－１）非硬化性粘着剤組成物
非硬化性の粘着剤組成物としては、例えば、アクリル系粘着剤組成物、ゴム系粘着剤組成物、シリコーン系粘着剤組成物、ウレタン系粘着剤組成物、ポリエステル系粘着剤組成物、ポリビニルエーテル系粘着剤組成物等が挙げられ、中でもアクリル系粘着剤組成物が好ましい。アクリル系粘着剤組成物としては、従来公知の（メタ）アクリル酸エステル重合体を含有するものを用いることができる。なお、本明細書における「重合体」には「共重合体」の概念も含まれるものとする。 (1-1) Non-curable pressure-sensitive adhesive composition Examples of the non-curable pressure-sensitive adhesive composition include acrylic pressure-sensitive adhesive compositions, rubber-based pressure-sensitive adhesive compositions, silicone-based pressure-sensitive adhesive compositions, and urethane-based pressure-sensitive adhesives. Examples thereof include a composition, a polyester-based pressure-sensitive adhesive composition, a polyvinyl ether-based pressure-sensitive adhesive composition, and among them, an acrylic pressure-sensitive adhesive composition is preferable. As an acrylic adhesive composition, what contains a conventionally well-known (meth) acrylic acid ester polymer can be used. In the present specification, the term “polymer” includes the concept of “copolymer”.
非硬化性の粘着剤組成物としては、例えば、アクリル系粘着剤組成物、ゴム系粘着剤組成物、シリコーン系粘着剤組成物、ウレタン系粘着剤組成物、ポリエステル系粘着剤組成物、ポリビニルエーテル系粘着剤組成物等が挙げられ、中でもアクリル系粘着剤組成物が好ましい。アクリル系粘着剤組成物としては、従来公知の（メタ）アクリル酸エステル重合体を含有するものを用いることができる。なお、本明細書における「重合体」には「共重合体」の概念も含まれるものとする。 (1-1) Non-curable pressure-sensitive adhesive composition Examples of the non-curable pressure-sensitive adhesive composition include acrylic pressure-sensitive adhesive compositions, rubber-based pressure-sensitive adhesive compositions, silicone-based pressure-sensitive adhesive compositions, and urethane-based pressure-sensitive adhesives. Examples thereof include a composition, a polyester-based pressure-sensitive adhesive composition, a polyvinyl ether-based pressure-sensitive adhesive composition, and among them, an acrylic pressure-sensitive adhesive composition is preferable. As an acrylic adhesive composition, what contains a conventionally well-known (meth) acrylic acid ester polymer can be used. In the present specification, the term “polymer” includes the concept of “copolymer”.
アクリル系粘着剤組成物に含まれる（メタ）アクリル酸エステル重合体（Ａ）は、１種類の（メタ）アクリル酸エステルモノマーから形成された単独重合体であってもよいし、複数種類の（メタ）アクリル酸エステルモノマーから形成された共重合体であってもよいし、１種類または複数種類の（メタ）アクリル酸エステルモノマーと（メタ）アクリル酸エステルモノマー以外のモノマーとから形成された共重合体であってもよい。また、（メタ）アクリル酸エステル重合体（Ａ）は、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。（メタ）アクリル酸エステルモノマーとなる化合物の具体的な種類は特に限定されず、（メタ）アクリル酸、（メタ）アクリル酸エステル、その誘導体（アクリロニトリル、イタコン酸など）が具体例として挙げられる。（メタ）アクリル酸エステルについてさらに具体例を示せば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート等の鎖状骨格を有する（メタ）アクリレート；シクロへキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、イミド（メタ）アクリレート、（メタ）アクリロイルモルフォリン等の環状骨格を有する（メタ）アクリレート；２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等のヒドロキシ基を有する（メタ）アクリレート；グリシジル（メタ）アクリレート、Ｎ－メチルアミノエチル（メタ）アクリレート等のヒドロキシ基以外の反応性官能基を有する（メタ）アクリレートが挙げられる。また、（メタ）アクリル酸エステルモノマー以外のモノマーとして、エチレン、ノルボルネン等のオレフィン、酢酸ビニル、スチレンなどが例示される。なお、（メタ）アクリル酸エステルモノマーがアルキル（メタ）アクリレートである場合には、そのアルキル基の炭素数は１～１８の範囲であることが好ましい。また、本明細書において、（メタ）アクリル酸とは、アクリル酸およびメタクリル酸の両方を意味する。他の類似用語も同様である。
The (meth) acrylic acid ester polymer (A) contained in the acrylic pressure-sensitive adhesive composition may be a homopolymer formed from one type of (meth) acrylic acid ester monomer, or a plurality of types of ( The copolymer may be a copolymer formed from a (meth) acrylate monomer, or a copolymer formed from one or more types of (meth) acrylate monomers and monomers other than (meth) acrylate monomers. It may be a polymer. Moreover, a (meth) acrylic acid ester polymer (A) may be used individually by 1 type, and may be used in combination of 2 or more type. Specific types of the compound that becomes the (meth) acrylic acid ester monomer are not particularly limited, and specific examples include (meth) acrylic acid, (meth) acrylic acid ester, and derivatives thereof (acrylonitrile, itaconic acid, and the like). Specific examples of (meth) acrylic acid esters include chain skeletons such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. (Meth) acrylate having cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, imide (meth) acrylate, (meth) acryloylmorpholine, etc. (Meth) acrylates having a cyclic skeleton; such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Having Dorokishi group (meth) acrylate; glycidyl (meth) acrylate, (meth) acrylates having reactive functional groups other than hydroxy group, such as N- methylaminoethyl (meth) acrylate. Examples of monomers other than (meth) acrylic acid ester monomers include olefins such as ethylene and norbornene, vinyl acetate, and styrene. When the (meth) acrylic acid ester monomer is an alkyl (meth) acrylate, the alkyl group preferably has 1 to 18 carbon atoms. Moreover, in this specification, (meth) acrylic acid means both acrylic acid and methacrylic acid. The same applies to other similar terms.
本実施形態における粘着剤層を形成する粘着剤組成物が、後述する架橋剤を含有する場合には、（メタ）アクリル酸エステル重合体（Ａ）は、粘着剤組成物にそのまま含有されていてもよく、また少なくともその一部が架橋剤と架橋反応を行って架橋物として含有されていてもよい。この場合において、（メタ）アクリル酸エステル重合体（Ａ）は、架橋剤と反応する反応性官能基を有することが好ましい。反応性官能基の種類は特に限定されず、架橋剤の種類などに基づいて適宜決定すればよい。
When the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer in the present embodiment contains a crosslinking agent described later, the (meth) acrylic acid ester polymer (A) is directly contained in the pressure-sensitive adhesive composition. In addition, at least a part thereof may be contained as a crosslinked product by performing a crosslinking reaction with a crosslinking agent. In this case, the (meth) acrylic acid ester polymer (A) preferably has a reactive functional group that reacts with the crosslinking agent. The type of the reactive functional group is not particularly limited, and may be appropriately determined based on the type of the crosslinking agent.
例えば、架橋剤がポリイソシアネート化合物である場合には、（メタ）アクリル酸エステル重合体（Ａ）が有する反応性官能基として、ヒドロキシ基、カルボキシル基、アミノ基などが例示され、中でもイソシアネート基との反応性の高いヒドロキシ基が好ましい。また、架橋剤がエポキシ系化合物である場合には、（メタ）アクリル酸エステル重合体（Ａ）が有する反応性官能基として、カルボキシル基、アミノ基、アミド基などが例示され、中でもエポキシ基との反応性の高いカルボキシル基が好ましい。
For example, when the crosslinking agent is a polyisocyanate compound, examples of the reactive functional group of the (meth) acrylic acid ester polymer (A) include a hydroxy group, a carboxyl group, and an amino group. These highly reactive hydroxy groups are preferred. Further, when the crosslinking agent is an epoxy compound, examples of the reactive functional group of the (meth) acrylic acid ester polymer (A) include a carboxyl group, an amino group, an amide group, etc. These highly reactive carboxyl groups are preferred.
（メタ）アクリル酸エステル重合体（Ａ）に反応性官能基を導入する方法は特に限定されず、一例として、反応性官能基を有するモノマーを用いて（メタ）アクリル酸エステル重合体（Ａ）を形成し、反応性官能基を有するモノマーに基づく構成単位を重合体の骨格に含有させる方法が挙げられる。例えば、（メタ）アクリル酸エステル重合体（Ａ）にカルボキシル基を導入する場合は、（メタ）アクリル酸などのカルボキシル基を有するモノマーを用いて（メタ）アクリル酸エステル重合体（Ａ）を形成すればよい。
The method for introducing the reactive functional group into the (meth) acrylic acid ester polymer (A) is not particularly limited. As an example, the (meth) acrylic acid ester polymer (A) using a monomer having a reactive functional group is used. And a constitutional unit based on a monomer having a reactive functional group is contained in the polymer skeleton. For example, when a carboxyl group is introduced into the (meth) acrylic acid ester polymer (A), a (meth) acrylic acid ester polymer (A) is formed using a monomer having a carboxyl group such as (meth) acrylic acid. do it.
（メタ）アクリル酸エステル重合体（Ａ）が反応性官能基を有する場合には、架橋の程度を良好な範囲にする観点から、（メタ）アクリル酸エステル重合体（Ａ）全体の質量に占める反応性官能基を有するモノマー由来の構造部分の質量の割合が、１～２０質量％程度であることが好ましく、２～１０質量％であることがより好ましい。
When the (meth) acrylic acid ester polymer (A) has a reactive functional group, it accounts for the total mass of the (meth) acrylic acid ester polymer (A) from the viewpoint of making the degree of crosslinking a good range. The proportion of the mass of the structural portion derived from the monomer having a reactive functional group is preferably about 1 to 20% by mass, and more preferably 2 to 10% by mass.
（メタ）アクリル酸エステル重合体（Ａ）の重量平均分子量（Ｍｗ）は、塗布時の造膜性の観点から１万～２００万であることが好ましく、１０万～１５０万であることがより好ましい。なお、本明細書において、（メタ）アクリル酸エステル重合体（Ａ）ならびに後述する（メタ）アクリル酸エステル重合体（Ｂ１）および（Ｂ３）の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定した標準ポリスチレン換算の値であり、測定方法の詳細は後述する実施例にて示す。また、（メタ）アクリル酸エステル重合体（Ａ）のガラス転移温度Ｔｇは、好ましくは－７０℃～３０℃、さらに好ましくは－６０℃～２０℃の範囲にある。ガラス転移温度は、Ｆｏｘ式より計算することができる。
The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (A) is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,500,000 from the viewpoint of film forming properties at the time of coating. preferable. In addition, in this specification, the weight average molecular weights of the (meth) acrylic acid ester polymer (A) and the (meth) acrylic acid ester polymers (B1) and (B3) described later are gel permeation chromatography (GPC). It is a value in terms of standard polystyrene measured by the method, and details of the measuring method are shown in the examples described later. The glass transition temperature Tg of the (meth) acrylic acid ester polymer (A) is preferably in the range of −70 ° C. to 30 ° C., more preferably in the range of −60 ° C. to 20 ° C. The glass transition temperature can be calculated from the Fox equation.
（１－２）活性エネルギー線硬化性粘着剤組成物
活性エネルギー線硬化性粘着剤組成物は、活性エネルギー線硬化性化合物（Ｂ２）、および側鎖に活性エネルギー線硬化性基が導入された（メタ）アクリル酸エステル重合体（Ｂ３）のうち少なくともいずれか一方を含有するものであることが好ましい。ここで、活性エネルギー線硬化性粘着剤組成物は、活性エネルギー線硬化性化合物（Ｂ２）、および側鎖に活性エネルギー線硬化性基が導入された（メタ）アクリル酸エステル重合体（Ｂ３）のうちいずれか一方を含有するものであってもよいが、両方を含有するものであることが好ましい。これらの場合において、活性エネルギー線硬化性粘着剤組成物は、さらに活性エネルギー線硬化性を有しない（メタ）アクリル酸エステル重合体（Ｂ１）を含有してもよい。 (1-2) Active energy ray-curable pressure-sensitive adhesive composition The active energy ray-curable pressure-sensitive adhesive composition has an active energy ray-curable compound (B2) and an active energy ray-curable group introduced into the side chain ( It is preferable that at least one of the (meth) acrylic acid ester polymer (B3) is contained. Here, the active energy ray-curable pressure-sensitive adhesive composition is composed of the active energy ray-curable compound (B2) and the (meth) acrylic acid ester polymer (B3) in which an active energy ray-curable group is introduced into the side chain. One of them may be contained, but it is preferred that both are contained. In these cases, the active energy ray-curable pressure-sensitive adhesive composition may further contain a (meth) acrylic acid ester polymer (B1) having no active energy ray curability.
活性エネルギー線硬化性粘着剤組成物は、活性エネルギー線硬化性化合物（Ｂ２）、および側鎖に活性エネルギー線硬化性基が導入された（メタ）アクリル酸エステル重合体（Ｂ３）のうち少なくともいずれか一方を含有するものであることが好ましい。ここで、活性エネルギー線硬化性粘着剤組成物は、活性エネルギー線硬化性化合物（Ｂ２）、および側鎖に活性エネルギー線硬化性基が導入された（メタ）アクリル酸エステル重合体（Ｂ３）のうちいずれか一方を含有するものであってもよいが、両方を含有するものであることが好ましい。これらの場合において、活性エネルギー線硬化性粘着剤組成物は、さらに活性エネルギー線硬化性を有しない（メタ）アクリル酸エステル重合体（Ｂ１）を含有してもよい。 (1-2) Active energy ray-curable pressure-sensitive adhesive composition The active energy ray-curable pressure-sensitive adhesive composition has an active energy ray-curable compound (B2) and an active energy ray-curable group introduced into the side chain ( It is preferable that at least one of the (meth) acrylic acid ester polymer (B3) is contained. Here, the active energy ray-curable pressure-sensitive adhesive composition is composed of the active energy ray-curable compound (B2) and the (meth) acrylic acid ester polymer (B3) in which an active energy ray-curable group is introduced into the side chain. One of them may be contained, but it is preferred that both are contained. In these cases, the active energy ray-curable pressure-sensitive adhesive composition may further contain a (meth) acrylic acid ester polymer (B1) having no active energy ray curability.
（１－２－１）活性エネルギー線硬化性を有しない（メタ）アクリル酸エステル重合体（Ｂ１）
本実施形態における粘着剤層を形成する粘着剤組成物が活性エネルギー線硬化性を有しない（メタ）アクリル酸エステル重合体（Ｂ１）を含有する場合、当該（メタ）アクリル酸エステル重合体（Ｂ１）は、粘着剤組成物にそのまま含有されていてもよく、また少なくともその一部が後述する架橋剤と架橋反応を行って架橋物として含有されていてもよい。（メタ）アクリル酸エステル重合体（Ｂ１）としては、非硬化性粘着剤組成物に関して前述した（メタ）アクリル酸エステル重合体（Ａ）と同様のものを用いることができる。 (1-2-1) (Meth) acrylic acid ester polymer having no active energy ray curability (B1)
When the adhesive composition which forms the adhesive layer in this embodiment contains the (meth) acrylic acid ester polymer (B1) which does not have active energy ray curability, the said (meth) acrylic acid ester polymer (B1) ) May be contained in the pressure-sensitive adhesive composition as it is, or at least a part thereof may be contained as a crosslinked product by performing a crosslinking reaction with a crosslinking agent described later. As (meth) acrylic acid ester polymer (B1), the same thing as the (meth) acrylic acid ester polymer (A) mentioned above regarding the non-curable adhesive composition can be used.
本実施形態における粘着剤層を形成する粘着剤組成物が活性エネルギー線硬化性を有しない（メタ）アクリル酸エステル重合体（Ｂ１）を含有する場合、当該（メタ）アクリル酸エステル重合体（Ｂ１）は、粘着剤組成物にそのまま含有されていてもよく、また少なくともその一部が後述する架橋剤と架橋反応を行って架橋物として含有されていてもよい。（メタ）アクリル酸エステル重合体（Ｂ１）としては、非硬化性粘着剤組成物に関して前述した（メタ）アクリル酸エステル重合体（Ａ）と同様のものを用いることができる。 (1-2-1) (Meth) acrylic acid ester polymer having no active energy ray curability (B1)
When the adhesive composition which forms the adhesive layer in this embodiment contains the (meth) acrylic acid ester polymer (B1) which does not have active energy ray curability, the said (meth) acrylic acid ester polymer (B1) ) May be contained in the pressure-sensitive adhesive composition as it is, or at least a part thereof may be contained as a crosslinked product by performing a crosslinking reaction with a crosslinking agent described later. As (meth) acrylic acid ester polymer (B1), the same thing as the (meth) acrylic acid ester polymer (A) mentioned above regarding the non-curable adhesive composition can be used.
（１－２－２）活性エネルギー線硬化性化合物（Ｂ２）
活性エネルギー線硬化性化合物（Ｂ２）は、活性エネルギー線硬化性基を有し、紫外線、電子線等の活性エネルギー線の照射を受けると重合する化合物である。活性エネルギー線硬化性化合物（Ｂ２）が有する活性エネルギー線硬化性基は、例えば活性エネルギー線硬化性の炭素－炭素二重結合を含む基であり、具体的には、（メタ）アクリロイル基、ビニル基などを例示することができる。 (1-2-2) Active energy ray-curable compound (B2)
The active energy ray curable compound (B2) is a compound having an active energy ray curable group and polymerized when irradiated with active energy rays such as ultraviolet rays and electron beams. The active energy ray-curable group possessed by the active energy ray-curable compound (B2) is, for example, a group containing an active energy ray-curable carbon-carbon double bond, and specifically includes a (meth) acryloyl group, vinyl Examples include groups.
活性エネルギー線硬化性化合物（Ｂ２）は、活性エネルギー線硬化性基を有し、紫外線、電子線等の活性エネルギー線の照射を受けると重合する化合物である。活性エネルギー線硬化性化合物（Ｂ２）が有する活性エネルギー線硬化性基は、例えば活性エネルギー線硬化性の炭素－炭素二重結合を含む基であり、具体的には、（メタ）アクリロイル基、ビニル基などを例示することができる。 (1-2-2) Active energy ray-curable compound (B2)
The active energy ray curable compound (B2) is a compound having an active energy ray curable group and polymerized when irradiated with active energy rays such as ultraviolet rays and electron beams. The active energy ray-curable group possessed by the active energy ray-curable compound (B2) is, for example, a group containing an active energy ray-curable carbon-carbon double bond, and specifically includes a (meth) acryloyl group, vinyl Examples include groups.
活性エネルギー線硬化性化合物（Ｂ２）の例としては、上記の活性エネルギー線硬化性基を有していれば特に限定されないが、汎用性の観点から低分子量化合物（単官能、多官能のモノマーおよびオリゴマー）であることが好ましい。低分子量の活性エネルギー線硬化性化合物（Ｂ２）の具体例としては、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールモノヒドロキシペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートあるいは１，４－ブチレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ジシクロペンタジエンジメトキシジ（メタ）アクリレート、イソボルニル（メタ）アクリレートなどの環状脂肪族骨格含有（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、オリゴエステル（メタ）アクリレート、ウレタン（メタ）アクリレートオリゴマー、エポキシ変性（メタ）アクリレート、ポリエーテル（メタ）アクリレート、などのアクリレート系化合物が挙げられ、これらは１種を単独でまたは２種以上を組み合わせて用いることができる。
Examples of the active energy ray-curable compound (B2) are not particularly limited as long as the active energy ray-curable group has the above-mentioned active energy ray-curable group. However, low molecular weight compounds (monofunctional and polyfunctional monomers and Oligomer) is preferable. Specific examples of the low molecular weight active energy ray-curable compound (B2) include trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol monohydroxypenta. (Meth) acrylate, dipentaerythritol hexa (meth) acrylate or 1,4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dicyclopentadiene dimethoxydi (meth) acrylate, isobornyl ( Cyclic aliphatic skeleton-containing (meth) acrylates such as (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoester (meth) acrylate, urethane (meth) acrylate Oligomers, epoxy-modified (meth) acrylate, polyether (meth) acrylates, include acrylate compounds such as these may be used alone or in admixture.
活性エネルギー線硬化性化合物（Ｂ２）は、通常は分子量が１００～３００００、好ましくは３００～１００００程度である。
The active energy ray-curable compound (B2) usually has a molecular weight of 100 to 30,000, preferably about 300 to 10,000.
活性エネルギー線硬化性粘着剤組成物における活性エネルギー線硬化性化合物（Ｂ２）の含有量および他の成分との含有量比は特に制限されないが、活性エネルギー線硬化性粘着剤組成物が、活性エネルギー線硬化性化合物（Ｂ２）と活性エネルギー線硬化性を有しない（メタ）アクリル酸エステル重合体（Ｂ１）とを含有する場合、活性エネルギー線硬化性化合物（Ｂ２）は、上記（メタ）アクリル酸エステル重合体（Ｂ１）１００質量部に対し、好ましくは１０～４００質量部、より好ましくは３０～３５０質量部程度の割合で用いられる。また、活性エネルギー線硬化性化合物（Ｂ２）と、後述する側鎖に活性エネルギー線硬化性基が導入された（メタ）アクリル酸エステル重合体（Ｂ３）とを含有する場合には、当該（メタ）アクリル酸エステル重合体（Ｂ３）１００質量部に対して、活性エネルギー線硬化性化合物（Ｂ２）の含有量が上記の範囲であることが好ましい。さらに、活性エネルギー線硬化性粘着剤組成物が、活性エネルギー線硬化性化合物（Ｂ２）と、上記（メタ）アクリル酸エステル重合体（Ｂ１）および側鎖に活性エネルギー線硬化性基が導入された（メタ）アクリル酸エステル重合体（Ｂ３）とを含有する場合には、（メタ）アクリル酸エステル重合体（Ｂ１）および（メタ）アクリル酸エステル重合体（Ｂ３）の合計量１００質量部に対して、活性エネルギー線硬化性化合物（Ｂ２）の含有量が上記の範囲であることが好ましい。
The content of the active energy ray-curable compound (B2) in the active energy ray-curable adhesive composition and the content ratio with other components are not particularly limited, but the active energy ray-curable adhesive composition is active energy. In the case of containing the linear curable compound (B2) and the (meth) acrylic acid ester polymer (B1) having no active energy ray curable, the active energy ray curable compound (B2) is the above (meth) acrylic acid. The amount is preferably 10 to 400 parts by mass, more preferably about 30 to 350 parts by mass with respect to 100 parts by mass of the ester polymer (B1). Moreover, when it contains the active energy ray-curable compound (B2) and the (meth) acrylic acid ester polymer (B3) in which an active energy ray-curable group is introduced in the side chain described later, ) The content of the active energy ray-curable compound (B2) is preferably in the above range with respect to 100 parts by mass of the acrylic ester polymer (B3). Furthermore, the active energy ray-curable pressure-sensitive adhesive composition has the active energy ray-curable compound (B2), the (meth) acrylic acid ester polymer (B1), and the active energy ray-curable group introduced into the side chain. When it contains the (meth) acrylic acid ester polymer (B3), the total amount of the (meth) acrylic acid ester polymer (B1) and the (meth) acrylic acid ester polymer (B3) is 100 parts by mass. The content of the active energy ray-curable compound (B2) is preferably in the above range.
（１－２－３）側鎖に活性エネルギー線硬化性基が導入された（メタ）アクリル酸エステル重合体（Ｂ３）
本実施形態における活性エネルギー線硬化性粘着剤組成物が側鎖に活性エネルギー線硬化性基が導入された（メタ）アクリル酸エステル重合体（Ｂ３）を含有する場合、かかる（メタ）アクリル酸エステル重合体（Ｂ３）は、粘着剤組成物にそのまま含有されていてもよく、また少なくともその一部が後述する架橋剤と架橋反応を行って架橋物として含有されていてもよい。 (1-2-3) (Meth) acrylic acid ester polymer (B3) having an active energy ray-curable group introduced in the side chain
When the active energy ray-curable pressure-sensitive adhesive composition in the present embodiment contains a (meth) acrylic acid ester polymer (B3) having an active energy ray-curable group introduced in the side chain, such (meth) acrylic acid ester The polymer (B3) may be contained in the pressure-sensitive adhesive composition as it is, or at least a part thereof may be contained as a crosslinked product by performing a crosslinking reaction with a crosslinking agent described later.
本実施形態における活性エネルギー線硬化性粘着剤組成物が側鎖に活性エネルギー線硬化性基が導入された（メタ）アクリル酸エステル重合体（Ｂ３）を含有する場合、かかる（メタ）アクリル酸エステル重合体（Ｂ３）は、粘着剤組成物にそのまま含有されていてもよく、また少なくともその一部が後述する架橋剤と架橋反応を行って架橋物として含有されていてもよい。 (1-2-3) (Meth) acrylic acid ester polymer (B3) having an active energy ray-curable group introduced in the side chain
When the active energy ray-curable pressure-sensitive adhesive composition in the present embodiment contains a (meth) acrylic acid ester polymer (B3) having an active energy ray-curable group introduced in the side chain, such (meth) acrylic acid ester The polymer (B3) may be contained in the pressure-sensitive adhesive composition as it is, or at least a part thereof may be contained as a crosslinked product by performing a crosslinking reaction with a crosslinking agent described later.
側鎖に活性エネルギー線硬化性基が導入された（メタ）アクリル酸エステル重合体（Ｂ３）の主骨格は特に限定はされず、前述の（メタ）アクリル酸エステル重合体（Ｂ１）と同様のものが例示される。
The main skeleton of the (meth) acrylic acid ester polymer (B3) in which the active energy ray-curable group is introduced into the side chain is not particularly limited, and is the same as that of the aforementioned (meth) acrylic acid ester polymer (B1). Are illustrated.
（メタ）アクリル酸エステル重合体（Ｂ３）の側鎖に導入される活性エネルギー線硬化性基は、例えば活性エネルギー線硬化性の炭素－炭素二重結合を含む基であり、具体的には（メタ）アクリロイル基等を例示することができる。活性エネルギー線硬化性基は、アルキレン基、アルキレンオキシ基、ポリアルキレンオキシ基等を介して（メタ）アクリル酸エステル重合体（Ｂ３）に結合していてもよい。
The active energy ray-curable group introduced into the side chain of the (meth) acrylate polymer (B3) is, for example, a group containing an active energy ray-curable carbon-carbon double bond. A meth) acryloyl group etc. can be illustrated. The active energy ray-curable group may be bonded to the (meth) acrylic acid ester polymer (B3) via an alkylene group, an alkyleneoxy group, a polyalkyleneoxy group, or the like.
側鎖に活性エネルギー線硬化性基が導入された（メタ）アクリル酸エステル重合体（Ｂ３）は、例えば、ヒドロキシ基、カルボキシル基、アミノ基、置換アミノ基、エポキシ基等の官能基を含有する（メタ）アクリル酸エステル重合体と、当該官能基と反応する置換基および活性エネルギー線硬化性炭素－炭素二重結合を１分子毎に１～５個を有する硬化性基含有化合物とを反応させて得られる。かかる（メタ）アクリル酸エステル重合体は、ヒドロキシ基、カルボキシル基、アミノ基、置換アミノ基、エポキシ基等の官能基を有する（メタ）アクリル酸エステルモノマーまたはその誘導体と、前述した成分（Ｂ１）を構成するモノマーとから共重合することで得られる。また、上記硬化性基含有化合物としては、（メタ）アクリロイルオキシエチルイソシアネート、メタ－イソプロペニル－α，α－ジメチルベンジルイソシアネート、（メタ）アクリロイルイソシアネート、アリルイソシアネート、グリシジル（メタ）アクリレート、（メタ）アクリル酸等が挙げられ、これらは１種を単独でまたは２種以上を組み合わせて用いることができる。
The (meth) acrylic acid ester polymer (B3) in which an active energy ray-curable group is introduced into the side chain contains, for example, a functional group such as a hydroxy group, a carboxyl group, an amino group, a substituted amino group, and an epoxy group. A (meth) acrylic acid ester polymer is reacted with a substituent that reacts with the functional group and a curable group-containing compound having 1 to 5 active energy ray-curable carbon-carbon double bonds per molecule. Obtained. Such a (meth) acrylic acid ester polymer includes a (meth) acrylic acid ester monomer or a derivative thereof having a functional group such as a hydroxy group, a carboxyl group, an amino group, a substituted amino group, and an epoxy group, and the component (B1) described above. It can be obtained by copolymerizing with a monomer that constitutes. Examples of the curable group-containing compound include (meth) acryloyloxyethyl isocyanate, meta-isopropenyl-α, α-dimethylbenzyl isocyanate, (meth) acryloyl isocyanate, allyl isocyanate, glycidyl (meth) acrylate, (meth) Acrylic acid etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types.
また、本実施形態における粘着剤層を形成する粘着剤組成物が、後述する架橋剤を含有する場合には、側鎖に活性エネルギー線硬化性基が導入された（メタ）アクリル酸エステル重合体（Ｂ３）は、架橋剤と反応する反応性官能基を有することが好ましい。反応性官能基の種類は特に限定されず、前述した（メタ）アクリル酸エステル重合体（Ｂ１）（および非硬化性粘着剤組成物に関して前述した（メタ）アクリル酸エステル重合体（Ａ））と同様のものを例示することができる。
Moreover, when the adhesive composition which forms the adhesive layer in this embodiment contains the crosslinking agent mentioned later, the active energy ray hardening group was introduce | transduced into the side chain (meth) acrylic acid ester polymer (B3) preferably has a reactive functional group that reacts with the crosslinking agent. The kind of the reactive functional group is not particularly limited, and the (meth) acrylic acid ester polymer (B1) described above (and the (meth) acrylic acid ester polymer (A) described above with respect to the non-curable pressure-sensitive adhesive composition) and The same thing can be illustrated.
側鎖に活性エネルギー線硬化性基が導入された（メタ）アクリル酸エステル重合体（Ｂ３）の重量平均分子量（Ｍｗ）は、１０万～２００万であることが好ましく、３０万～１５０万であることがより好ましい。
The weight average molecular weight (Mw) of the (meth) acrylic acid ester polymer (B3) having an active energy ray-curable group introduced in the side chain is preferably 100,000 to 2,000,000, and 300,000 to 1,500,000. More preferably.
また、（メタ）アクリル酸エステル重合体（Ｂ３）のガラス転移温度（Ｔｇ）は、好ましくは－７０～３０℃、より好ましくは－６０～２０℃の範囲にある。なお、本明細書において（メタ）アクリル酸エステル重合体（Ｂ３）のガラス転移温度（Ｔｇ）は、硬化性基含有化合物と反応させる前の（メタ）アクリル酸エステル重合体のものを指す。
The glass transition temperature (Tg) of the (meth) acrylic acid ester polymer (B3) is preferably in the range of −70 to 30 ° C., more preferably in the range of −60 to 20 ° C. In addition, in this specification, the glass transition temperature (Tg) of the (meth) acrylic acid ester polymer (B3) refers to that of the (meth) acrylic acid ester polymer before being reacted with the curable group-containing compound.
（１－３）熱硬化性粘着剤組成物
熱硬化型粘着剤組成物としては、エポキシ樹脂、フェノール樹脂などを含有するものが挙げられる。 (1-3) Thermosetting pressure-sensitive adhesive composition Examples of the thermosetting pressure-sensitive adhesive composition include those containing an epoxy resin, a phenol resin, and the like.
熱硬化型粘着剤組成物としては、エポキシ樹脂、フェノール樹脂などを含有するものが挙げられる。 (1-3) Thermosetting pressure-sensitive adhesive composition Examples of the thermosetting pressure-sensitive adhesive composition include those containing an epoxy resin, a phenol resin, and the like.
（１－４）架橋剤
本実施形態における粘着剤層を形成する粘着剤組成物は、前述した粘着剤組成物に含まれる重合体と反応し得る架橋剤を含有してもよい。この場合には、本実施形態における粘着剤層は、粘着剤組成物に含まれる重合体（（メタ）アクリル酸エステル重合体（Ａ）、（Ｂ１）、（Ｂ３）等）と架橋剤との架橋反応により得られた架橋物を含有する。 (1-4) Crosslinking agent The adhesive composition forming the adhesive layer in this embodiment may contain a crosslinking agent capable of reacting with the polymer contained in the above-mentioned adhesive composition. In this case, the pressure-sensitive adhesive layer in this embodiment comprises a polymer ((meth) acrylic acid ester polymer (A), (B1), (B3), etc.) contained in the pressure-sensitive adhesive composition and a crosslinking agent. Contains a cross-linked product obtained by a cross-linking reaction.
本実施形態における粘着剤層を形成する粘着剤組成物は、前述した粘着剤組成物に含まれる重合体と反応し得る架橋剤を含有してもよい。この場合には、本実施形態における粘着剤層は、粘着剤組成物に含まれる重合体（（メタ）アクリル酸エステル重合体（Ａ）、（Ｂ１）、（Ｂ３）等）と架橋剤との架橋反応により得られた架橋物を含有する。 (1-4) Crosslinking agent The adhesive composition forming the adhesive layer in this embodiment may contain a crosslinking agent capable of reacting with the polymer contained in the above-mentioned adhesive composition. In this case, the pressure-sensitive adhesive layer in this embodiment comprises a polymer ((meth) acrylic acid ester polymer (A), (B1), (B3), etc.) contained in the pressure-sensitive adhesive composition and a crosslinking agent. Contains a cross-linked product obtained by a cross-linking reaction.
架橋剤の種類としては、例えば、ポリイソシアネート系化合物、エポキシ系化合物、金属キレート系化合物、アジリジン系化合物等のポリイミン化合物、メラミン樹脂、尿素樹脂、ジアルデヒド類、メチロールポリマー、金属アルコキシド、金属塩等が挙げられ、１種を単独でまたは２種以上を組み合わせて用いることができる。これらの中でも、架橋反応を制御し易いことなどの理由により、エポキシ系化合物またはポリイソシアネート化合物であることが好ましい。
Examples of the crosslinking agent include polyimine compounds such as polyisocyanate compounds, epoxy compounds, metal chelate compounds, and aziridine compounds, melamine resins, urea resins, dialdehydes, methylol polymers, metal alkoxides, metal salts, and the like. 1 type can be used individually or in combination of 2 or more types. Among these, an epoxy compound or a polyisocyanate compound is preferable because it is easy to control the crosslinking reaction.
ポリイソシアネート化合物は、１分子当たりイソシアネート基を２個以上有する化合物である。具体的には、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、キシリレンジイソシアネート等の芳香族ポリイソシアネート、ヘキサメチレンジイソシアネート等の脂肪族ポリイソシアネート、イソホロンジイソシアネート、水素添加ジフェニルメタンジイソシアネート等の脂環式ポリイソシアネートなど、及びそれらのビウレット体、イソシアヌレート体、さらにはエチレングリコール、プロピレングリコール、ネオペンチルグリコール、トリメチロールプロパン、ヒマシ油等の低分子活性水素含有化合物との反応物であるアダクト体などが挙げられる。
A polyisocyanate compound is a compound having two or more isocyanate groups per molecule. Specifically, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and the like Biuret bodies, isocyanurate bodies, and adduct bodies that are a reaction product with a low molecular active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, and the like.
エポキシ系化合物としては、例えば、１，３－ビス（Ｎ，Ｎ’－ジグリシジルアミノメチル）シクロヘキサン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシリレンジアミン、エチレングリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、トリメチロールプロパンジグリシジルエーテル、ジグリシジルアニリン、ジグリシジルアミン等が挙げられる。
Examples of the epoxy compound include 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, ethylene glycol diglycidyl ether. 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidylaniline, diglycidylamine and the like.
粘着剤層を形成する粘着剤組成物の架橋剤の含有量は、粘着剤組成物に含まれる重合体（例えば、（メタ）アクリル酸エステル重合体（Ａ）、（Ｂ１）および（Ｂ３））の合計量１００質量部に対し、０．０１～５０質量部であることが好ましく、０．０２～１０質量部、０．０３～５質量部であることがより好ましく、０．０５～２質量部であることがより好ましく、０．０８～０．５質量部であることが特に好ましい。
The content of the crosslinking agent in the pressure-sensitive adhesive composition that forms the pressure-sensitive adhesive layer is the polymer contained in the pressure-sensitive adhesive composition (for example, (meth) acrylic acid ester polymers (A), (B1) and (B3)). Is preferably 0.01 to 50 parts by mass, more preferably 0.02 to 10 parts by mass, and more preferably 0.03 to 5 parts by mass with respect to 100 parts by mass of the total amount of Part is more preferable, and 0.08 to 0.5 part by mass is particularly preferable.
本実施形態における粘着剤層を形成する粘着剤組成物が架橋剤を含有する場合には、その架橋剤の種類などに応じて、適切な架橋促進剤を含有してもよい。
When the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer in the present embodiment contains a crosslinking agent, an appropriate crosslinking accelerator may be contained depending on the type of the crosslinking agent.
（１－５）その他の成分
本実施形態における粘着剤層を形成する粘着剤組成物は、上記の成分に加えて、光重合開始剤、光増感剤、架橋促進剤、染料や顔料等の着色材料、難燃剤、充填材、熱伝導剤、粘着付与剤、可塑剤、帯電防止剤などの各種添加剤を含有してもよい。特に、粘着剤組成物が紫外線等の活性エネルギー線によって硬化する活性エネルギー線硬化性を有する場合は、当該粘着剤組成物は、光重合開始剤を含有することが好ましい。 (1-5) Other components The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer in the present embodiment includes, in addition to the above components, a photopolymerization initiator, a photosensitizer, a crosslinking accelerator, a dye, a pigment, and the like. You may contain various additives, such as a coloring material, a flame retardant, a filler, a heat conductive agent, a tackifier, a plasticizer, and an antistatic agent. In particular, when the pressure-sensitive adhesive composition has active energy ray curability that is cured by active energy rays such as ultraviolet rays, the pressure-sensitive adhesive composition preferably contains a photopolymerization initiator.
本実施形態における粘着剤層を形成する粘着剤組成物は、上記の成分に加えて、光重合開始剤、光増感剤、架橋促進剤、染料や顔料等の着色材料、難燃剤、充填材、熱伝導剤、粘着付与剤、可塑剤、帯電防止剤などの各種添加剤を含有してもよい。特に、粘着剤組成物が紫外線等の活性エネルギー線によって硬化する活性エネルギー線硬化性を有する場合は、当該粘着剤組成物は、光重合開始剤を含有することが好ましい。 (1-5) Other components The pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer in the present embodiment includes, in addition to the above components, a photopolymerization initiator, a photosensitizer, a crosslinking accelerator, a dye, a pigment, and the like. You may contain various additives, such as a coloring material, a flame retardant, a filler, a heat conductive agent, a tackifier, a plasticizer, and an antistatic agent. In particular, when the pressure-sensitive adhesive composition has active energy ray curability that is cured by active energy rays such as ultraviolet rays, the pressure-sensitive adhesive composition preferably contains a photopolymerization initiator.
光重合開始剤としては、ベンゾイン化合物、アセトフェノン化合物、アシルフォスフィンオキサイド化合物、チタノセン化合物、チオキサントン化合物、パーオキサイド化合物等の光開始剤、アミンやキノン等の光増感剤などが挙げられ、具体的には、１－ヒドロキシシクロヘキシルフェニルケトン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンジルジフェニルサルファイド、テトラメチルチウラムモノサルファイド、アゾビスイソブチロニトリル、ジベンジル、ジアセチル、β－クロールアンスラキノン、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイドなどが例示され、これらは１種を単独でまたは２種以上を組み合わせて用いることができる。エネルギー線として紫外線を用いる場合には、光重合開始剤を配合することにより照射時間、照射量を少なくすることができる。
Examples of photopolymerization initiators include photoinitiators such as benzoin compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, thioxanthone compounds, and peroxide compounds, and photosensitizers such as amines and quinones. 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldiphenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, β- chloranthraquinone 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like, and these can be used alone or in combination of two or more. When ultraviolet rays are used as energy rays, the irradiation time and irradiation amount can be reduced by blending a photopolymerization initiator.
（２）気室
本実施形態において、粘着剤層は、その内部に気室を有する。本実施形態においては、後述する減圧処理により、気室中の気体が膨張し、これにより気室が膨張する方向の圧力が気室に付与され、その結果、粘着シートの粘着力が低下する。 (2) Air chamber In this embodiment, an adhesive layer has an air chamber in the inside. In the present embodiment, the gas in the air chamber expands due to the decompression process to be described later, whereby a pressure in the direction in which the air chamber expands is applied to the air chamber, and as a result, the adhesive force of the adhesive sheet decreases.
本実施形態において、粘着剤層は、その内部に気室を有する。本実施形態においては、後述する減圧処理により、気室中の気体が膨張し、これにより気室が膨張する方向の圧力が気室に付与され、その結果、粘着シートの粘着力が低下する。 (2) Air chamber In this embodiment, an adhesive layer has an air chamber in the inside. In the present embodiment, the gas in the air chamber expands due to the decompression process to be described later, whereby a pressure in the direction in which the air chamber expands is applied to the air chamber, and as a result, the adhesive force of the adhesive sheet decreases.
気室中に含まれる気体は、特に限定されないが、例えば、空気であってもよく、また窒素、二酸化炭素、アルゴン等の不活性ガスであってもよい。
The gas contained in the air chamber is not particularly limited, but may be, for example, air or an inert gas such as nitrogen, carbon dioxide, or argon.
気室の形状は、形成のしやすさの観点から、略球状であることが典型的であるが、これに限定されるものではない。
気室の平均直径は特に限定されないが、例えば、０．１～５００μｍであることが好ましく、１～１００μｍであることがより好ましく、１０～５０μｍであることが特に好ましい。また、粘着剤層に占める気室の体積割合は、例えば、０．５～２０．０％であることが好ましく、１．０～１０．０％であることがより好ましく、１．５～５．０％であることが特に好ましい。
気室の平均直径や粘着剤層に占める気室の体積割合が上記範囲内にあると、減圧前においては、粘着シートが所望の粘着力を維持しやすく、被着体をより確実に固定しやすくなり、減圧後においては、気室中の気体の膨張による粘着力の減少効果がより優れたものとなり、粘着シートと被着体との剥離がより容易になる。 The shape of the air chamber is typically substantially spherical from the viewpoint of ease of formation, but is not limited thereto.
The average diameter of the air chamber is not particularly limited, but is preferably, for example, 0.1 to 500 μm, more preferably 1 to 100 μm, and particularly preferably 10 to 50 μm. Further, the volume ratio of the air chamber in the pressure-sensitive adhesive layer is, for example, preferably 0.5 to 20.0%, more preferably 1.0 to 10.0%, and more preferably 1.5 to 5%. Particularly preferred is 0.0%.
When the average diameter of the air chambers or the volume ratio of the air chambers in the pressure-sensitive adhesive layer is within the above range, the pressure-sensitive adhesive sheet can easily maintain a desired adhesive force before decompression, and the adherend can be more securely fixed. After pressure reduction, the effect of reducing the adhesive force due to the expansion of the gas in the air chamber becomes more excellent, and the adhesive sheet and the adherend are more easily separated.
気室の平均直径は特に限定されないが、例えば、０．１～５００μｍであることが好ましく、１～１００μｍであることがより好ましく、１０～５０μｍであることが特に好ましい。また、粘着剤層に占める気室の体積割合は、例えば、０．５～２０．０％であることが好ましく、１．０～１０．０％であることがより好ましく、１．５～５．０％であることが特に好ましい。
気室の平均直径や粘着剤層に占める気室の体積割合が上記範囲内にあると、減圧前においては、粘着シートが所望の粘着力を維持しやすく、被着体をより確実に固定しやすくなり、減圧後においては、気室中の気体の膨張による粘着力の減少効果がより優れたものとなり、粘着シートと被着体との剥離がより容易になる。 The shape of the air chamber is typically substantially spherical from the viewpoint of ease of formation, but is not limited thereto.
The average diameter of the air chamber is not particularly limited, but is preferably, for example, 0.1 to 500 μm, more preferably 1 to 100 μm, and particularly preferably 10 to 50 μm. Further, the volume ratio of the air chamber in the pressure-sensitive adhesive layer is, for example, preferably 0.5 to 20.0%, more preferably 1.0 to 10.0%, and more preferably 1.5 to 5%. Particularly preferred is 0.0%.
When the average diameter of the air chambers or the volume ratio of the air chambers in the pressure-sensitive adhesive layer is within the above range, the pressure-sensitive adhesive sheet can easily maintain a desired adhesive force before decompression, and the adherend can be more securely fixed. After pressure reduction, the effect of reducing the adhesive force due to the expansion of the gas in the air chamber becomes more excellent, and the adhesive sheet and the adherend are more easily separated.
なお、気室の平均直径は、例えば、粘着剤層をデジタル顕微鏡または走査型電子顕微鏡（ＳＥＭ）にて撮影し、直径０．１μｍ以上の気室を、好ましくは１０個以上の気室について、それらの気室の直径を測定した結果を算術平均することにより求めることができる。このとき、非球状の形状の気室については、同等の体積を有する球状の気室に換算して平均直径を求めるものとする。また、粘着剤層に占める気室の体積割合は、粘着剤層をデジタル顕微鏡またはＳＥＭにて撮影し、その所定範囲における気室部分の面積割合を測定し、好ましくは５箇所以上の撮影画像について、それらの気室部分の面積割合を測定した結果から、気室の体積割合として求めることができる。
In addition, the average diameter of the air chamber is, for example, photographed the pressure-sensitive adhesive layer with a digital microscope or a scanning electron microscope (SEM), and the air chamber having a diameter of 0.1 μm or more, preferably about 10 or more air chambers, It can obtain | require by arithmetically averaging the result of having measured the diameter of those air chambers. At this time, for the non-spherical shaped air chamber, the average diameter is calculated in terms of a spherical air chamber having an equivalent volume. In addition, the volume ratio of the air chambers in the pressure-sensitive adhesive layer is obtained by photographing the pressure-sensitive adhesive layer with a digital microscope or SEM and measuring the area ratio of the air chamber portion in the predetermined range, preferably about five or more photographed images. From the result of measuring the area ratio of the air chamber portions, the volume ratio of the air chamber can be obtained.
粘着剤層の内部に気室を形成する方法は特に限定されず、公知の方法を適宜採用することができる。例えば、粘着剤層を形成するための粘着剤組成物を強撹拌し空気等の気体を意図的に混入させる方法、粘着剤組成物に気体を注入（バブリング）する方法、中空フィラー（内部に気体を含有する）を粘着剤組成物に配合する方法、熱発泡剤等を粘着剤組成物に配合し粘着剤層を形成した後に発泡させて気室を形成する方法、などが挙げられる。
The method for forming the air chamber in the pressure-sensitive adhesive layer is not particularly limited, and a known method can be appropriately employed. For example, a method in which the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer is vigorously stirred and a gas such as air is intentionally mixed, a method in which gas is injected (bubbled) into the pressure-sensitive adhesive composition, a hollow filler (a gas in the interior) And the like, and a method of forming an air chamber by foaming after forming a pressure-sensitive adhesive layer by blending a thermal foaming agent or the like into the pressure-sensitive adhesive composition.
なお、気体の混入・注入等による気室の形成容易性や、また形成された気室の安定性の観点から、粘着剤組成物に界面活性剤を配合してもよい。このような界面活性剤としては、例えば、イオン性界面活性剤、炭化水素系界面活性剤、シリコーン系界面活性剤、フッ素系界面活性剤等が挙げられる。
It should be noted that a surfactant may be added to the pressure-sensitive adhesive composition from the viewpoint of easy formation of the air chamber by mixing and injection of gas and the stability of the formed air chamber. Examples of such surfactants include ionic surfactants, hydrocarbon surfactants, silicone surfactants, and fluorine surfactants.
（３）粘着剤層の物性等
（３－１）厚さ
本実施形態における粘着剤層の厚さは、５～１００μｍであることが好ましく、１０～５０μｍであることが特に好ましく、１５～３０μｍであることがさらに好ましい。粘着剤層の厚さが５μｍ以上であると、減圧時の空間をより多く確保できるため、好ましい。粘着剤層の厚さが１００μｍ以下であると、塗布時の膜厚精度が確保できるため、好ましい。 (3) Physical properties of pressure-sensitive adhesive layer, etc. (3-1) Thickness The thickness of the pressure-sensitive adhesive layer in this embodiment is preferably 5 to 100 μm, particularly preferably 10 to 50 μm, and 15 to 30 μm. More preferably. It is preferable that the pressure-sensitive adhesive layer has a thickness of 5 μm or more because more space can be secured during decompression. It is preferable for the thickness of the pressure-sensitive adhesive layer to be 100 μm or less because the film thickness accuracy during application can be ensured.
（３－１）厚さ
本実施形態における粘着剤層の厚さは、５～１００μｍであることが好ましく、１０～５０μｍであることが特に好ましく、１５～３０μｍであることがさらに好ましい。粘着剤層の厚さが５μｍ以上であると、減圧時の空間をより多く確保できるため、好ましい。粘着剤層の厚さが１００μｍ以下であると、塗布時の膜厚精度が確保できるため、好ましい。 (3) Physical properties of pressure-sensitive adhesive layer, etc. (3-1) Thickness The thickness of the pressure-sensitive adhesive layer in this embodiment is preferably 5 to 100 μm, particularly preferably 10 to 50 μm, and 15 to 30 μm. More preferably. It is preferable that the pressure-sensitive adhesive layer has a thickness of 5 μm or more because more space can be secured during decompression. It is preferable for the thickness of the pressure-sensitive adhesive layer to be 100 μm or less because the film thickness accuracy during application can be ensured.
（３－２）粘着力
粘着シートの粘着力は、０．５～５０Ｎ／２５ｍｍであることが好ましく、２～４０Ｎ／２５ｍｍであることがより好ましく、５～３０Ｎ／２５ｍｍであることが特に好ましい。粘着シートの粘着力が上記の範囲内にあることで、被着体を確実に固定することができ、例えば、被着体の加工工程における被着体の仮固定に非常に有用である。 (3-2) Adhesive strength The adhesive strength of the adhesive sheet is preferably 0.5 to 50 N / 25 mm, more preferably 2 to 40 N / 25 mm, and particularly preferably 5 to 30 N / 25 mm. . When the adhesive strength of the pressure-sensitive adhesive sheet is within the above range, the adherend can be reliably fixed. For example, it is very useful for temporarily fixing the adherend in the processing step of the adherend.
粘着シートの粘着力は、０．５～５０Ｎ／２５ｍｍであることが好ましく、２～４０Ｎ／２５ｍｍであることがより好ましく、５～３０Ｎ／２５ｍｍであることが特に好ましい。粘着シートの粘着力が上記の範囲内にあることで、被着体を確実に固定することができ、例えば、被着体の加工工程における被着体の仮固定に非常に有用である。 (3-2) Adhesive strength The adhesive strength of the adhesive sheet is preferably 0.5 to 50 N / 25 mm, more preferably 2 to 40 N / 25 mm, and particularly preferably 5 to 30 N / 25 mm. . When the adhesive strength of the pressure-sensitive adhesive sheet is within the above range, the adherend can be reliably fixed. For example, it is very useful for temporarily fixing the adherend in the processing step of the adherend.
なお、ここでいう粘着力は、後述する減圧処理を行っていない（粘着剤組成物が活性エネルギー線硬化性または熱硬化性を有する場合は、さらに活性エネルギー線の照射および加熱を行っていない）粘着シートについて、シリコンミラーウェハを被着体とし、その鏡面に粘着シートを貼り合わせ、ＪＩＳ Ｚ０２３７：２００９に準じた１８０°引き剥がし法により測定した粘着力（Ｎ／２５ｍｍ）とする。
In addition, the adhesive force here does not perform the pressure reduction process mentioned later (When the adhesive composition has active energy ray curable property or thermosetting property, irradiation and heating of the active energy ray are not further performed). For the adhesive sheet, a silicon mirror wafer is used as an adherend, and the adhesive sheet is bonded to the mirror surface, and the adhesive strength (N / 25 mm) measured by the 180 ° peeling method according to JIS Z0237: 2009 is used.
（３－３）粘着力減少率
粘着シートの粘着力減少率は、５％以上であることが好ましく、１０％以上であることがより好ましく、３０％以上であることが特に好ましい。粘着シートの粘着力が上記の範囲内にあることで、本実施形態において粘着シートと被着体との剥離がさらに容易になる。 (3-3) Adhesive strength reduction rate The adhesive strength reduction rate of the adhesive sheet is preferably 5% or more, more preferably 10% or more, and particularly preferably 30% or more. When the adhesive strength of the adhesive sheet is within the above range, in this embodiment, the adhesive sheet and the adherend are more easily separated.
粘着シートの粘着力減少率は、５％以上であることが好ましく、１０％以上であることがより好ましく、３０％以上であることが特に好ましい。粘着シートの粘着力が上記の範囲内にあることで、本実施形態において粘着シートと被着体との剥離がさらに容易になる。 (3-3) Adhesive strength reduction rate The adhesive strength reduction rate of the adhesive sheet is preferably 5% or more, more preferably 10% or more, and particularly preferably 30% or more. When the adhesive strength of the adhesive sheet is within the above range, in this embodiment, the adhesive sheet and the adherend are more easily separated.
なお、ここでいう粘着力減少率は、後述する減圧処理を行う前（粘着剤組成物が活性エネルギー線硬化性または熱硬化性を有する場合は、活性エネルギー線の照射または加熱を行った後）の粘着シートと、減圧処理を行った後（粘着剤組成物が活性エネルギー線硬化性または熱硬化性を有する場合は、活性エネルギー線の照射および加熱を行った後）の粘着シートとのそれぞれにおいて、前述したように粘着力を測定し、得られた値に基づき以下の式によって算出される。
粘着力減少率（％）＝（減圧前粘着力－減圧後粘着力）／（減圧後粘着力）×１００ In addition, the adhesive force decreasing rate here is before performing the pressure reduction process mentioned later (When the adhesive composition has active energy ray curable or thermosetting, after irradiation or heating of active energy rays) In each of the pressure-sensitive adhesive sheet and the pressure-sensitive adhesive sheet after being subjected to reduced pressure treatment (when the pressure-sensitive adhesive composition has active energy ray curable or thermosetting properties, after irradiation and heating with active energy rays) The adhesive strength is measured as described above, and is calculated by the following formula based on the obtained value.
Adhesive strength reduction rate (%) = (adhesive strength before decompression−adhesive strength after decompression) / (adhesive strength after decompression) × 100
粘着力減少率（％）＝（減圧前粘着力－減圧後粘着力）／（減圧後粘着力）×１００ In addition, the adhesive force decreasing rate here is before performing the pressure reduction process mentioned later (When the adhesive composition has active energy ray curable or thermosetting, after irradiation or heating of active energy rays) In each of the pressure-sensitive adhesive sheet and the pressure-sensitive adhesive sheet after being subjected to reduced pressure treatment (when the pressure-sensitive adhesive composition has active energy ray curable or thermosetting properties, after irradiation and heating with active energy rays) The adhesive strength is measured as described above, and is calculated by the following formula based on the obtained value.
Adhesive strength reduction rate (%) = (adhesive strength before decompression−adhesive strength after decompression) / (adhesive strength after decompression) × 100
なお、後述するとおり、粘着剤組成物が活性エネルギー線硬化性または熱硬化性を有する場合の活性エネルギー線の照射または加熱は、減圧処理の前であっても後であってもよいが、いずれの場合であっても粘着力減少率は上記式によって算出されるものとする。
As will be described later, the irradiation or heating of the active energy ray when the pressure-sensitive adhesive composition has active energy ray curable property or thermosetting property may be before or after the decompression treatment, Even in this case, the adhesive strength reduction rate is calculated by the above formula.
（３－４）応力緩和率
本実施形態において、粘着剤層の応力緩和率の下限値は、３０％以上であることが好ましく、４５％以上であることが特に好ましく、６０％以上であることがさらに好ましい。粘着剤層の応力緩和率の上限値は、１００％以下であることが好ましく、９０％以下であることが特に好ましく、８０％以下であることがさらに好ましい。応力緩和率を前述の範囲に設定することで、粘着剤層が減圧時にバランス良く安定的に変形することができる。 (3-4) Stress relaxation rate In the present embodiment, the lower limit of the stress relaxation rate of the pressure-sensitive adhesive layer is preferably 30% or more, particularly preferably 45% or more, and 60% or more. Is more preferable. The upper limit of the stress relaxation rate of the pressure-sensitive adhesive layer is preferably 100% or less, particularly preferably 90% or less, and further preferably 80% or less. By setting the stress relaxation rate within the above-described range, the pressure-sensitive adhesive layer can be stably deformed with good balance during decompression.
本実施形態において、粘着剤層の応力緩和率の下限値は、３０％以上であることが好ましく、４５％以上であることが特に好ましく、６０％以上であることがさらに好ましい。粘着剤層の応力緩和率の上限値は、１００％以下であることが好ましく、９０％以下であることが特に好ましく、８０％以下であることがさらに好ましい。応力緩和率を前述の範囲に設定することで、粘着剤層が減圧時にバランス良く安定的に変形することができる。 (3-4) Stress relaxation rate In the present embodiment, the lower limit of the stress relaxation rate of the pressure-sensitive adhesive layer is preferably 30% or more, particularly preferably 45% or more, and 60% or more. Is more preferable. The upper limit of the stress relaxation rate of the pressure-sensitive adhesive layer is preferably 100% or less, particularly preferably 90% or less, and further preferably 80% or less. By setting the stress relaxation rate within the above-described range, the pressure-sensitive adhesive layer can be stably deformed with good balance during decompression.
なお、ここでいう粘着剤層の応力緩和率は、後述する減圧処理を行っていない（粘着剤組成物が活性エネルギー線硬化性または熱硬化性を有する場合は、さらに活性エネルギー線の照射または加熱を行っていない）粘着剤層について、引張試験にて３００％伸長させて３００秒保持した後の応力緩和率をいう。引張試験は、具体的には、厚さ５００μｍ、幅１５ｍｍ、長さ５５ｍｍ（このうち測定範囲は２５ｍｍ）に成形した粘着剤を、２３℃、５０％ＲＨの環境下で、２００ｍｍ／分の速度で３００％伸長させて行うものとする。
Note that the stress relaxation rate of the pressure-sensitive adhesive layer here is not subjected to a decompression treatment described later (if the pressure-sensitive adhesive composition has active energy ray curable or thermosetting properties, irradiation or heating with active energy rays is further performed. For the pressure-sensitive adhesive layer, the stress relaxation rate after being stretched by 300% in a tensile test and held for 300 seconds. Specifically, the tensile test was performed at a speed of 200 mm / min with an adhesive formed into a thickness of 500 μm, a width of 15 mm, and a length of 55 mm (of which the measurement range is 25 mm) in an environment of 23 ° C. and 50% RH. It is assumed that the stretching is performed by 300%.
（３－５）破断伸度
本実施形態において、粘着剤層の破断伸度の下限値は、２００％以上であることが好ましく、５００％以上であることが特に好ましく、１０００％以上であることがさらに好ましい。また、粘着剤層の破断伸度の上限値は、５０００％以下であることが好ましく、４０００％以下であることが特に好ましく、３０００％以下であることがさらに好ましい。粘着剤層の破断伸度を前述の範囲に設定することで、粘着剤層が減圧時にバランス良く安定的に変形することができる。 (3-5) Breaking Elongation In this embodiment, the lower limit of the breaking elongation of the pressure-sensitive adhesive layer is preferably 200% or more, particularly preferably 500% or more, and preferably 1000% or more. Is more preferable. Moreover, the upper limit of the elongation at break of the pressure-sensitive adhesive layer is preferably 5000% or less, particularly preferably 4000% or less, and further preferably 3000% or less. By setting the breaking elongation of the pressure-sensitive adhesive layer within the above-described range, the pressure-sensitive adhesive layer can be stably deformed with a good balance during decompression.
本実施形態において、粘着剤層の破断伸度の下限値は、２００％以上であることが好ましく、５００％以上であることが特に好ましく、１０００％以上であることがさらに好ましい。また、粘着剤層の破断伸度の上限値は、５０００％以下であることが好ましく、４０００％以下であることが特に好ましく、３０００％以下であることがさらに好ましい。粘着剤層の破断伸度を前述の範囲に設定することで、粘着剤層が減圧時にバランス良く安定的に変形することができる。 (3-5) Breaking Elongation In this embodiment, the lower limit of the breaking elongation of the pressure-sensitive adhesive layer is preferably 200% or more, particularly preferably 500% or more, and preferably 1000% or more. Is more preferable. Moreover, the upper limit of the elongation at break of the pressure-sensitive adhesive layer is preferably 5000% or less, particularly preferably 4000% or less, and further preferably 3000% or less. By setting the breaking elongation of the pressure-sensitive adhesive layer within the above-described range, the pressure-sensitive adhesive layer can be stably deformed with a good balance during decompression.
なお、ここでいう粘着剤層の破断伸度は、後述する減圧処理を行っていない（粘着剤組成物が活性エネルギー線硬化性または熱硬化性を有する場合は、さらに活性エネルギー線の照射または加熱を行なっていない）粘着剤層について、基材等を伴わない単独の粘着剤層として測定し、具体的には、厚さ５００μｍ、幅１５ｍｍ、長さ５５ｍｍ（このうち測定範囲は２５ｍｍ）に成形した粘着剤を、２３℃、５０％ＲＨの環境下で、２００ｍｍ／分の速度で伸長させて行うものとする。
Note that the elongation at break of the pressure-sensitive adhesive layer here is not subjected to a decompression treatment described later (if the pressure-sensitive adhesive composition has active energy ray curable or thermosetting properties, irradiation or heating with active energy rays is further performed. The pressure-sensitive adhesive layer was measured as a single pressure-sensitive adhesive layer without a substrate or the like, and specifically, molded into a thickness of 500 μm, a width of 15 mm, and a length of 55 mm (of which the measurement range is 25 mm). The obtained adhesive is stretched at a speed of 200 mm / min in an environment of 23 ° C. and 50% RH.
（３－６）ゲル分率
本実施形態において、粘着剤層のゲル分率の下限値は、１％以上であることが好ましく、２％以上であることが特に好ましく、３％以上であることがさらに好ましい。粘着剤層のゲル分率の上限値は、８０％以下であることが好ましく、７０％以下であることが特に好ましく、６０％以下であることがさらに好ましい。粘着剤層のゲル分率の下限値が１％以上であると、架橋による粘着剤どうしの反応により、粘着シートとしての安定性が確保できる。一方、粘着剤層のゲル分率の上限値が８０％以下であると粘着シート上にタックを付与し易く、良好な仮固定性を得ることができる。 (3-6) Gel fraction In this embodiment, the lower limit of the gel fraction of the pressure-sensitive adhesive layer is preferably 1% or more, particularly preferably 2% or more, and 3% or more. Is more preferable. The upper limit of the gel fraction of the pressure-sensitive adhesive layer is preferably 80% or less, particularly preferably 70% or less, and further preferably 60% or less. When the lower limit of the gel fraction of the pressure-sensitive adhesive layer is 1% or more, stability as a pressure-sensitive adhesive sheet can be ensured by reaction between the pressure-sensitive adhesives due to crosslinking. On the other hand, if the upper limit of the gel fraction of the pressure-sensitive adhesive layer is 80% or less, it is easy to impart tack to the pressure-sensitive adhesive sheet, and good temporary fixability can be obtained.
本実施形態において、粘着剤層のゲル分率の下限値は、１％以上であることが好ましく、２％以上であることが特に好ましく、３％以上であることがさらに好ましい。粘着剤層のゲル分率の上限値は、８０％以下であることが好ましく、７０％以下であることが特に好ましく、６０％以下であることがさらに好ましい。粘着剤層のゲル分率の下限値が１％以上であると、架橋による粘着剤どうしの反応により、粘着シートとしての安定性が確保できる。一方、粘着剤層のゲル分率の上限値が８０％以下であると粘着シート上にタックを付与し易く、良好な仮固定性を得ることができる。 (3-6) Gel fraction In this embodiment, the lower limit of the gel fraction of the pressure-sensitive adhesive layer is preferably 1% or more, particularly preferably 2% or more, and 3% or more. Is more preferable. The upper limit of the gel fraction of the pressure-sensitive adhesive layer is preferably 80% or less, particularly preferably 70% or less, and further preferably 60% or less. When the lower limit of the gel fraction of the pressure-sensitive adhesive layer is 1% or more, stability as a pressure-sensitive adhesive sheet can be ensured by reaction between the pressure-sensitive adhesives due to crosslinking. On the other hand, if the upper limit of the gel fraction of the pressure-sensitive adhesive layer is 80% or less, it is easy to impart tack to the pressure-sensitive adhesive sheet, and good temporary fixability can be obtained.
なお、ここでいう粘着剤層のゲル分率は、後述する減圧処理を行っていない（粘着剤組成物が活性エネルギー線硬化性または熱硬化性を有する場合は、さらに活性エネルギー線の照射または加熱を行っていない）粘着剤層についての貼付時（シーズニング期間経過後）での値である。具体的には、粘着剤を剥離シートに塗布し、加熱乾燥した後、２３℃、５０％ＲＨの環境下にて７日間保管した後のゲル分率をいう。なお、粘着剤のゲル分率は、シーズニング期間経過後であれば安定することから、シーズニング期間が経過しているかどうか不明の場合、改めて、２３℃、５０％ＲＨの環境下にて７日間保管した後、測定すればよい。
In addition, the gel fraction of an adhesive layer here is not performing the pressure reduction process mentioned later (When an adhesive composition has active energy ray sclerosis | hardenability or thermosetting property, irradiation or heating of an active energy ray is further carried out. It is the value at the time of sticking (after the seasoning period has elapsed) about the pressure-sensitive adhesive layer. Specifically, it refers to the gel fraction after the pressure-sensitive adhesive is applied to a release sheet, dried by heating, and stored for 7 days in an environment of 23 ° C. and 50% RH. In addition, since the gel fraction of the adhesive is stable after the seasoning period has elapsed, if it is unclear whether the seasoning period has elapsed, it is stored again in an environment of 23 ° C. and 50% RH for 7 days. And then measure.
（４）基材
本実施形態に係る粘着シートは、粘着剤層に加えて、基材を備えていてもよい。ここで、基材は、粘着シートが被着体の加工工程などの所望の工程において適切に機能できる限り、その構成材料は特に限定されず、例えば、紙基材、樹脂フィルム又はシート、紙基材を樹脂でラミネートした基材等が挙げられ、本実施形態の一態様の粘着シートの用途に応じて適宜選択することができる。中でも、減圧効果に対する有利さから、樹脂系の材料を主材とするフィルムから構成されることが好ましい。そのフィルムの具体例として、エチレン－酢酸ビニル共重合体フィルム、エチレン－（メタ）アクリル酸共重合体フィルム、エチレン－（メタ）アクリル酸エステル共重合体フィルム等のエチレン系共重合フィルム；低密度ポリエチレン（ＬＤＰＥ）フィルム、直鎖低密度ポリエチレン（ＬＬＤＰＥ）フィルム、高密度ポリエチレン（ＨＤＰＥ）フィルム等のポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、エチレン－ノルボルネン共重合体フィルム、ノルボルネン樹脂フィルム等のポリオレフィン系フィルム；ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム等のポリ塩化ビニル系フィルム；ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム等のポリエステル系フィルム；ポリウレタンフィルム；ポリイミドフィルム；ポリスチレンフィルム；ポリカーボネートフィルム；フッ素樹脂フィルムなどが挙げられる。またこれらの架橋フィルム、アイオノマーフィルムのような変性フィルムも用いられる。上記の基材はこれらの１種からなるフィルムでもよいし、さらにこれらを２種類以上組み合わせた積層フィルムであってもよい。 (4) Base material The pressure-sensitive adhesive sheet according to this embodiment may include a base material in addition to the pressure-sensitive adhesive layer. Here, the base material is not particularly limited as long as the pressure-sensitive adhesive sheet can appropriately function in a desired process such as an adherend processing process. For example, a paper base material, a resin film or sheet, a paper base The base material etc. which laminated the material with resin are mentioned, According to the use of the adhesive sheet of 1 aspect of this embodiment, it can select suitably. Among them, it is preferable that the film is composed of a resin-based material as a main material because of its advantage against the pressure reduction effect. Specific examples of such films include ethylene-copolymer films such as ethylene-vinyl acetate copolymer films, ethylene- (meth) acrylic acid copolymer films, and ethylene- (meth) acrylic acid ester copolymer films; low density Polyethylene film such as polyethylene (LDPE) film, linear low density polyethylene (LLDPE) film, high density polyethylene (HDPE) film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, ethylene-norbornene copolymer film, Polyolefin film such as norbornene resin film; Polyvinyl chloride film such as polyvinyl chloride film and vinyl chloride copolymer film; Polyethylene terephthalate film, Polybutylene tele Polyester film of tallate films; polyurethane film; polyimide film; polystyrene films; polycarbonate films; and fluorine resin film. Further, modified films such as these crosslinked films and ionomer films are also used. The substrate may be a film made of one of these, or may be a laminated film in which two or more of these are combined.
本実施形態に係る粘着シートは、粘着剤層に加えて、基材を備えていてもよい。ここで、基材は、粘着シートが被着体の加工工程などの所望の工程において適切に機能できる限り、その構成材料は特に限定されず、例えば、紙基材、樹脂フィルム又はシート、紙基材を樹脂でラミネートした基材等が挙げられ、本実施形態の一態様の粘着シートの用途に応じて適宜選択することができる。中でも、減圧効果に対する有利さから、樹脂系の材料を主材とするフィルムから構成されることが好ましい。そのフィルムの具体例として、エチレン－酢酸ビニル共重合体フィルム、エチレン－（メタ）アクリル酸共重合体フィルム、エチレン－（メタ）アクリル酸エステル共重合体フィルム等のエチレン系共重合フィルム；低密度ポリエチレン（ＬＤＰＥ）フィルム、直鎖低密度ポリエチレン（ＬＬＤＰＥ）フィルム、高密度ポリエチレン（ＨＤＰＥ）フィルム等のポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、エチレン－ノルボルネン共重合体フィルム、ノルボルネン樹脂フィルム等のポリオレフィン系フィルム；ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム等のポリ塩化ビニル系フィルム；ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム等のポリエステル系フィルム；ポリウレタンフィルム；ポリイミドフィルム；ポリスチレンフィルム；ポリカーボネートフィルム；フッ素樹脂フィルムなどが挙げられる。またこれらの架橋フィルム、アイオノマーフィルムのような変性フィルムも用いられる。上記の基材はこれらの１種からなるフィルムでもよいし、さらにこれらを２種類以上組み合わせた積層フィルムであってもよい。 (4) Base material The pressure-sensitive adhesive sheet according to this embodiment may include a base material in addition to the pressure-sensitive adhesive layer. Here, the base material is not particularly limited as long as the pressure-sensitive adhesive sheet can appropriately function in a desired process such as an adherend processing process. For example, a paper base material, a resin film or sheet, a paper base The base material etc. which laminated the material with resin are mentioned, According to the use of the adhesive sheet of 1 aspect of this embodiment, it can select suitably. Among them, it is preferable that the film is composed of a resin-based material as a main material because of its advantage against the pressure reduction effect. Specific examples of such films include ethylene-copolymer films such as ethylene-vinyl acetate copolymer films, ethylene- (meth) acrylic acid copolymer films, and ethylene- (meth) acrylic acid ester copolymer films; low density Polyethylene film such as polyethylene (LDPE) film, linear low density polyethylene (LLDPE) film, high density polyethylene (HDPE) film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, ethylene-norbornene copolymer film, Polyolefin film such as norbornene resin film; Polyvinyl chloride film such as polyvinyl chloride film and vinyl chloride copolymer film; Polyethylene terephthalate film, Polybutylene tele Polyester film of tallate films; polyurethane film; polyimide film; polystyrene films; polycarbonate films; and fluorine resin film. Further, modified films such as these crosslinked films and ionomer films are also used. The substrate may be a film made of one of these, or may be a laminated film in which two or more of these are combined.
基材を構成するフィルムは、エチレン系共重合フィルムおよびポリオレフィン系フィルムの少なくとも一種を備えることが好ましい。エチレン系共重合フィルムは共重合比を変えることなどによりその機械特性を広範な範囲で制御することが容易である。このため、エチレン系共重合フィルムを備える基材は本実施形態に係る粘着シートの基材として求められる機械特性を満たし易い。また、エチレン系共重合フィルムは粘着剤層に対する密着性が比較的高いため、粘着シートとして使用した際に基材と粘着剤層との界面での剥離が生じ難い。
The film constituting the base material preferably includes at least one of an ethylene copolymer film and a polyolefin film. It is easy to control the mechanical characteristics of an ethylene copolymer film in a wide range by changing the copolymerization ratio. For this reason, the base material provided with the ethylene-based copolymer film easily satisfies the mechanical properties required as the base material of the pressure-sensitive adhesive sheet according to this embodiment. Moreover, since the ethylene copolymer film has relatively high adhesion to the pressure-sensitive adhesive layer, peeling at the interface between the base material and the pressure-sensitive adhesive layer hardly occurs when used as a pressure-sensitive adhesive sheet.
本実施形態において用いる基材には、上記の樹脂系材料を主材とするフィルム内に、顔料、染料、難燃剤、可塑剤、帯電防止剤、滑剤、フィラー等の各種添加剤が含まれていてもよい。顔料としては、例えば、二酸化チタン、カーボンブラック等が挙げられる。また、フィラーとしては、メラミン樹脂のような有機系材料、ヒュームドシリカのような無機系材料およびニッケル粒子のような金属系材料が例示される。こうした添加剤の含有量は特に限定されないが、基材が所望の機能を発揮し、平滑性や柔軟性を失わない範囲に留めるべきである。
The base material used in the present embodiment contains various additives such as pigments, dyes, flame retardants, plasticizers, antistatic agents, lubricants, fillers, etc., in the film mainly composed of the above-mentioned resin-based material. May be. Examples of the pigment include titanium dioxide and carbon black. Examples of the filler include organic materials such as melamine resin, inorganic materials such as fumed silica, and metal materials such as nickel particles. The content of such an additive is not particularly limited, but should be within a range where the substrate exhibits a desired function and does not lose smoothness and flexibility.
粘着剤層を硬化させるために照射するエネルギー線として紫外線を用い、基材側から照射する場合には、基材は紫外線に対して透過性を有することが好ましい。また、エネルギー線として電子線を用いる場合には、基材は電子線の透過性を有していることが好ましい。ただし、被着体がエネルギー線透過性を有し、エネルギー線を被着体側から照射する場合は、基材がエネルギー線透過性を有している必要はない。
When ultraviolet rays are used as the energy rays to be irradiated to cure the pressure-sensitive adhesive layer and irradiation is performed from the substrate side, the substrate is preferably permeable to ultraviolet rays. Moreover, when using an electron beam as an energy beam, it is preferable that the base material has the transparency of an electron beam. However, when the adherend has energy ray permeability and the energy beam is irradiated from the adherend side, the substrate does not need to have energy ray permeability.
また、基材の粘着剤層側の面（以下「基材被着面」ともいう。）には、カルボキシル基、ならびにそのイオンおよび塩からなる群から選ばれる１種または２種以上を有する成分が存在することが好ましい。基材における上記の成分と粘着剤層に係る成分（粘着剤層を構成する成分および架橋剤などの粘着剤層を形成するにあたり使用される成分が例示される。）とが化学的に相互作用することにより、これらの間で剥離が生じる可能性を低減させることができる。基材被着面にそのような成分を存在させるための具体的な手法は特に限定されない。例えば、基材自体をエチレン－（メタ）アクリル酸共重合体フィルム、アイオノマー樹脂フィルム等として、基材を構成する材料となる樹脂がカルボキシル基、ならびにそのイオンおよび塩からなる群から選ばれる１種または２種以上を有するものとするのであってもよい。基材被着面に上記成分を存在させる他の手法として、基材は例えばポリオレフィン系フィルムであって、基材被着面側にコロナ処理が施されていたり、プライマー層が設けられていたりしてもよい。また、基材の基材被着面と反対側の面には各種の塗膜が設けられていてもよい。
In addition, a component having one or more kinds selected from the group consisting of a carboxyl group and its ions and salts is provided on the surface of the substrate on the side of the pressure-sensitive adhesive layer (hereinafter also referred to as “substrate-coated surface”). Is preferably present. The above-mentioned component in the substrate and the component related to the pressure-sensitive adhesive layer (components used for forming the pressure-sensitive adhesive layer such as the component constituting the pressure-sensitive adhesive layer and the cross-linking agent are exemplified) chemically. By doing, possibility that peeling will generate | occur | produce between these can be reduced. The specific method for making such a component exist in a base-material adhesion surface is not specifically limited. For example, the base material itself is an ethylene- (meth) acrylic acid copolymer film, an ionomer resin film, etc., and the resin constituting the base material is selected from the group consisting of carboxyl groups, ions and salts thereof. Or you may have 2 or more types. As another method for causing the above components to be present on the substrate-adhered surface, the substrate is, for example, a polyolefin film, and the substrate-adhered surface side is subjected to corona treatment or a primer layer is provided. May be. Various coating films may be provided on the surface of the substrate opposite to the substrate deposition surface.
基材の厚さは、粘着シートが所望の工程において適切に機能できる限り限定されないが、取扱性及び経済性の観点から、好ましくは５～１０００μｍ、より好ましくは１０～５００μｍ、更に好ましくは１２～２５０μｍ、より更に好ましくは１５～１５０μｍである。
The thickness of the substrate is not limited as long as the pressure-sensitive adhesive sheet can function properly in a desired process, but it is preferably 5 to 1000 μm, more preferably 10 to 500 μm, and still more preferably 12 to 12 from the viewpoint of handleability and economy. The thickness is 250 μm, more preferably 15 to 150 μm.
（５）剥離シート
本実施形態に係る粘着シートは、被着体に粘着剤層を貼付するまでの間、粘着剤層を保護する目的で、粘着剤層の粘着面に、剥離シートが積層されていてもよい。剥離シートの構成は任意であり、プラスチックフィルムを剥離剤等により剥離処理したものが例示される。プラスチックフィルムの具体例としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム、およびポリプロピレンやポリエチレン等のポリオレフィンフィルムが挙げられる。剥離剤としては、シリコーン系、フッ素系、長鎖アルキル系等を用いることができるが、これらの中で、安価で安定した性能が得られるシリコーン系が好ましい。剥離シートの厚さについては特に制限はないが、通常２０～２５０μｍ程度である。 (5) Release sheet The release sheet is laminated on the adhesive surface of the adhesive layer for the purpose of protecting the adhesive layer until the adhesive layer is applied to the adherend. It may be. The configuration of the release sheet is arbitrary, and examples include a release film of a plastic film with a release agent. Specific examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. As the release agent, silicone-based, fluorine-based, long-chain alkyl-based, and the like can be used, and among these, a silicone-based material that is inexpensive and provides stable performance is preferable. The thickness of the release sheet is not particularly limited, but is usually about 20 to 250 μm.
本実施形態に係る粘着シートは、被着体に粘着剤層を貼付するまでの間、粘着剤層を保護する目的で、粘着剤層の粘着面に、剥離シートが積層されていてもよい。剥離シートの構成は任意であり、プラスチックフィルムを剥離剤等により剥離処理したものが例示される。プラスチックフィルムの具体例としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム、およびポリプロピレンやポリエチレン等のポリオレフィンフィルムが挙げられる。剥離剤としては、シリコーン系、フッ素系、長鎖アルキル系等を用いることができるが、これらの中で、安価で安定した性能が得られるシリコーン系が好ましい。剥離シートの厚さについては特に制限はないが、通常２０～２５０μｍ程度である。 (5) Release sheet The release sheet is laminated on the adhesive surface of the adhesive layer for the purpose of protecting the adhesive layer until the adhesive layer is applied to the adherend. It may be. The configuration of the release sheet is arbitrary, and examples include a release film of a plastic film with a release agent. Specific examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. As the release agent, silicone-based, fluorine-based, long-chain alkyl-based, and the like can be used, and among these, a silicone-based material that is inexpensive and provides stable performance is preferable. The thickness of the release sheet is not particularly limited, but is usually about 20 to 250 μm.
（６）粘着シートの製造方法
粘着シートの製造方法は、前述の粘着剤組成物から形成される粘着剤層を形成し、かつ、粘着剤層の内部に気室を形成することができる方法であれば、詳細な方法は特に限定されない。例えば、基材と粘着剤層とからなる粘着シートの製造方法としては、前述の粘着剤組成物から形成される粘着剤層を基材の一の面に積層できればよい。一例を挙げれば、前述の粘着剤組成物、および所望によりさらに溶媒または分散媒を含有する塗布用組成物を調製する。気室を形成するためには、かかる塗布用組成物を強撹拌し空気等の気体を意図的に混入させてもよく、塗布用組成物に気体を注入（バブリング）してもよい。また、中空フィラー（内部に気体を含有する）や熱発泡剤等を用いて気室を形成する場合は、塗布用組成物に中空フィラーや熱発泡剤等を配合してもよい。 (6) Manufacturing method of adhesive sheet The manufacturing method of an adhesive sheet is a method which can form the adhesive layer formed from the above-mentioned adhesive composition, and can form an air chamber inside an adhesive layer. If there is, the detailed method is not particularly limited. For example, as a method for producing a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer, it is only necessary that a pressure-sensitive adhesive layer formed from the above-mentioned pressure-sensitive adhesive composition can be laminated on one surface of the base material. As an example, a coating composition containing the above-mentioned pressure-sensitive adhesive composition and optionally further containing a solvent or a dispersion medium is prepared. In order to form an air chamber, the coating composition may be vigorously stirred and a gas such as air may be intentionally mixed, or a gas may be injected (bubbled) into the coating composition. Moreover, when forming an air chamber using a hollow filler (it contains gas inside), a thermal foaming agent, etc., you may mix | blend a hollow filler, a thermal foaming agent, etc. with the composition for application | coating.
粘着シートの製造方法は、前述の粘着剤組成物から形成される粘着剤層を形成し、かつ、粘着剤層の内部に気室を形成することができる方法であれば、詳細な方法は特に限定されない。例えば、基材と粘着剤層とからなる粘着シートの製造方法としては、前述の粘着剤組成物から形成される粘着剤層を基材の一の面に積層できればよい。一例を挙げれば、前述の粘着剤組成物、および所望によりさらに溶媒または分散媒を含有する塗布用組成物を調製する。気室を形成するためには、かかる塗布用組成物を強撹拌し空気等の気体を意図的に混入させてもよく、塗布用組成物に気体を注入（バブリング）してもよい。また、中空フィラー（内部に気体を含有する）や熱発泡剤等を用いて気室を形成する場合は、塗布用組成物に中空フィラーや熱発泡剤等を配合してもよい。 (6) Manufacturing method of adhesive sheet The manufacturing method of an adhesive sheet is a method which can form the adhesive layer formed from the above-mentioned adhesive composition, and can form an air chamber inside an adhesive layer. If there is, the detailed method is not particularly limited. For example, as a method for producing a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer, it is only necessary that a pressure-sensitive adhesive layer formed from the above-mentioned pressure-sensitive adhesive composition can be laminated on one surface of the base material. As an example, a coating composition containing the above-mentioned pressure-sensitive adhesive composition and optionally further containing a solvent or a dispersion medium is prepared. In order to form an air chamber, the coating composition may be vigorously stirred and a gas such as air may be intentionally mixed, or a gas may be injected (bubbled) into the coating composition. Moreover, when forming an air chamber using a hollow filler (it contains gas inside), a thermal foaming agent, etc., you may mix | blend a hollow filler, a thermal foaming agent, etc. with the composition for application | coating.
このようにして得られた塗布用組成物を、基材の一の面上に、ダイコーター、カーテンコーター、スプレーコーター、スリットコーター、ナイフコーター等により塗布して塗膜を形成し、当該塗膜を乾燥させることにより、粘着剤層と基材とからなる粘着シートを形成することができる。さらに、この粘着シートの粘着剤層における基材側の面と反対側の面に剥離シートを貼付して、粘着シートと剥離シートとの積層体を得てもよい。この積層体における剥離シートは工程材料として剥離してもよいし、電子部材や光学部材等の被着体に貼付するまでの間、粘着剤層を保護していてもよい。
The coating composition thus obtained is applied on one surface of the substrate by a die coater, curtain coater, spray coater, slit coater, knife coater, etc. to form a coating film, and the coating film By drying this, a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer and a substrate can be formed. Furthermore, you may stick a peeling sheet to the surface on the opposite side to the surface of the base material side in the adhesive layer of this adhesive sheet, and you may obtain the laminated body of an adhesive sheet and a peeling sheet. The release sheet in this laminate may be peeled off as a process material, or the adhesive layer may be protected until being attached to an adherend such as an electronic member or an optical member.
この場合において、塗布用組成物は、塗布を行うことが可能であればその性状は特に限定されず、粘着剤層を形成するための成分を溶質として含有する場合もあれば、分散質として含有する場合もある。また、塗布用組成物が熱発泡剤を含有する場合には、上記の乾燥の条件（温度、時間など）を変えることにより、または加熱処理を別途設けることにより、熱発泡剤を発泡させ、気室を形成してもよい。さらに、塗布用組成物が架橋剤を含有する場合には、上記の乾燥の条件（温度、時間など）を変えることにより、または加熱処理を別途設けることにより、塗膜内の（メタ）アクリル酸エステル重合体（Ａ）、（Ｂ１）または（Ｂ３）と架橋剤との架橋反応を進行させ、粘着剤層内に所望の存在密度で架橋構造を形成させればよい。この架橋反応を十分に進行させるために、上記の方法などによって基材に粘着剤層を積層させた後、得られた粘着シートを、例えば２３℃、相対湿度５０％の環境に数日間静置するといった養生を通常行う。
なお、本明細書において粘着剤の「架橋」とは、粘着シートを被着体に貼着する前に行われる反応をいい、被着体に貼着する前とは、例えば、前述した粘着剤層を形成する段階が挙げられる。そのため、粘着剤の「架橋」は、後述する「硬化」とは明確に区別される。 In this case, the properties of the coating composition are not particularly limited as long as it can be applied, and may contain a component for forming the pressure-sensitive adhesive layer as a solute or a dispersoid. There is also a case. When the coating composition contains a thermal foaming agent, the thermal foaming agent is foamed by changing the drying conditions (temperature, time, etc.) or by separately providing a heat treatment. A chamber may be formed. Further, when the coating composition contains a cross-linking agent, (meth) acrylic acid in the coating film can be obtained by changing the drying conditions (temperature, time, etc.) or by separately providing a heat treatment. What is necessary is just to advance the crosslinking reaction of ester polymer (A), (B1) or (B3), and a crosslinking agent, and to form a crosslinked structure in a desired presence density in an adhesive layer. In order to sufficiently proceed with this crosslinking reaction, after the pressure-sensitive adhesive layer is laminated on the substrate by the above-described method, the obtained pressure-sensitive adhesive sheet is allowed to stand for several days in an environment of 23 ° C. and 50% relative humidity, for example. It is usually done with curing.
In the present specification, “crosslinking” of the pressure-sensitive adhesive refers to a reaction performed before sticking the pressure-sensitive adhesive sheet to the adherend, and before sticking to the adherend is, for example, the pressure-sensitive adhesive described above. A step of forming a layer may be mentioned. Therefore, “crosslinking” of the pressure-sensitive adhesive is clearly distinguished from “curing” described later.
なお、本明細書において粘着剤の「架橋」とは、粘着シートを被着体に貼着する前に行われる反応をいい、被着体に貼着する前とは、例えば、前述した粘着剤層を形成する段階が挙げられる。そのため、粘着剤の「架橋」は、後述する「硬化」とは明確に区別される。 In this case, the properties of the coating composition are not particularly limited as long as it can be applied, and may contain a component for forming the pressure-sensitive adhesive layer as a solute or a dispersoid. There is also a case. When the coating composition contains a thermal foaming agent, the thermal foaming agent is foamed by changing the drying conditions (temperature, time, etc.) or by separately providing a heat treatment. A chamber may be formed. Further, when the coating composition contains a cross-linking agent, (meth) acrylic acid in the coating film can be obtained by changing the drying conditions (temperature, time, etc.) or by separately providing a heat treatment. What is necessary is just to advance the crosslinking reaction of ester polymer (A), (B1) or (B3), and a crosslinking agent, and to form a crosslinked structure in a desired presence density in an adhesive layer. In order to sufficiently proceed with this crosslinking reaction, after the pressure-sensitive adhesive layer is laminated on the substrate by the above-described method, the obtained pressure-sensitive adhesive sheet is allowed to stand for several days in an environment of 23 ° C. and 50% relative humidity, for example. It is usually done with curing.
In the present specification, “crosslinking” of the pressure-sensitive adhesive refers to a reaction performed before sticking the pressure-sensitive adhesive sheet to the adherend, and before sticking to the adherend is, for example, the pressure-sensitive adhesive described above. A step of forming a layer may be mentioned. Therefore, “crosslinking” of the pressure-sensitive adhesive is clearly distinguished from “curing” described later.
粘着シートの製造方法の別の一例としては、前述の剥離シートの剥離面上に塗布用組成物を塗布して塗膜を形成し、これを乾燥させて粘着剤層と剥離シートとからなる積層体を形成し、この積層体の粘着剤層における剥離シート側の面と反対側の面を基材に貼付して、粘着シートと剥離シートとの積層体を得てもよい。この積層体における剥離シートは工程材料として剥離してもよいし、電子部材や光学部材等の被着体に貼付するまでの間、粘着剤層を保護していてもよい。
As another example of the method for producing the pressure-sensitive adhesive sheet, a coating film is formed on the release surface of the above-described release sheet to form a coating film, which is dried to form a laminate composed of the pressure-sensitive adhesive layer and the release sheet. A laminate of the pressure-sensitive adhesive sheet and the release sheet may be obtained by forming a body and attaching the surface of the pressure-sensitive adhesive layer of the laminate opposite to the surface on the release sheet side to the substrate. The release sheet in this laminate may be peeled off as a process material, or the adhesive layer may be protected until being attached to an adherend such as an electronic member or an optical member.
また、基材を備えていない粘着シートのうち、粘着剤層の両面に２層の剥離シートがそれぞれ積層された粘着シートの製造方法としては、前述の剥離シートの剥離面上に塗布用組成物を塗布して塗膜を形成し、これを乾燥させて粘着剤層と剥離シートとからなる積層体を形成し、この積層体の粘着剤層における剥離シート側の面と反対側の面を他の剥離シートの剥離面に貼付して、剥離シート／粘着シート／剥離シートからなる積層体を得ることができる。この積層体における剥離シートは工程材料として剥離してもよいし、電子部材や光学部材等の被着体に貼付するまでの間、粘着剤層を保護していてもよい。
Moreover, as a manufacturing method of the adhesive sheet in which two release sheets were respectively laminated on both sides of the adhesive layer among the adhesive sheets not provided with a base material, the composition for coating on the release surface of the aforementioned release sheet Is applied to form a coating film, which is dried to form a laminate composed of a pressure-sensitive adhesive layer and a release sheet, and the surface on the side opposite to the release sheet side of the pressure-sensitive adhesive layer of this laminate is It can affix on the peeling surface of this release sheet, and can obtain the laminated body which consists of a release sheet / adhesive sheet / release sheet. The release sheet in this laminate may be peeled off as a process material, or the adhesive layer may be protected until being attached to an adherend such as an electronic member or an optical member.
〔粘着シートの剥離方法，加工物の製造方法〕
以上述べた粘着シートを用い、粘着シートと、粘着剤層の粘着面に貼着された被着体とを剥離する方法について、図２を参照しながら以下に説明する。 [Peeling method of adhesive sheet, manufacturing method of processed products]
A method for separating the pressure-sensitive adhesive sheet and the adherend adhered to the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer using the pressure-sensitive adhesive sheet described above will be described below with reference to FIG.
以上述べた粘着シートを用い、粘着シートと、粘着剤層の粘着面に貼着された被着体とを剥離する方法について、図２を参照しながら以下に説明する。 [Peeling method of adhesive sheet, manufacturing method of processed products]
A method for separating the pressure-sensitive adhesive sheet and the adherend adhered to the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer using the pressure-sensitive adhesive sheet described above will be described below with reference to FIG.
（１）貼着工程
まず、本実施形態の剥離方法に付すにあたり、図２（ａ）に示すように、被着体としてのワークＷを、粘着シート１が備える粘着剤層２の粘着面Ｐに、あらかじめ貼着する。 (1) Adhesion process First, when attaching | subjecting to the peeling method of this embodiment, as shown to Fig.2 (a), the adhesive surface P of theadhesive layer 2 with which the adhesive sheet 1 is equipped with the workpiece | work W as a to-be-adhered body. Adhere in advance.
まず、本実施形態の剥離方法に付すにあたり、図２（ａ）に示すように、被着体としてのワークＷを、粘着シート１が備える粘着剤層２の粘着面Ｐに、あらかじめ貼着する。 (1) Adhesion process First, when attaching | subjecting to the peeling method of this embodiment, as shown to Fig.2 (a), the adhesive surface P of the
本実施形態に係る剥離方法の対象となるワークＷとしては、例えば、半導体ウェハ、半導体パッケージ、多層基板、セラミックグリーンシート積層体、一括封止モジュール等の電子部材；液晶ディスプレイ部材、有機ＥＬディスプレイ部材、光学フィルター、偏光板、位相差板等の光学部材などが挙げられる。
Examples of the workpiece W to be subjected to the peeling method according to this embodiment include electronic members such as a semiconductor wafer, a semiconductor package, a multilayer substrate, a ceramic green sheet laminate, a batch sealing module; a liquid crystal display member, and an organic EL display member. And optical members such as an optical filter, a polarizing plate, and a retardation plate.
ワークＷと粘着シート１との貼着は、大気圧下で行ってもよく、後述する圧力制御装置１０により雰囲気圧力が制御されたチャンバー内で行ってもよい。ここで、貼着工程が行われる大気圧またはチャンバー内の雰囲気圧力は、その後の工程における気室３中の気体の圧力に相当し、かかる雰囲気圧力を適宜調整したうえで貼着工程を行うと、減圧処理における気体の膨張量を制御することが容易になる。
The attachment of the workpiece W and the pressure-sensitive adhesive sheet 1 may be performed under atmospheric pressure, or may be performed in a chamber in which the atmospheric pressure is controlled by the pressure control device 10 described later. Here, the atmospheric pressure in which the sticking process is performed or the atmospheric pressure in the chamber corresponds to the pressure of the gas in the air chamber 3 in the subsequent process, and the sticking process is performed after appropriately adjusting the atmospheric pressure. It becomes easy to control the amount of gas expansion in the decompression process.
（２）加工工程
貼着工程により粘着シート１に貼着されたワークＷは、粘着シート１に貼着された状態で、各種の加工工程に付すことができる（図２（ｂ））。加工工程の例としては、ワークＷが半導体ウェハであれば、バックグラインド工程、回路形成工程、ダイシング工程やダイソート工程等が挙げられ、ワークＷが表示装置構成部材であれば、積層工程や移送工程等が挙げられる。これら各種加工工程により、ワークＷは加工物Ｗ’に加工される。ここで、粘着シート１は、ワークＷの加工工程の後、後述するようにワークＷから剥離されるため、加工工程の間ワークＷを仮固定するために用いられるということができる。 (2) Processing process The workpiece | work W stuck on theadhesive sheet 1 by the sticking process can be attached | subjected to various processing processes in the state stuck on the adhesive sheet 1 (FIG.2 (b)). Examples of processing steps include a back grinding process, a circuit forming process, a dicing process, a die sort process, and the like if the work W is a semiconductor wafer, and a laminating process and a transfer process if the work W is a display device component. Etc. Through these various processing steps, the workpiece W is processed into a workpiece W ′. Here, since the adhesive sheet 1 is peeled from the workpiece W as described later after the processing step of the workpiece W, it can be said that it is used for temporarily fixing the workpiece W during the processing step.
貼着工程により粘着シート１に貼着されたワークＷは、粘着シート１に貼着された状態で、各種の加工工程に付すことができる（図２（ｂ））。加工工程の例としては、ワークＷが半導体ウェハであれば、バックグラインド工程、回路形成工程、ダイシング工程やダイソート工程等が挙げられ、ワークＷが表示装置構成部材であれば、積層工程や移送工程等が挙げられる。これら各種加工工程により、ワークＷは加工物Ｗ’に加工される。ここで、粘着シート１は、ワークＷの加工工程の後、後述するようにワークＷから剥離されるため、加工工程の間ワークＷを仮固定するために用いられるということができる。 (2) Processing process The workpiece | work W stuck on the
（３）剥離工程
次に、加工物Ｗ’が貼着された状態の粘着シート１を、圧力制御装置１０のチャンバー内に載置する（図２（ｃ））。ここで、後述する減圧処理において気室３を効果的に膨張させるため、加工物Ｗ’が貼着された状態の粘着シート１を、加工物Ｗ’が粘着シート１の下側となるように、チャンバー内に載置することが好ましい。ただし、加工物Ｗ’の重さが十分に小さい等（特に、加工物Ｗ’が粘着シート１よりも軽い場合）、減圧処理において気室３を膨張させることができる場合は、加工物Ｗ’が粘着シート１の上側となるように、チャンバー内に載置してもよい。 (3) Peeling process Next, theadhesive sheet 1 in a state where the workpiece W ′ is adhered is placed in the chamber of the pressure control device 10 (FIG. 2C). Here, in order to effectively expand the air chamber 3 in the decompression process to be described later, the pressure-sensitive adhesive sheet 1 in a state where the workpiece W ′ is adhered is placed so that the workpiece W ′ is on the lower side of the pressure-sensitive adhesive sheet 1. It is preferable to place in the chamber. However, when the weight of the workpiece W ′ is sufficiently small (particularly when the workpiece W ′ is lighter than the pressure-sensitive adhesive sheet 1), the workpiece W ′ can be expanded when the air chamber 3 can be expanded in the decompression process. It may be placed in the chamber so that is on the upper side of the adhesive sheet 1.
次に、加工物Ｗ’が貼着された状態の粘着シート１を、圧力制御装置１０のチャンバー内に載置する（図２（ｃ））。ここで、後述する減圧処理において気室３を効果的に膨張させるため、加工物Ｗ’が貼着された状態の粘着シート１を、加工物Ｗ’が粘着シート１の下側となるように、チャンバー内に載置することが好ましい。ただし、加工物Ｗ’の重さが十分に小さい等（特に、加工物Ｗ’が粘着シート１よりも軽い場合）、減圧処理において気室３を膨張させることができる場合は、加工物Ｗ’が粘着シート１の上側となるように、チャンバー内に載置してもよい。 (3) Peeling process Next, the
続いて、チャンバー内圧力を低下させる（減圧処理，図２（ｄ））。すると、気室３中の気体の圧力は、チャンバー内圧力に比べて相対的に高い状態となるため、かかる気室３中の気体が体積膨張することにより、粘着剤層２内において気室３を膨張させるような圧力が粘着剤層２に付与される。
Subsequently, the pressure in the chamber is reduced (decompression treatment, FIG. 2 (d)). Then, since the pressure of the gas in the air chamber 3 becomes relatively higher than the pressure in the chamber, the gas in the air chamber 3 expands in volume, and thus the air chamber 3 in the pressure-sensitive adhesive layer 2. Is applied to the pressure-sensitive adhesive layer 2.
上記減圧処理は、貼付環境の雰囲気圧力よりも低くすることが好ましく、チャンバー内の雰囲気圧力が貼付環境の雰囲気圧力よりも１０ｋＰａ以上の差を有するように低くすることがより好ましく、当該雰囲気圧力の差が３０ｋＰａ以上とすることがさらに好ましく、５０ｋＰａ以上とすることがよりさらに好ましく、８０ｋＰａ以上とすることがさらに好ましく、９０ｋＰａ以上とすることが特に好ましい。貼付環境の雰囲気圧力よりも低くなるように上記減圧処理を行うことにより、気室３中の気体をより効果的に膨張させることができる。なお、チャンバー内の圧力の下限値は特に限定されないが、技術的な観点から、通常は１０－７Ｐａ以上であり、好ましくは１０－５Ｐａ以上、より好ましくは１０－１Ｐａ以上、よりさらに好ましくは１０Ｐａ以上、よりさらに好ましくは１００Ｐａ以上、特に好ましくは１０００Ｐａ以上である。
The pressure reduction treatment is preferably lower than the atmospheric pressure of the pasting environment, more preferably lower so that the atmospheric pressure in the chamber has a difference of 10 kPa or more than the atmospheric pressure of the pasting environment. The difference is more preferably 30 kPa or more, still more preferably 50 kPa or more, further preferably 80 kPa or more, and particularly preferably 90 kPa or more. By performing the decompression process so as to be lower than the atmospheric pressure of the pasting environment, the gas in the air chamber 3 can be expanded more effectively. The lower limit value of the pressure in the chamber is not particularly limited, but is usually 10 −7 Pa or more, preferably 10 −5 Pa or more, more preferably 10 −1 Pa or more, and even more, from a technical viewpoint. Preferably it is 10 Pa or more, More preferably, it is 100 Pa or more, Especially preferably, it is 1000 Pa or more.
かかる減圧処理の結果、粘着剤層２が比較的軟質である場合には、図２（ｄ）に示されるように、気室３の膨張に追従して粘着面Ｐの一部に凸部が生じる。ここで、減圧による気室３の膨張に伴い、複数の気室３どうしが連通して、より大きな気室３を形成する場合もある。より大きな気室３が形成されると、減圧による膨張の効果がより顕著になるため、好ましい。また、粘着面Ｐの近傍の気室３が膨張した場合は、粘着面Ｐ上に表出し、気室３であった部分が粘着面Ｐの凹部になる場合もある。このような結果、粘着面Ｐに凹凸が形成される。これにより、粘着剤層２と加工物Ｗ’との接着面積が減少し、粘着シート１の加工物Ｗ’に対する粘着力が低下するものと考えられる。これにより、粘着剤の縦方向へ基材を押し上げる力が、被着体との粘着力を上回る場合、その箇所から粘着剤層２は加工物Ｗ’から一部または全て剥離する（図２（ｅ））。
If the pressure-sensitive adhesive layer 2 is relatively soft as a result of the decompression process, a convex portion is formed on a part of the pressure-sensitive adhesive surface P following the expansion of the air chamber 3 as shown in FIG. Arise. Here, with the expansion of the air chamber 3 due to decompression, the plurality of air chambers 3 may communicate with each other to form a larger air chamber 3. It is preferable to form a larger air chamber 3 because the expansion effect due to the reduced pressure becomes more remarkable. Further, when the air chamber 3 in the vicinity of the adhesive surface P expands, it may be exposed on the adhesive surface P, and the portion that was the air chamber 3 may become a concave portion of the adhesive surface P. As a result, irregularities are formed on the adhesive surface P. Thereby, it is considered that the adhesive area between the pressure-sensitive adhesive layer 2 and the workpiece W ′ decreases, and the adhesive force of the pressure-sensitive adhesive sheet 1 to the workpiece W ′ decreases. Thereby, when the force which pushes up a base material to the vertical direction of an adhesive exceeds the adhesive force with a to-be-adhered body, the adhesive layer 2 peels a part or all from the workpiece W 'from the location (FIG. 2 ( e)).
一方、粘着剤層２が比較的硬質である場合には、図２（ｄ）に示すような気室３の膨張および粘着面Ｐの変形がほとんど認められない状態で、粘着シート１の加工物Ｗ’に対する粘着力が低下し、図２（ｅ）に示すように粘着剤層２が加工物Ｗ’から剥離する場合もある。これは、粘着剤が比較的硬質であることにより、粘着剤の膨張よりも粘着剤の縦方向へ基材を押し上げる力が優先されるためであると考えられる。
On the other hand, when the pressure-sensitive adhesive layer 2 is relatively hard, the processed product of the pressure-sensitive adhesive sheet 1 with almost no expansion of the air chamber 3 and deformation of the pressure-sensitive adhesive surface P as shown in FIG. In some cases, the adhesive strength to W ′ decreases, and the adhesive layer 2 peels from the workpiece W ′ as shown in FIG. This is considered to be because the force that pushes up the base material in the longitudinal direction of the adhesive is prioritized over the expansion of the adhesive because the adhesive is relatively hard.
以上のようにして、粘着剤層２の加工物Ｗ’への粘着力が低下することにより、粘着シート１と加工物Ｗ’とを容易に剥離させることができる。ここで、粘着シート１と加工物Ｗ’とは、図２（ｅ）の状態でそのまま剥離させることもできるし、例えば、加工物Ｗ’が粘着シート１の上側となるようにチャンバー内に載置して減圧した場合は、減圧したチャンバー内で加工物Ｗ’と粘着シート１とを１８０°反転させることで、加工物Ｗ’の自重により粘着シート１と加工物Ｗ’とを剥離させることもできる。
As described above, the pressure-sensitive adhesive sheet 1 and the workpiece W ′ can be easily peeled off by decreasing the adhesive force of the pressure-sensitive adhesive layer 2 to the workpiece W ′. Here, the pressure-sensitive adhesive sheet 1 and the workpiece W ′ can be peeled as they are in the state shown in FIG. 2E. For example, the pressure-sensitive adhesive sheet 1 is placed in the chamber so that the workpiece W ′ is on the upper side of the pressure-sensitive adhesive sheet 1. When the pressure is reduced by placing the workpiece W ′ and the pressure-sensitive adhesive sheet 1 in 180 ° in a reduced pressure chamber, the pressure-sensitive adhesive sheet 1 and the workpiece W ′ are peeled off by the weight of the workpiece W ′. You can also.
また、粘着剤層２を形成する粘着剤組成物が活性エネルギー線硬化性または熱硬化性を有する場合は、前述した加工工程の後であって、減圧処理の前または後に、活性エネルギー線照射または加熱により、粘着剤層２を硬化させることが好ましい。ここで、減圧処理の前に粘着剤層２を硬化させる場合、減圧処理の段階で粘着剤層２が比較的硬質となっているため、前述したとおり、気室３の膨張および粘着面Ｐの凹凸形成がほとんど起こらずに、粘着剤層２と加工物Ｗ’と粘着力を低下させることができる。一方、減圧処理の後に粘着剤層２を硬化させると、減圧処理の段階では粘着剤層２は比較的軟質であるため、気室３の膨張および粘着面Ｐの凹凸形成（図２（ｄ））がなされた後、粘着剤層２を硬化させることでさらに粘着力を低下させることができ、やはり粘着剤層２と加工物Ｗ’との剥離が容易になる。
なお、本明細書において粘着剤の「硬化」とは、粘着シート１を被着体（ワークＷ，加工物Ｗ’）に貼着したのちに行われる反応をいう。そのため、例えば前述した粘着剤の「架橋」とは明確に区別される。 Further, when the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer 2 has active energy ray curable or thermosetting property, the active energy ray irradiation or after the above-described processing step and before or after the decompression treatment. It is preferable to cure the pressure-sensitive adhesive layer 2 by heating. Here, when the pressure-sensitive adhesive layer 2 is cured before the pressure reduction treatment, the pressure-sensitive adhesive layer 2 is relatively hard at the stage of the pressure reduction treatment. The pressure-sensitive adhesive layer 2, the workpiece W ′, and the adhesive force can be reduced with almost no unevenness formation. On the other hand, when the pressure-sensitive adhesive layer 2 is cured after the pressure reduction treatment, the pressure-sensitive adhesive layer 2 is relatively soft at the stage of the pressure reduction treatment, so that the expansion of the air chamber 3 and the formation of irregularities on the pressure-sensitive adhesive surface P (FIG. 2D) ), The pressure-sensitive adhesive force can be further reduced by curing the pressure-sensitive adhesive layer 2, and the pressure-sensitive adhesive layer 2 and the workpiece W ′ can be easily separated from each other.
In this specification, “curing” of the pressure-sensitive adhesive refers to a reaction performed after the pressure-sensitive adhesive sheet 1 is adhered to an adherend (work W, workpiece W ′). Therefore, for example, it is clearly distinguished from the above-mentioned “crosslinking” of the pressure-sensitive adhesive.
なお、本明細書において粘着剤の「硬化」とは、粘着シート１を被着体（ワークＷ，加工物Ｗ’）に貼着したのちに行われる反応をいう。そのため、例えば前述した粘着剤の「架橋」とは明確に区別される。 Further, when the pressure-sensitive adhesive composition forming the pressure-
In this specification, “curing” of the pressure-sensitive adhesive refers to a reaction performed after the pressure-
粘着剤組成物が活性エネルギー線硬化性を有する場合、粘着剤組成物を硬化させるための活性エネルギー線としては、電離放射線、すなわち、紫外線、Ｘ線、電子線などが挙げられる。これらのうちでも、比較的照射設備の導入の容易な紫外線が好ましい。
When the pressure-sensitive adhesive composition has active energy ray curability, examples of the active energy ray for curing the pressure-sensitive adhesive composition include ionizing radiation, that is, ultraviolet rays, X-rays, and electron beams. Among these, ultraviolet rays that are relatively easy to introduce irradiation equipment are preferable.
電離放射線として紫外線を用いる場合には、取り扱いの容易さから波長２００～３８０ｎｍ程度の紫外線を含む近紫外線を用いればよい。光量としては、活性エネルギー線硬化性粘着剤組成物が有する活性エネルギー線硬化性基の種類や粘着剤層２の厚さに応じて適宜選択すればよく、通常５０～１５００ｍＪ／ｃｍ２程度であり、２００～１０００ｍＪ／ｃｍ２が好ましく、３００～８００ｍＪ／ｃｍ２がより好ましい。また、紫外線照度は、通常５０～１５００ｍＷ／ｃｍ２程度であり、２００～１０００ｍＷ／ｃｍ２が好ましく、３００～８００ｍＷ／ｃｍ２がより好ましい。紫外線源としては特に制限はなく、例えば無電極ランプ、高圧水銀ランプ、メタルハライドランプ、ＵＶ－ＬＥＤなどが用いられる。
When ultraviolet rays are used as the ionizing radiation, near ultraviolet rays including ultraviolet rays having a wavelength of about 200 to 380 nm may be used for ease of handling. The amount of light may be appropriately selected according to the type of active energy ray-curable group possessed by the active energy ray-curable pressure-sensitive adhesive composition and the thickness of the pressure-sensitive adhesive layer 2, and is usually about 50 to 1500 mJ / cm 2 . 200 to 1000 mJ / cm 2 is preferable, and 300 to 800 mJ / cm 2 is more preferable. The ultraviolet illumination is usually 50 ~ 1500mW / cm 2 or so, preferably 200 ~ 1000mW / cm 2, more preferably 300 ~ 800mW / cm 2. The ultraviolet light source is not particularly limited, and for example, an electrodeless lamp, a high-pressure mercury lamp, a metal halide lamp, a UV-LED, or the like is used.
電離放射線として電子線を用いる場合には、その加速電圧については、活性エネルギー線硬化性粘着剤組成物が有する活性エネルギー線硬化性基の種類や粘着剤層２の厚さに応じて適宜選定すればよく、通常加速電圧１０～１０００ｋＶ程度であることが好ましい。また、照射線量は、活性エネルギー線硬化性粘着剤組成物が適切に硬化する範囲に設定すればよく、通常１０～１０００ｋｒａｄの範囲で選定される。電子線源としては、特に制限はなく、例えばコッククロフトワルトン型、バンデグラフ型、共振変圧器型、絶縁コア変圧器型、あるいは直線型、ダイナミトロン型、高周波型などの各種電子線加速器を用いることができる。
When an electron beam is used as the ionizing radiation, the acceleration voltage is appropriately selected according to the type of active energy ray-curable group possessed by the active energy ray-curable adhesive composition and the thickness of the adhesive layer 2. Usually, the acceleration voltage is preferably about 10 to 1000 kV. The irradiation dose may be set within a range where the active energy ray-curable pressure-sensitive adhesive composition is appropriately cured, and is usually selected within a range of 10 to 1000 krad. The electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockcroft Walton type, a bandegraph type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type may be used. it can.
粘着剤組成物を効果的に硬化させる観点から、これらの活性エネルギー線は、粘着シート１における粘着面Ｐ（加工物Ｗ’が貼着された面）とは反対の面側から照射することが好ましい。
From the viewpoint of effectively curing the pressure-sensitive adhesive composition, these active energy rays may be irradiated from the surface opposite to the pressure-sensitive adhesive surface P (the surface on which the workpiece W ′ is adhered) in the pressure-sensitive adhesive sheet 1. preferable.
一方、粘着剤組成物が熱硬化性を有する場合、粘着剤組成物を硬化させるための加熱手段としては、例えば、ホットプレート、熱風乾燥機、近赤外線ランプなどの適当な手段を採用することができる。加熱条件は、粘着剤層２の熱硬化に要する加熱温度、所望の剥離性、ワークＷや加工物Ｗ’等の耐熱性、加熱手段等により適宜設定される。一般的な加熱条件として、例えばホットプレートを用いる場合、温度８０～２５０℃、加熱時間５秒～６０秒間等が例示される。
On the other hand, when the pressure-sensitive adhesive composition has thermosetting properties, as a heating means for curing the pressure-sensitive adhesive composition, for example, an appropriate means such as a hot plate, a hot air dryer, or a near infrared lamp can be adopted. it can. The heating conditions are appropriately set depending on the heating temperature required for the thermosetting of the pressure-sensitive adhesive layer 2, the desired peelability, the heat resistance of the workpiece W and the workpiece W ', the heating means, and the like. As general heating conditions, for example, when a hot plate is used, a temperature of 80 to 250 ° C., a heating time of 5 seconds to 60 seconds, and the like are exemplified.
以上述べた本実施形態に係る粘着シートの剥離方法によれば、粘着シート１の粘着剤層２がその内部に気室３を有し、かかる気室３中の気体を膨張させる減圧処理により、粘着シート１の被着体への粘着力を低下させる。かかる方法によれば、減圧処理により気体を膨張させるとの新規な作用機構により、所望のタイミングで粘着力を低下させることができ、これにより粘着シートと被着体との剥離を容易にすることができる。
According to the pressure-sensitive adhesive sheet peeling method according to the present embodiment described above, the pressure-sensitive adhesive layer 2 of the pressure-sensitive adhesive sheet 1 has an air chamber 3 therein, and a decompression process for expanding the gas in the air chamber 3, The adhesive force to the adherend of the adhesive sheet 1 is reduced. According to such a method, the adhesive force can be reduced at a desired timing by a novel mechanism of expanding the gas by the decompression process, thereby facilitating the peeling between the adhesive sheet and the adherend. Can do.
ここで、活性エネルギー線硬化性または熱硬化性のみを利用して粘着剤層２の粘着力を低下させる場合は、硬化反応（すなわち化学反応）を十分に進行させるため、材料の選択が限定されてしまう。しかし、本実施形態によれば、減圧処理による気体の膨張により粘着力を低下させることができるため、活性エネルギー線硬化性もしくは熱硬化性を全く利用しないか、部分的に利用すればよいこととなるため、粘着剤層２を構成する材料の自由度を大きいものとすることができる。また、熱硬化性を利用して粘着剤層２の粘着力を低下させる場合は、ワークＷの加工工程の中に加熱する工程が含まれていると、粘着剤層２の粘着力が低下し加工工程中のワークＷの仮固定が十分に行えないおそれがあるが、本実施形態においては、熱硬化性を全く利用しないか、または部分的にのみ利用すればよいため、ワークＷの加工工程の中に加熱工程が含まれる場合であっても、ワークＷを十分に仮固定することができる。
Here, when the adhesive force of the pressure-sensitive adhesive layer 2 is reduced using only active energy ray curable or thermosetting, the selection of materials is limited because the curing reaction (that is, chemical reaction) is sufficiently advanced. End up. However, according to the present embodiment, the adhesive force can be reduced by the expansion of the gas due to the decompression process, so that the active energy ray curable property or thermosetting property is not used at all or only partially used. Therefore, the freedom degree of the material which comprises the adhesive layer 2 can be made large. Moreover, when reducing the adhesive strength of the adhesive layer 2 using thermosetting, if the process of heating the workpiece W is included, the adhesive strength of the adhesive layer 2 decreases. Although there is a possibility that the temporary fixing of the workpiece W during the processing step may not be sufficiently performed, in the present embodiment, the thermosetting property is not used at all or only partially used. Even if a heating process is included in the workpiece, the workpiece W can be sufficiently temporarily fixed.
以上説明した実施形態は、本発明の理解を容易にするために記載されたものであって、本発明を限定するために記載されたものではない。したがって、上記実施形態に開示された各要素は、本発明の技術的範囲に属する全ての設計変更、均等物および均等方法をも含む趣旨である。
The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes, equivalents, and equivalent methods belonging to the technical scope of the present invention.
例えば、上記粘着シート１における基材４と粘着剤層２との間には、他の層が介在していてもよい。
For example, another layer may be interposed between the base material 4 and the pressure-sensitive adhesive layer 2 in the pressure-sensitive adhesive sheet 1.
また、別の実施形態においては、粘着シートは、基材を備えず、粘着剤層のみからなる両面粘着シートであってもよい。例えば、他の一実施形態においては、第１の粘着面および第２の粘着面を有する両面粘着シートと、第１の粘着面に貼着された第１の被着体とを剥離する方法とすることができる。第２の粘着面には、例えば、第２の被着体が貼着されていてもよい。この場合において、前述した実施形態と同様に、粘着剤層の内部には気室が形成されている。かかる粘着剤層のみからなる粘着シートと、第１の被着体（および第２の被着体）とに対し減圧処理を行うことにより、気室中の気体が膨張し、第１の被着体（および第２の被着体）に対する両面粘着シートの粘着力が低下することにより、第１の被着体と粘着シートとを剥離させることができる。
In another embodiment, the pressure-sensitive adhesive sheet may be a double-sided pressure-sensitive adhesive sheet comprising only a pressure-sensitive adhesive layer without a base material. For example, in another embodiment, a method of peeling a double-sided pressure-sensitive adhesive sheet having a first pressure-sensitive adhesive surface and a second pressure-sensitive adhesive surface, and a first adherend adhered to the first pressure-sensitive adhesive surface; can do. For example, a second adherend may be attached to the second adhesive surface. In this case, as in the above-described embodiment, an air chamber is formed inside the pressure-sensitive adhesive layer. By subjecting the pressure-sensitive adhesive sheet consisting only of the pressure-sensitive adhesive layer and the first adherend (and the second adherend) to a decompression process, the gas in the air chamber expands, and the first adherend When the adhesive force of the double-sided pressure-sensitive adhesive sheet to the body (and the second adherend) decreases, the first adherend and the pressure-sensitive adhesive sheet can be peeled off.
以下、実施例等により本発明をさらに具体的に説明するが、本発明の範囲はこれらの実施例等に限定されるものではない。
Hereinafter, the present invention will be described more specifically with reference to examples and the like, but the scope of the present invention is not limited to these examples and the like.
〔製造例１〕
ブチルアクリレート（ＢＡ）９０質量部、アクリル酸（ＡＡｃ）１０質量部を共重合してなるアクリル酸エステル共重合体（質量平均分子量：４７万，溶媒：酢酸エチルとトルエンの混合溶剤，ガラス転移温度：－３４℃，固形分濃度３０質量％）１００質量部（固形分）と、イソシアネート系架橋剤（東ソー株式会社製，製品名「コロネートＬ」）０．１質量部（固形分）とを混合し、割り箸による強撹拌により意図的に気泡を混入させて、粘着剤（１）を調製した。 [Production Example 1]
Acrylate ester copolymer obtained by copolymerizing 90 parts by mass of butyl acrylate (BA) and 10 parts by mass of acrylic acid (AAc) (mass average molecular weight: 470,000, solvent: mixed solvent of ethyl acetate and toluene, glass transition temperature : -34 ° C., solid content concentration of 30% by mass) 100 parts by mass (solid content) and 0.1 part by mass (solid content) of an isocyanate-based crosslinking agent (product name “Coronate L” manufactured by Tosoh Corporation) Then, bubbles were intentionally mixed by vigorous stirring with the split chopsticks to prepare the adhesive (1).
ブチルアクリレート（ＢＡ）９０質量部、アクリル酸（ＡＡｃ）１０質量部を共重合してなるアクリル酸エステル共重合体（質量平均分子量：４７万，溶媒：酢酸エチルとトルエンの混合溶剤，ガラス転移温度：－３４℃，固形分濃度３０質量％）１００質量部（固形分）と、イソシアネート系架橋剤（東ソー株式会社製，製品名「コロネートＬ」）０．１質量部（固形分）とを混合し、割り箸による強撹拌により意図的に気泡を混入させて、粘着剤（１）を調製した。 [Production Example 1]
Acrylate ester copolymer obtained by copolymerizing 90 parts by mass of butyl acrylate (BA) and 10 parts by mass of acrylic acid (AAc) (mass average molecular weight: 470,000, solvent: mixed solvent of ethyl acetate and toluene, glass transition temperature : -34 ° C., solid content concentration of 30% by mass) 100 parts by mass (solid content) and 0.1 part by mass (solid content) of an isocyanate-based crosslinking agent (product name “Coronate L” manufactured by Tosoh Corporation) Then, bubbles were intentionally mixed by vigorous stirring with the split chopsticks to prepare the adhesive (1).
剥離シート（リンテック株式会社製，製品名「ＳＰ－ＰＥＴ３８１０３１」，厚さ３８μｍ，ポリエチレンテレフタレートフィルムにシリコーン系剥離剤を積層させたもの）の剥離処理面に、上記（１）で調製した粘着剤（１）をアプリケータで塗布し、１００℃で１分間乾燥させて粘着剤層を形成した。乾燥後の粘着剤層の厚さは２５μｍであった。得られた粘着剤層に、基材としてポリエチレンテレフタレートフィルム（東レ株式会社製，製品名「ルミラー Ｔ－６０」，厚さ５０μｍ）を貼り合わせ、その後、２３℃、相対湿度５０％の条件下で７日間シーズニングして、これを粘着シートとした。
得られた粘着シートについて、基材側よりデジタル顕微鏡にて観察し、粘着剤層における気室の平均直径および体積割合を測定した。気室の平均直径は２１μｍであった。また、粘着剤層に占める気室の体積割合は２．１％であった。 The pressure-sensitive adhesive prepared in (1) above was applied to the release-treated surface of a release sheet (product of Lintec Co., Ltd., product name “SP-PET381031”, thickness 38 μm, polyethylene terephthalate film laminated with a silicone release agent). 1) was applied with an applicator and dried at 100 ° C. for 1 minute to form an adhesive layer. The thickness of the pressure-sensitive adhesive layer after drying was 25 μm. A polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name “Lumirror T-60”, thickness 50 μm) is bonded to the obtained pressure-sensitive adhesive layer, and then, under conditions of 23 ° C. and relative humidity 50%. This was seasoned for 7 days and used as an adhesive sheet.
About the obtained adhesive sheet, it observed with the digital microscope from the base material side, and measured the average diameter and volume ratio of the air chamber in an adhesive layer. The average diameter of the air chamber was 21 μm. Moreover, the volume ratio of the air chamber which occupies for an adhesive layer was 2.1%.
得られた粘着シートについて、基材側よりデジタル顕微鏡にて観察し、粘着剤層における気室の平均直径および体積割合を測定した。気室の平均直径は２１μｍであった。また、粘着剤層に占める気室の体積割合は２．１％であった。 The pressure-sensitive adhesive prepared in (1) above was applied to the release-treated surface of a release sheet (product of Lintec Co., Ltd., product name “SP-PET381031”, thickness 38 μm, polyethylene terephthalate film laminated with a silicone release agent). 1) was applied with an applicator and dried at 100 ° C. for 1 minute to form an adhesive layer. The thickness of the pressure-sensitive adhesive layer after drying was 25 μm. A polyethylene terephthalate film (manufactured by Toray Industries, Inc., product name “Lumirror T-60”, thickness 50 μm) is bonded to the obtained pressure-sensitive adhesive layer, and then, under conditions of 23 ° C. and relative humidity 50%. This was seasoned for 7 days and used as an adhesive sheet.
About the obtained adhesive sheet, it observed with the digital microscope from the base material side, and measured the average diameter and volume ratio of the air chamber in an adhesive layer. The average diameter of the air chamber was 21 μm. Moreover, the volume ratio of the air chamber which occupies for an adhesive layer was 2.1%.
〔製造例２〕
ブチルアクリレート（ＢＡ）８０質量部、アクリル酸（ＡＡｃ）２０質量部を共重合してなるアクリル酸エステル共重合体に、メタクリロイルオキシエチルイソシアネート（ＭＯＩ）を（メタ）アクリル酸エステル共重合体のカルボキシル基１００当量に対して３０当量を添加して反応させ、エネルギー線硬化型アクリル酸エステル共重合体（質量平均分子量：６０万，溶媒：酢酸エチルとトルエンとＭＥＫの混合溶剤，ガラス転移温度：－３４℃，固形分濃度３０質量％）を得た。 [Production Example 2]
An acrylic acid ester copolymer obtained by copolymerizing 80 parts by mass of butyl acrylate (BA) and 20 parts by mass of acrylic acid (AAc) is mixed with methacryloyloxyethyl isocyanate (MOI) as a carboxyl of (meth) acrylic acid ester copolymer. 30 equivalents were added to react with 100 equivalents of the group, and the energy ray curable acrylate copolymer (mass average molecular weight: 600,000, solvent: mixed solvent of ethyl acetate, toluene and MEK, glass transition temperature:- 34 ° C., solid content concentration of 30% by mass).
ブチルアクリレート（ＢＡ）８０質量部、アクリル酸（ＡＡｃ）２０質量部を共重合してなるアクリル酸エステル共重合体に、メタクリロイルオキシエチルイソシアネート（ＭＯＩ）を（メタ）アクリル酸エステル共重合体のカルボキシル基１００当量に対して３０当量を添加して反応させ、エネルギー線硬化型アクリル酸エステル共重合体（質量平均分子量：６０万，溶媒：酢酸エチルとトルエンとＭＥＫの混合溶剤，ガラス転移温度：－３４℃，固形分濃度３０質量％）を得た。 [Production Example 2]
An acrylic acid ester copolymer obtained by copolymerizing 80 parts by mass of butyl acrylate (BA) and 20 parts by mass of acrylic acid (AAc) is mixed with methacryloyloxyethyl isocyanate (MOI) as a carboxyl of (meth) acrylic acid ester copolymer. 30 equivalents were added to react with 100 equivalents of the group, and the energy ray curable acrylate copolymer (mass average molecular weight: 600,000, solvent: mixed solvent of ethyl acetate, toluene and MEK, glass transition temperature:- 34 ° C., solid content concentration of 30% by mass).
前述のエネルギー線硬化型アクリル酸エステル共重合体１００質量部（固形分）と、エネルギー線重合性基含有オリゴマーとして、エネルギー線硬化型アクリレート系多官能モノマーおよびオリゴマーからなる組成物（日本化薬株式会社製，製品名「ＫＡＹＡＲＡＤ ＮＫＲ－００１」）８０質量部（固形分）およびエネルギー線硬化型ウレタンアクリレート系オリゴマー（日本合成化学工業株式会社製，製品名「ＵＶ－３２１０ＥＡ」，質量平均分子量：９０００，ガラス転移温度：－２７℃）２０質量部（固形分）と、イソシアネート系架橋剤（東ソー株式会社製，製品名「コロネートＬ」）０．１質量部（固形分）と、光重合開始剤として１－ヒドロキシ－シクロヘキシル－フェニル－ケトン（チバスペシャリティーケミカルズ社製，製品名「イルガキュア１８４」）３．０質量部（固形分）とを混合し、割り箸による強撹拌により意図的に気泡を混入させて、粘着剤（２）を調製した。
Composition comprising 100 parts by mass (solid content) of the above-mentioned energy beam curable acrylic ester copolymer and energy beam curable acrylate polyfunctional monomer and oligomer as an energy beam polymerizable group-containing oligomer (Nippon Kayaku Co., Ltd.) 80 parts by mass (solid name) manufactured by company, product name “KAYARAD NKR-001” and energy ray curable urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., product name “UV-3210EA”, mass average molecular weight: 9000 , Glass transition temperature: −27 ° C.) 20 parts by mass (solid content), isocyanate-based crosslinking agent (product name “Coronate L” manufactured by Tosoh Corporation), 0.1 part by mass (solid content), and photopolymerization initiator 1-Hydroxy-cyclohexyl-phenyl-ketone (Ciba Specialty Chemicals) Mixed product name "Irgacure 184") 3.0 parts by mass and (solids), intentionally by mixing air bubbles with vigorous stirring by chopsticks, pressure-sensitive adhesive (2) was prepared.
得られた粘着剤（２）を、粘着剤（１）に替えて用いた以外は、製造例１と同様にして粘着シートを製造した。
得られた粘着シートについて、製造例１の粘着シートと同様に気室の平均直径および体積割合を測定した。気室の平均直径は１８μｍであった。また、粘着剤層に占める気室の体積割合は１．６％であった。 A pressure-sensitive adhesive sheet was produced in the same manner as in Production Example 1 except that the obtained pressure-sensitive adhesive (2) was used in place of the pressure-sensitive adhesive (1).
About the obtained adhesive sheet, the average diameter and volume ratio of the air chamber were measured in the same manner as the adhesive sheet of Production Example 1. The average diameter of the air chamber was 18 μm. Moreover, the volume ratio of the air chamber which occupies for an adhesive layer was 1.6%.
得られた粘着シートについて、製造例１の粘着シートと同様に気室の平均直径および体積割合を測定した。気室の平均直径は１８μｍであった。また、粘着剤層に占める気室の体積割合は１．６％であった。 A pressure-sensitive adhesive sheet was produced in the same manner as in Production Example 1 except that the obtained pressure-sensitive adhesive (2) was used in place of the pressure-sensitive adhesive (1).
About the obtained adhesive sheet, the average diameter and volume ratio of the air chamber were measured in the same manner as the adhesive sheet of Production Example 1. The average diameter of the air chamber was 18 μm. Moreover, the volume ratio of the air chamber which occupies for an adhesive layer was 1.6%.
〔製造例３〕
製造例１における粘着剤の調製において、最後の割り箸による強撹拌に替えて、割り箸による通常の撹拌を行った後に目視で気泡が消失するまで静置させて、粘着剤（３）を調製した。得られた粘着剤（３）を、粘着剤（１）に替えて用いた以外は、製造例１と同様にして粘着シートを製造した。
得られた粘着シートについて、製造例１の粘着シートと同様に、粘着剤層における気室を基材側よりデジタル顕微鏡にて観察したが、直径０．１μｍ以上の気室は認められなかった。 [Production Example 3]
In the preparation of the pressure-sensitive adhesive in Production Example 1, instead of the strong stirring with the last chopsticks, after normal stirring with the chopping chopsticks, the pressure-sensitive adhesive (3) was prepared by standing until the bubbles disappeared visually. A pressure-sensitive adhesive sheet was produced in the same manner as in Production Example 1 except that the obtained pressure-sensitive adhesive (3) was used in place of the pressure-sensitive adhesive (1).
About the obtained adhesive sheet, the air chamber in an adhesive layer was observed with the digital microscope from the base material side similarly to the adhesive sheet of manufacture example 1, but the air chamber of diameter 0.1 micrometer or more was not recognized.
製造例１における粘着剤の調製において、最後の割り箸による強撹拌に替えて、割り箸による通常の撹拌を行った後に目視で気泡が消失するまで静置させて、粘着剤（３）を調製した。得られた粘着剤（３）を、粘着剤（１）に替えて用いた以外は、製造例１と同様にして粘着シートを製造した。
得られた粘着シートについて、製造例１の粘着シートと同様に、粘着剤層における気室を基材側よりデジタル顕微鏡にて観察したが、直径０．１μｍ以上の気室は認められなかった。 [Production Example 3]
In the preparation of the pressure-sensitive adhesive in Production Example 1, instead of the strong stirring with the last chopsticks, after normal stirring with the chopping chopsticks, the pressure-sensitive adhesive (3) was prepared by standing until the bubbles disappeared visually. A pressure-sensitive adhesive sheet was produced in the same manner as in Production Example 1 except that the obtained pressure-sensitive adhesive (3) was used in place of the pressure-sensitive adhesive (1).
About the obtained adhesive sheet, the air chamber in an adhesive layer was observed with the digital microscope from the base material side similarly to the adhesive sheet of manufacture example 1, but the air chamber of diameter 0.1 micrometer or more was not recognized.
ここで、ポリスチレン換算重量平均分子量は、ゲル浸透クロマトグラフ装置（東ソー株式会社製，製品名「ＨＬＣ－８０２０」）を用い、下記条件にて測定（ＧＰＣ測定）した標準ポリスチレン換算値である。
Here, the polystyrene equivalent weight average molecular weight is a standard polystyrene equivalent value measured (GPC measurement) under the following conditions using a gel permeation chromatograph (manufactured by Tosoh Corporation, product name “HLC-8020”).
＜ＧＰＣ測定条件＞
・カラム ：「ＴＳＫ ｇｕａｒｄ ｃｏｌｕｍｎ ＨＸＬ－Ｌ」、「ＴＳＫ ｇｅｌ Ｇ２５００ＨＸＬ」、「ＴＳＫ ｇｅｌ Ｇ２０００ＨＸＬ」、「ＴＳＫ ｇｅｌ Ｇ１０００ＨＸＬ」（いずれも東ソー株式会社製）を順次連結したもの
・カラム温度：４０℃
・展開溶媒 ：テトラヒドロフラン
・流速 ：１．０ｍＬ／ｍｉｎ
・検出器 ：示差屈折計
・標準試料 ：ポリスチレン <GPC measurement conditions>
Column: “TSK guard column HXL-L”, “TSK gel G2500HXL”, “TSK gel G2000HXL”, “TSK gel G1000HXL” (all manufactured by Tosoh Corporation) • Column temperature: 40 ° C.
・ Developing solvent: Tetrahydrofuran ・ Flow rate: 1.0 mL / min
・ Detector: Differential refractometer ・ Standard sample: Polystyrene
・カラム ：「ＴＳＫ ｇｕａｒｄ ｃｏｌｕｍｎ ＨＸＬ－Ｌ」、「ＴＳＫ ｇｅｌ Ｇ２５００ＨＸＬ」、「ＴＳＫ ｇｅｌ Ｇ２０００ＨＸＬ」、「ＴＳＫ ｇｅｌ Ｇ１０００ＨＸＬ」（いずれも東ソー株式会社製）を順次連結したもの
・カラム温度：４０℃
・展開溶媒 ：テトラヒドロフラン
・流速 ：１．０ｍＬ／ｍｉｎ
・検出器 ：示差屈折計
・標準試料 ：ポリスチレン <GPC measurement conditions>
Column: “TSK guard column HXL-L”, “TSK gel G2500HXL”, “TSK gel G2000HXL”, “TSK gel G1000HXL” (all manufactured by Tosoh Corporation) • Column temperature: 40 ° C.
・ Developing solvent: Tetrahydrofuran ・ Flow rate: 1.0 mL / min
・ Detector: Differential refractometer ・ Standard sample: Polystyrene
＜粘着力の測定＞
（１）減圧前粘着力の測定（実施例１～２，比較例１）
各製造例で得られた粘着シートを縦２５ｍｍ×横３００ｍｍの大きさに切断した後、２３℃、５０％ＲＨ（相対湿度）の環境下で、ガラス板（日本板硝子株式会社製，ソーダライムガラス，縦１５０ｍｍ×横７０ｍｍ×厚さ２ｍｍ）に貼付し、同じ環境下で２４時間静置した。静置後、ＪＩＳ Ｚ０２３７：２０００に基づき、１８０°引き剥がし法により、引っ張り速度３００ｍｍ／分にて、各粘着シートの粘着力を測定し、得られた値を減圧前粘着力とした。測定結果を表１に示す。 <Measurement of adhesive strength>
(1) Measurement of adhesive strength before decompression (Examples 1 and 2, Comparative Example 1)
After the pressure-sensitive adhesive sheet obtained in each production example was cut into a size of 25 mm in length and 300 mm in width, a glass plate (manufactured by Nippon Sheet Glass Co., Ltd., soda lime glass) in an environment of 23 ° C. and 50% RH (relative humidity) , Length 150 mm × width 70 mm ×thickness 2 mm) and allowed to stand for 24 hours in the same environment. After standing, based on JIS Z0237: 2000, the adhesive strength of each pressure-sensitive adhesive sheet was measured at a pulling speed of 300 mm / min by a 180 ° peeling method, and the obtained value was defined as the adhesive strength before decompression. The measurement results are shown in Table 1.
（１）減圧前粘着力の測定（実施例１～２，比較例１）
各製造例で得られた粘着シートを縦２５ｍｍ×横３００ｍｍの大きさに切断した後、２３℃、５０％ＲＨ（相対湿度）の環境下で、ガラス板（日本板硝子株式会社製，ソーダライムガラス，縦１５０ｍｍ×横７０ｍｍ×厚さ２ｍｍ）に貼付し、同じ環境下で２４時間静置した。静置後、ＪＩＳ Ｚ０２３７：２０００に基づき、１８０°引き剥がし法により、引っ張り速度３００ｍｍ／分にて、各粘着シートの粘着力を測定し、得られた値を減圧前粘着力とした。測定結果を表１に示す。 <Measurement of adhesive strength>
(1) Measurement of adhesive strength before decompression (Examples 1 and 2, Comparative Example 1)
After the pressure-sensitive adhesive sheet obtained in each production example was cut into a size of 25 mm in length and 300 mm in width, a glass plate (manufactured by Nippon Sheet Glass Co., Ltd., soda lime glass) in an environment of 23 ° C. and 50% RH (relative humidity) , Length 150 mm × width 70 mm ×
（２）減圧後粘着力の測定（実施例１～２，比較例１）
また、各実施例で得られた粘着シートを縦２５ｍｍ×横３００ｍｍの大きさに切断した後、２３℃、５０％ＲＨ（相対湿度）の環境下で、ガラス板（日本板硝子株式会社製，ソーダライムガラス，縦１５０ｍｍ×横７０ｍｍ×厚さ２ｍｍ）に貼付し、同じ環境下で２４時間静置した。静置後、石英ガラス製のチャンバーの中に静置し、チャンバーとホースで接続した減圧器を用いて、チャンバー内の雰囲気圧力が２ｋＰａになるまで減圧して１０秒間保持した後、減圧状態を開放して、チャンバーから粘着シートとガラス板を取り出して、ＪＩＳ Ｚ０２３７：２０００に基づき、１８０°引き剥がし法により、引っ張り速度３００ｍｍ／分にて、各粘着シートの粘着力を測定した。得られた値を減圧後粘着力とした。測定結果を表１に示す。 (2) Measurement of adhesive strength after decompression (Examples 1 and 2, Comparative Example 1)
In addition, the adhesive sheet obtained in each example was cut into a size of 25 mm in length and 300 mm in width, and then a glass plate (manufactured by Nippon Sheet Glass Co., Ltd., soda) in an environment of 23 ° C. and 50% RH (relative humidity). Lime glass, length 150 mm × width 70 mm ×thickness 2 mm), and allowed to stand in the same environment for 24 hours. After being left standing, it was left in a quartz glass chamber, and the pressure inside the chamber was reduced to 2 kPa using a pressure reducer connected to the chamber with a hose and held for 10 seconds. After opening, the pressure-sensitive adhesive sheet and the glass plate were taken out from the chamber, and the pressure-sensitive adhesive force of each pressure-sensitive adhesive sheet was measured at a pulling speed of 300 mm / min by a 180 ° peeling method based on JIS Z0237: 2000. The obtained value was defined as the adhesive strength after decompression. The measurement results are shown in Table 1.
また、各実施例で得られた粘着シートを縦２５ｍｍ×横３００ｍｍの大きさに切断した後、２３℃、５０％ＲＨ（相対湿度）の環境下で、ガラス板（日本板硝子株式会社製，ソーダライムガラス，縦１５０ｍｍ×横７０ｍｍ×厚さ２ｍｍ）に貼付し、同じ環境下で２４時間静置した。静置後、石英ガラス製のチャンバーの中に静置し、チャンバーとホースで接続した減圧器を用いて、チャンバー内の雰囲気圧力が２ｋＰａになるまで減圧して１０秒間保持した後、減圧状態を開放して、チャンバーから粘着シートとガラス板を取り出して、ＪＩＳ Ｚ０２３７：２０００に基づき、１８０°引き剥がし法により、引っ張り速度３００ｍｍ／分にて、各粘着シートの粘着力を測定した。得られた値を減圧後粘着力とした。測定結果を表１に示す。 (2) Measurement of adhesive strength after decompression (Examples 1 and 2, Comparative Example 1)
In addition, the adhesive sheet obtained in each example was cut into a size of 25 mm in length and 300 mm in width, and then a glass plate (manufactured by Nippon Sheet Glass Co., Ltd., soda) in an environment of 23 ° C. and 50% RH (relative humidity). Lime glass, length 150 mm × width 70 mm ×
（３）ＵＶ硬化後粘着力の測定（実施例３，４）
製造例２で得られた粘着シートを縦２５ｍｍ×横３００ｍｍの大きさに切断した後、２３℃、５０％ＲＨ（相対湿度）の環境下で、ガラス板（日本板硝子株式会社製，ソーダライムガラス，縦１５０ｍｍ×横７０ｍｍ×厚さ２ｍｍ）に貼付し、同じ環境下で２４時間静置した。その後、石英ガラス製のチャンバーの中に静置し、照射紫外線照射装置（ヘレウス社製、製品名「ライトハンマー １０ ＭＡＲＫ ＩＩ」、無電極ランプ）を用いて、石英ガラス上から２ｃｍの照射距離にて紫外線照射した後に、チャンバーから粘着シートとガラス板を取り出して、ＪＩＳ Ｚ０２３７：２０００に基づき、１８０°引き剥がし法により、引っ張り速度３００ｍｍ／分にて、各粘着シートの粘着力を測定した。得られた値をＵＶ硬化後粘着力とした。測定結果を表１に示す。
紫外線照射条件は、波長２００～３８０ｎｍの範囲において、照度７００ｍＷ／ｃｍ２、光量７００ｍＪ／ｃｍ２とし、当該照度及び光量は照度・光量計（ＥＩＴ社製、製品名「ＵＶ Ｐｏｗｅｒ Ｐｕｃｋ ＩＩ」）を用いて照度および光量を測定した。 (3) Measurement of adhesive strength after UV curing (Examples 3 and 4)
The pressure-sensitive adhesive sheet obtained in Production Example 2 was cut into a size of 25 mm in length and 300 mm in width, and then a glass plate (manufactured by Nippon Sheet Glass Co., Ltd., soda lime glass) in an environment of 23 ° C. and 50% RH (relative humidity). , Length 150 mm × width 70 mm ×thickness 2 mm) and allowed to stand for 24 hours in the same environment. Then, it is left still in a quartz glass chamber, and an irradiation distance of 2 cm from the quartz glass is used using an irradiation ultraviolet irradiation device (manufactured by Heraeus, product name “Light Hammer 10 MARK II”, electrodeless lamp). After the ultraviolet irradiation, the pressure-sensitive adhesive sheet and the glass plate were taken out from the chamber, and the pressure-sensitive adhesive strength of each pressure-sensitive adhesive sheet was measured at a pulling speed of 300 mm / min by a 180 ° peeling method based on JIS Z0237: 2000. The obtained value was defined as the adhesive strength after UV curing. The measurement results are shown in Table 1.
The ultraviolet irradiation conditions are an illuminance of 700 mW / cm 2 and a light amount of 700 mJ / cm 2 in a wavelength range of 200 to 380 nm. The illuminance and light amount are determined by an illuminance / light meter (product name “UV Power Pack II” manufactured by EIT). Used to measure illuminance and light intensity.
製造例２で得られた粘着シートを縦２５ｍｍ×横３００ｍｍの大きさに切断した後、２３℃、５０％ＲＨ（相対湿度）の環境下で、ガラス板（日本板硝子株式会社製，ソーダライムガラス，縦１５０ｍｍ×横７０ｍｍ×厚さ２ｍｍ）に貼付し、同じ環境下で２４時間静置した。その後、石英ガラス製のチャンバーの中に静置し、照射紫外線照射装置（ヘレウス社製、製品名「ライトハンマー １０ ＭＡＲＫ ＩＩ」、無電極ランプ）を用いて、石英ガラス上から２ｃｍの照射距離にて紫外線照射した後に、チャンバーから粘着シートとガラス板を取り出して、ＪＩＳ Ｚ０２３７：２０００に基づき、１８０°引き剥がし法により、引っ張り速度３００ｍｍ／分にて、各粘着シートの粘着力を測定した。得られた値をＵＶ硬化後粘着力とした。測定結果を表１に示す。
紫外線照射条件は、波長２００～３８０ｎｍの範囲において、照度７００ｍＷ／ｃｍ２、光量７００ｍＪ／ｃｍ２とし、当該照度及び光量は照度・光量計（ＥＩＴ社製、製品名「ＵＶ Ｐｏｗｅｒ Ｐｕｃｋ ＩＩ」）を用いて照度および光量を測定した。 (3) Measurement of adhesive strength after UV curing (Examples 3 and 4)
The pressure-sensitive adhesive sheet obtained in Production Example 2 was cut into a size of 25 mm in length and 300 mm in width, and then a glass plate (manufactured by Nippon Sheet Glass Co., Ltd., soda lime glass) in an environment of 23 ° C. and 50% RH (relative humidity). , Length 150 mm × width 70 mm ×
The ultraviolet irradiation conditions are an illuminance of 700 mW / cm 2 and a light amount of 700 mJ / cm 2 in a wavelength range of 200 to 380 nm. The illuminance and light amount are determined by an illuminance / light meter (product name “UV Power Pack II” manufactured by EIT). Used to measure illuminance and light intensity.
（４）減圧・ＵＶ硬化後粘着力の測定（実施例３）
製造例２で得られた粘着シートを縦２５ｍｍ×横３００ｍｍの大きさに切断した後、２３℃、５０％ＲＨ（相対湿度）の環境下で、ガラス板（日本板硝子株式会社製，ソーダライムガラス，縦１５０ｍｍ×横７０ｍｍ×厚さ２ｍｍ）に貼付し、同じ環境下で２４時間静置した。静置後、石英ガラス製のチャンバーの中に静置し、チャンバーとホースで接続した減圧器を用いて、チャンバー内の雰囲気圧力が２ｋＰａになるまで減圧して１０秒間保持しながら、照射紫外線照射装置（ヘレウス社製、製品名「ライトハンマー １０ ＭＡＲＫ ＩＩ」、無電極ランプ）を用いて、石英ガラス上から２ｃｍの照射距離にて紫外線照射した。その後、減圧状態を開放して、チャンバーから粘着シートとガラス板を取り出して、ＪＩＳ Ｚ０２３７：２０００に基づき、１８０°引き剥がし法により、引っ張り速度３００ｍｍ／分にて、各粘着シートの粘着力を測定した。得られた値を減圧・ＵＶ硬化後粘着力とした。測定結果を表１に示す。
紫外線照射条件は、（３）ＵＶ硬化後粘着力の測定 と同様の条件とした。 (4) Measurement of adhesive strength after reduced pressure and UV curing (Example 3)
The pressure-sensitive adhesive sheet obtained in Production Example 2 was cut into a size of 25 mm in length and 300 mm in width, and then a glass plate (manufactured by Nippon Sheet Glass Co., Ltd., soda lime glass) in an environment of 23 ° C. and 50% RH (relative humidity). , Length 150 mm × width 70 mm ×thickness 2 mm) and allowed to stand for 24 hours in the same environment. After standing, leave it in a quartz glass chamber and use a decompressor connected to the chamber with a hose to reduce the atmospheric pressure in the chamber to 2 kPa and hold it for 10 seconds while irradiating with ultraviolet rays. Using an apparatus (manufactured by Heraeus, product name “Light Hammer 10 MARK II”, electrodeless lamp), ultraviolet irradiation was performed at an irradiation distance of 2 cm from the quartz glass. Then, the pressure-reduced state is released, the pressure-sensitive adhesive sheet and the glass plate are taken out from the chamber, and the pressure-sensitive adhesive strength of each pressure-sensitive adhesive sheet is measured at a pulling speed of 300 mm / min by the 180 ° peeling method based on JIS Z0237: 2000. did. The obtained value was defined as the adhesive strength after reduced pressure and UV curing. The measurement results are shown in Table 1.
The ultraviolet irradiation conditions were the same as those in (3) Measurement of adhesive strength after UV curing.
製造例２で得られた粘着シートを縦２５ｍｍ×横３００ｍｍの大きさに切断した後、２３℃、５０％ＲＨ（相対湿度）の環境下で、ガラス板（日本板硝子株式会社製，ソーダライムガラス，縦１５０ｍｍ×横７０ｍｍ×厚さ２ｍｍ）に貼付し、同じ環境下で２４時間静置した。静置後、石英ガラス製のチャンバーの中に静置し、チャンバーとホースで接続した減圧器を用いて、チャンバー内の雰囲気圧力が２ｋＰａになるまで減圧して１０秒間保持しながら、照射紫外線照射装置（ヘレウス社製、製品名「ライトハンマー １０ ＭＡＲＫ ＩＩ」、無電極ランプ）を用いて、石英ガラス上から２ｃｍの照射距離にて紫外線照射した。その後、減圧状態を開放して、チャンバーから粘着シートとガラス板を取り出して、ＪＩＳ Ｚ０２３７：２０００に基づき、１８０°引き剥がし法により、引っ張り速度３００ｍｍ／分にて、各粘着シートの粘着力を測定した。得られた値を減圧・ＵＶ硬化後粘着力とした。測定結果を表１に示す。
紫外線照射条件は、（３）ＵＶ硬化後粘着力の測定 と同様の条件とした。 (4) Measurement of adhesive strength after reduced pressure and UV curing (Example 3)
The pressure-sensitive adhesive sheet obtained in Production Example 2 was cut into a size of 25 mm in length and 300 mm in width, and then a glass plate (manufactured by Nippon Sheet Glass Co., Ltd., soda lime glass) in an environment of 23 ° C. and 50% RH (relative humidity). , Length 150 mm × width 70 mm ×
The ultraviolet irradiation conditions were the same as those in (3) Measurement of adhesive strength after UV curing.
（５）ＵＶ硬化後・減圧後粘着力の測定（実施例４）
製造例２で得られた粘着シートを縦２５ｍｍ×横３００ｍｍの大きさに切断した後、２３℃、５０％ＲＨ（相対湿度）の環境下で、ガラス板（日本板硝子株式会社製，ソーダライムガラス，縦１５０ｍｍ×横７０ｍｍ×厚さ２ｍｍ）に貼付し、同じ環境下で２４時間静置した。静置後、石英ガラス製のチャンバーの中に静置し、照射紫外線照射装置（ヘレウス社製、製品名「ライトハンマー １０ ＭＡＲＫ ＩＩ」、無電極ランプ）を用いて、石英ガラス上から２ｃｍの照射距離にて紫外線照射した後に、チャンバーとホースで接続した減圧器を用いて、チャンバー内の雰囲気圧力が２ｋＰａになるまで減圧して１０秒間保持した後、減圧状態を開放して、チャンバーから粘着シートとガラス板を取り出して、ＪＩＳ Ｚ０２３７：２０００に基づき、１８０°引き剥がし法により、引っ張り速度３００ｍｍ／分にて、各粘着シートの粘着力を測定した。得られた結果をＵＶ硬化後・減圧後粘着力とした。測定結果を表１に示す。
紫外線照射条件は、（３）ＵＶ硬化後粘着力の測定 と同様の条件とした。 (5) Measurement of adhesive strength after UV curing and reduced pressure (Example 4)
The pressure-sensitive adhesive sheet obtained in Production Example 2 was cut into a size of 25 mm in length and 300 mm in width, and then a glass plate (manufactured by Nippon Sheet Glass Co., Ltd., soda lime glass) in an environment of 23 ° C. and 50% RH (relative humidity). , Length 150 mm × width 70 mm ×thickness 2 mm) and allowed to stand for 24 hours in the same environment. After standing, leave in a quartz glass chamber and irradiate 2 cm from the top of the quartz glass using an irradiation ultraviolet irradiation device (product name “Light Hammer 10 MARK II”, electrodeless lamp) manufactured by Heraeus. After irradiating with ultraviolet rays at a distance, using a decompressor connected to the chamber and a hose, the pressure inside the chamber is reduced to 2 kPa and held for 10 seconds, then the reduced pressure state is released, and the adhesive sheet is removed from the chamber. And the glass plate was taken out, and the adhesive force of each adhesive sheet was measured at a pulling speed of 300 mm / min by a 180 ° peeling method based on JIS Z0237: 2000. The obtained result was defined as the adhesive strength after UV curing and reduced pressure. The measurement results are shown in Table 1.
The ultraviolet irradiation conditions were the same as those in (3) Measurement of adhesive strength after UV curing.
製造例２で得られた粘着シートを縦２５ｍｍ×横３００ｍｍの大きさに切断した後、２３℃、５０％ＲＨ（相対湿度）の環境下で、ガラス板（日本板硝子株式会社製，ソーダライムガラス，縦１５０ｍｍ×横７０ｍｍ×厚さ２ｍｍ）に貼付し、同じ環境下で２４時間静置した。静置後、石英ガラス製のチャンバーの中に静置し、照射紫外線照射装置（ヘレウス社製、製品名「ライトハンマー １０ ＭＡＲＫ ＩＩ」、無電極ランプ）を用いて、石英ガラス上から２ｃｍの照射距離にて紫外線照射した後に、チャンバーとホースで接続した減圧器を用いて、チャンバー内の雰囲気圧力が２ｋＰａになるまで減圧して１０秒間保持した後、減圧状態を開放して、チャンバーから粘着シートとガラス板を取り出して、ＪＩＳ Ｚ０２３７：２０００に基づき、１８０°引き剥がし法により、引っ張り速度３００ｍｍ／分にて、各粘着シートの粘着力を測定した。得られた結果をＵＶ硬化後・減圧後粘着力とした。測定結果を表１に示す。
紫外線照射条件は、（３）ＵＶ硬化後粘着力の測定 と同様の条件とした。 (5) Measurement of adhesive strength after UV curing and reduced pressure (Example 4)
The pressure-sensitive adhesive sheet obtained in Production Example 2 was cut into a size of 25 mm in length and 300 mm in width, and then a glass plate (manufactured by Nippon Sheet Glass Co., Ltd., soda lime glass) in an environment of 23 ° C. and 50% RH (relative humidity). , Length 150 mm × width 70 mm ×
The ultraviolet irradiation conditions were the same as those in (3) Measurement of adhesive strength after UV curing.
＜粘着力減少率＞
実施例１～２および比較例１においては、下記式によって粘着力減少率を算出した。
粘着力減少率（％）＝（減圧前粘着力－減圧後粘着力）／（減圧前粘着力）×１００
一方、実施例３においては、上記式の減圧前粘着力に替えてＵＶ硬化後粘着力を用い、また減圧後粘着力に替えて減圧・ＵＶ硬化後粘着力を用い、上記式と同様にして粘着力減少率を算出した。
また、実施例４においては、上記式の減圧前粘着力に替えてＵＶ硬化後粘着力を用い、また減圧後粘着力に替えてＵＶ硬化後・減圧後粘着力を用い、上記式と同様にして粘着力減少率を算出した。
結果を表１に示す。 <Adhesion reduction rate>
In Examples 1 and 2 and Comparative Example 1, the adhesive force reduction rate was calculated by the following formula.
Adhesive strength reduction rate (%) = (adhesive strength before decompression−adhesive strength after decompression) / (adhesive strength before decompression) × 100
On the other hand, in Example 3, the adhesive force after UV curing is used instead of the adhesive force before decompression in the above formula, and the adhesive force after decompression and UV curing is used instead of the adhesive force after decompression, and the same formula as above. The adhesive strength reduction rate was calculated.
In Example 4, the adhesive strength after UV curing is used instead of the adhesive strength before decompression in the above formula, and the adhesive strength after UV curing and after decompression is used instead of the adhesive strength after decompression, and the same formula as above. The adhesive strength reduction rate was calculated.
The results are shown in Table 1.
実施例１～２および比較例１においては、下記式によって粘着力減少率を算出した。
粘着力減少率（％）＝（減圧前粘着力－減圧後粘着力）／（減圧前粘着力）×１００
一方、実施例３においては、上記式の減圧前粘着力に替えてＵＶ硬化後粘着力を用い、また減圧後粘着力に替えて減圧・ＵＶ硬化後粘着力を用い、上記式と同様にして粘着力減少率を算出した。
また、実施例４においては、上記式の減圧前粘着力に替えてＵＶ硬化後粘着力を用い、また減圧後粘着力に替えてＵＶ硬化後・減圧後粘着力を用い、上記式と同様にして粘着力減少率を算出した。
結果を表１に示す。 <Adhesion reduction rate>
In Examples 1 and 2 and Comparative Example 1, the adhesive force reduction rate was calculated by the following formula.
Adhesive strength reduction rate (%) = (adhesive strength before decompression−adhesive strength after decompression) / (adhesive strength before decompression) × 100
On the other hand, in Example 3, the adhesive force after UV curing is used instead of the adhesive force before decompression in the above formula, and the adhesive force after decompression and UV curing is used instead of the adhesive force after decompression, and the same formula as above. The adhesive strength reduction rate was calculated.
In Example 4, the adhesive strength after UV curing is used instead of the adhesive strength before decompression in the above formula, and the adhesive strength after UV curing and after decompression is used instead of the adhesive strength after decompression, and the same formula as above. The adhesive strength reduction rate was calculated.
The results are shown in Table 1.
＜応力緩和率＞
各製造例において、基材を重剥離シート（リンテック株式会社製，製品名「ＳＰ－ＰＥＴ３８２０５０」，厚さ３８μｍ，ポリエチレンテレフタレートフィルムにシリコーン系剥離剤を積層させたもの）に変更し、乾燥後の粘着剤層の厚さが５００μｍとなるように塗布したこと以外は製造例に記載の通りの手順で、２枚の剥離シートに挟持された基材レスの両面粘着シートを作成した。 <Stress relaxation rate>
In each production example, the substrate was changed to a heavy release sheet (product name “SP-PET 382050”, thickness 38 μm, polyethylene terephthalate film laminated with a silicone release agent) manufactured by Lintec Corporation, and dried. A substrate-less double-sided pressure-sensitive adhesive sheet sandwiched between two release sheets was prepared in the same manner as described in the production examples except that the pressure-sensitive adhesive layer was applied to have a thickness of 500 μm.
各製造例において、基材を重剥離シート（リンテック株式会社製，製品名「ＳＰ－ＰＥＴ３８２０５０」，厚さ３８μｍ，ポリエチレンテレフタレートフィルムにシリコーン系剥離剤を積層させたもの）に変更し、乾燥後の粘着剤層の厚さが５００μｍとなるように塗布したこと以外は製造例に記載の通りの手順で、２枚の剥離シートに挟持された基材レスの両面粘着シートを作成した。 <Stress relaxation rate>
In each production example, the substrate was changed to a heavy release sheet (product name “SP-PET 382050”, thickness 38 μm, polyethylene terephthalate film laminated with a silicone release agent) manufactured by Lintec Corporation, and dried. A substrate-less double-sided pressure-sensitive adhesive sheet sandwiched between two release sheets was prepared in the same manner as described in the production examples except that the pressure-sensitive adhesive layer was applied to have a thickness of 500 μm.
基材レスの両面粘着シートを２３℃、５０％ＲＨの雰囲気下で２週間放置した後、上記粘着剤層を複数層積層した粘着シートから１５ｍｍ幅×５５ｍｍ長のサンプルを切り出し、積層体の最表層に積層された剥離シートを剥し、サンプル測定範囲が１５ｍｍ幅×２５ｍｍ長になるようにサンプルを万能引張試験機（株式会社島津製作所製，オートグラフＡＧ－１０ｋＮＩＳ）にセットした。そして、２３℃、５０％ＲＨ（相対湿度）の環境下にて、引張速度２００ｍｍ／分でサンプルを伸長させ、３００％伸長時の応力Ａ（Ｐａ）と、伸長停止から３００秒後の応力Ｂ（Ｐａ）とを測定した。測定はＭＤ方向、つまり粘着剤の塗布方向と平行である方向のみを測定した。測定された応力Ａおよび応力Ｂから、以下の式を用いて、応力緩和率（％）を算出した。測定結果を表１に示す。
応力緩和率（％）＝{（Ａ－Ｂ）／Ａ}×１００（％） The substrate-less double-sided pressure-sensitive adhesive sheet was allowed to stand in an atmosphere of 23 ° C. and 50% RH for 2 weeks, and then a sample having a width of 15 mm × 55 mm was cut out from the pressure-sensitive adhesive sheet in which a plurality of the pressure-sensitive adhesive layers were laminated. The release sheet laminated on the surface layer was peeled off, and the sample was set in a universal tensile testing machine (manufactured by Shimadzu Corporation, Autograph AG-10kNIS) so that the sample measurement range was 15 mm wide × 25 mm long. Then, in an environment of 23 ° C. and 50% RH (relative humidity), the sample is stretched at a tensile rate of 200 mm / min, and stress A (Pa) at 300% elongation and stress B after 300 seconds from the stop of elongation. (Pa) was measured. The measurement was performed only in the MD direction, that is, the direction parallel to the adhesive application direction. From the measured stress A and stress B, the stress relaxation rate (%) was calculated using the following equation. The measurement results are shown in Table 1.
Stress relaxation rate (%) = {(AB) / A} × 100 (%)
応力緩和率（％）＝{（Ａ－Ｂ）／Ａ}×１００（％） The substrate-less double-sided pressure-sensitive adhesive sheet was allowed to stand in an atmosphere of 23 ° C. and 50% RH for 2 weeks, and then a sample having a width of 15 mm × 55 mm was cut out from the pressure-sensitive adhesive sheet in which a plurality of the pressure-sensitive adhesive layers were laminated. The release sheet laminated on the surface layer was peeled off, and the sample was set in a universal tensile testing machine (manufactured by Shimadzu Corporation, Autograph AG-10kNIS) so that the sample measurement range was 15 mm wide × 25 mm long. Then, in an environment of 23 ° C. and 50% RH (relative humidity), the sample is stretched at a tensile rate of 200 mm / min, and stress A (Pa) at 300% elongation and stress B after 300 seconds from the stop of elongation. (Pa) was measured. The measurement was performed only in the MD direction, that is, the direction parallel to the adhesive application direction. From the measured stress A and stress B, the stress relaxation rate (%) was calculated using the following equation. The measurement results are shown in Table 1.
Stress relaxation rate (%) = {(AB) / A} × 100 (%)
＜破断伸度＞
応力緩和率の測定に使用したサンプルと同じ形態、大きさのサンプルを、前述の応力緩和率の測定と同じ様にサンプル測定範囲が１５ｍｍ幅×２５ｍｍ長となるように万能引張試験機（株式会社島津製作所製，オートグラフＡＧ－１０ｋＮＩＳ）にセットした。そして、２３℃、５０％ＲＨ（相対湿度）の環境下にて、引張速度２００ｍｍ／分でサンプルを伸長させ破断した時のサンプルの長さＣ（ｍｍ）を測定した。測定はＭＤ方向、つまり粘着剤の塗布方向と平行である方向のみを測定した。破断した時のサンプルの長さＣ（ｍｍ）から、以下の式を用いて破断伸度（％）を算出した。測定結果を表１に示す。
破断伸度（％）＝｛Ｃ／測定前のサンプル長さ｝×１００（％） <Elongation at break>
Universal tensile testing machine (Co., Ltd.) with the same shape and size as the sample used for the measurement of the stress relaxation rate so that the sample measurement range is 15 mm wide x 25 mm long in the same way as the measurement of the stress relaxation rate described above. Shimadzu Corporation, Autograph AG-10k NIS). Then, in an environment of 23 ° C. and 50% RH (relative humidity), the length C (mm) of the sample when the sample was stretched and broken at a tensile speed of 200 mm / min was measured. The measurement was performed only in the MD direction, that is, the direction parallel to the adhesive application direction. The elongation at break (%) was calculated from the length C (mm) of the sample at the time of fracture using the following formula. The measurement results are shown in Table 1.
Elongation at break (%) = {C / sample length before measurement} × 100 (%)
応力緩和率の測定に使用したサンプルと同じ形態、大きさのサンプルを、前述の応力緩和率の測定と同じ様にサンプル測定範囲が１５ｍｍ幅×２５ｍｍ長となるように万能引張試験機（株式会社島津製作所製，オートグラフＡＧ－１０ｋＮＩＳ）にセットした。そして、２３℃、５０％ＲＨ（相対湿度）の環境下にて、引張速度２００ｍｍ／分でサンプルを伸長させ破断した時のサンプルの長さＣ（ｍｍ）を測定した。測定はＭＤ方向、つまり粘着剤の塗布方向と平行である方向のみを測定した。破断した時のサンプルの長さＣ（ｍｍ）から、以下の式を用いて破断伸度（％）を算出した。測定結果を表１に示す。
破断伸度（％）＝｛Ｃ／測定前のサンプル長さ｝×１００（％） <Elongation at break>
Universal tensile testing machine (Co., Ltd.) with the same shape and size as the sample used for the measurement of the stress relaxation rate so that the sample measurement range is 15 mm wide x 25 mm long in the same way as the measurement of the stress relaxation rate described above. Shimadzu Corporation, Autograph AG-10k NIS). Then, in an environment of 23 ° C. and 50% RH (relative humidity), the length C (mm) of the sample when the sample was stretched and broken at a tensile speed of 200 mm / min was measured. The measurement was performed only in the MD direction, that is, the direction parallel to the adhesive application direction. The elongation at break (%) was calculated from the length C (mm) of the sample at the time of fracture using the following formula. The measurement results are shown in Table 1.
Elongation at break (%) = {C / sample length before measurement} × 100 (%)
＜ゲル分率＞
応力緩和率の測定に使用した基材レスの粘着シートを８０ｍｍ×８０ｍｍの大きさに裁断して、剥離シートを除去した粘着剤層をポリエステル製メッシュ（メッシュ数：２００メッシュ／インチ）に包み、粘着剤のみの質量を精密天秤にて秤量した。このときの質量をＭ１とする。
次に、酢酸エチル溶剤に上記粘着剤のサンプルを室温（２３℃）で２４時間浸漬させた。その後粘着剤を取り出し、温度２３℃、５０％ＲＨの環境下で、２４時間風乾させ、さらに８０℃のオーブン中にて１２時間乾燥させた。乾燥後の粘着剤のみの質量を、精密天秤にて秤量した。このときの質量をＭ２とする。ゲル分率（％）は、（Ｍ２／Ｍ１）×１００で表される。測定結果を表１に示す。 <Gel fraction>
The base material-less pressure-sensitive adhesive sheet used for the measurement of the stress relaxation rate was cut into a size of 80 mm × 80 mm, and the pressure-sensitive adhesive layer from which the release sheet was removed was wrapped in a polyester mesh (number of meshes: 200 mesh / inch), The mass of only the adhesive was weighed with a precision balance. The mass at this time is M1.
Next, the pressure-sensitive adhesive sample was immersed in an ethyl acetate solvent at room temperature (23 ° C.) for 24 hours. Thereafter, the pressure-sensitive adhesive was taken out and air-dried for 24 hours in an environment of a temperature of 23 ° C. and 50% RH, and further dried in an oven at 80 ° C. for 12 hours. The mass of only the pressure-sensitive adhesive after drying was weighed with a precision balance. The mass at this time is M2. The gel fraction (%) is represented by (M2 / M1) × 100. The measurement results are shown in Table 1.
応力緩和率の測定に使用した基材レスの粘着シートを８０ｍｍ×８０ｍｍの大きさに裁断して、剥離シートを除去した粘着剤層をポリエステル製メッシュ（メッシュ数：２００メッシュ／インチ）に包み、粘着剤のみの質量を精密天秤にて秤量した。このときの質量をＭ１とする。
次に、酢酸エチル溶剤に上記粘着剤のサンプルを室温（２３℃）で２４時間浸漬させた。その後粘着剤を取り出し、温度２３℃、５０％ＲＨの環境下で、２４時間風乾させ、さらに８０℃のオーブン中にて１２時間乾燥させた。乾燥後の粘着剤のみの質量を、精密天秤にて秤量した。このときの質量をＭ２とする。ゲル分率（％）は、（Ｍ２／Ｍ１）×１００で表される。測定結果を表１に示す。 <Gel fraction>
The base material-less pressure-sensitive adhesive sheet used for the measurement of the stress relaxation rate was cut into a size of 80 mm × 80 mm, and the pressure-sensitive adhesive layer from which the release sheet was removed was wrapped in a polyester mesh (number of meshes: 200 mesh / inch), The mass of only the adhesive was weighed with a precision balance. The mass at this time is M1.
Next, the pressure-sensitive adhesive sample was immersed in an ethyl acetate solvent at room temperature (23 ° C.) for 24 hours. Thereafter, the pressure-sensitive adhesive was taken out and air-dried for 24 hours in an environment of a temperature of 23 ° C. and 50% RH, and further dried in an oven at 80 ° C. for 12 hours. The mass of only the pressure-sensitive adhesive after drying was weighed with a precision balance. The mass at this time is M2. The gel fraction (%) is represented by (M2 / M1) × 100. The measurement results are shown in Table 1.
表１に示される通り、実施例１～４のいずれにおいても、減圧処理を行うことにより粘着力が低下し、粘着シートと被着体との剥離が容易になることが確認された。
As shown in Table 1, in any of Examples 1 to 4, it was confirmed that the pressure-sensitive adhesive treatment reduced the adhesive strength and facilitated peeling between the adhesive sheet and the adherend.
１…粘着シート
２…粘着剤層
３…気室
４…基材
Ｐ…粘着面
Ｗ…ワーク
Ｗ’…加工物
１０…圧力制御装置 DESCRIPTION OFSYMBOLS 1 ... Adhesive sheet 2 ... Adhesive layer 3 ... Air chamber 4 ... Base material P ... Adhesive surface W ... Work W '... Workpiece 10 ... Pressure control apparatus
２…粘着剤層
３…気室
４…基材
Ｐ…粘着面
Ｗ…ワーク
Ｗ’…加工物
１０…圧力制御装置 DESCRIPTION OF
Claims (11)
- 少なくとも粘着剤層を備える粘着シートと、前記粘着剤層の粘着面に貼着された被着体とを剥離する粘着シートの剥離方法であって、
前記粘着剤層は、内部に気室を有しており、
少なくとも前記被着体が貼着された前記粘着シートに対し、前記気室中の気体を膨張させる減圧処理を行うことにより、前記粘着剤層の粘着力を低下させ、前記粘着シートと前記被着体とを剥離する
ことを特徴とする粘着シートの剥離方法。 A pressure-sensitive adhesive sheet peeling method for peeling a pressure-sensitive adhesive sheet having at least a pressure-sensitive adhesive layer and an adherend adhered to the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer,
The pressure-sensitive adhesive layer has an air chamber inside,
At least the pressure-sensitive adhesive sheet to which the adherend is adhered is subjected to a decompression process for expanding the gas in the air chamber, thereby reducing the adhesive strength of the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive sheet and the adhesion A method for peeling a pressure-sensitive adhesive sheet, comprising peeling off a body. - 前記減圧処理は、前記粘着シートを前記被着体に貼着した環境の雰囲気圧力よりも低くすることを特徴とする請求項１に記載の粘着シートの剥離方法。 2. The pressure-sensitive adhesive sheet peeling method according to claim 1, wherein the pressure reduction treatment is performed at a pressure lower than an atmospheric pressure of an environment in which the pressure-sensitive adhesive sheet is adhered to the adherend.
- 前記粘着剤層を形成する粘着剤組成物は、活性エネルギー線硬化性および熱硬化性を有さないことを特徴とする請求項１または２に記載の粘着シートの剥離方法。 The pressure-sensitive adhesive sheet peeling method according to claim 1 or 2, wherein the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer does not have active energy ray curability and thermosetting.
- 前記粘着剤組成物は（メタ）アクリル酸エステル重合体を含有することを特徴とする請求項３に記載の粘着シートの剥離方法。 The pressure-sensitive adhesive sheet peeling method according to claim 3, wherein the pressure-sensitive adhesive composition contains a (meth) acrylic acid ester polymer.
- 前記粘着剤層を形成する粘着剤組成物は活性エネルギー線硬化性または熱硬化性を有することを特徴とする請求項１または２に記載の粘着シートの剥離方法。 The pressure-sensitive adhesive sheet peeling method according to claim 1 or 2, wherein the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer has active energy ray curability or thermosetting.
- 前記活性エネルギー線硬化型粘着剤組成物は、側鎖に活性エネルギー線硬化性基を有する（メタ）アクリル酸エステル重合体を含有することを特徴とする請求項５に記載の粘着シートの剥離方法。 The said active energy ray hardening-type adhesive composition contains the (meth) acrylic acid ester polymer which has an active energy ray hardening group in a side chain, The peeling method of the adhesive sheet of Claim 5 characterized by the above-mentioned. .
- 前記粘着剤層に対しエネルギー線を照射して前記粘着剤層を硬化させたのち、前記減圧処理を行うことを特徴とする請求項５または６に記載の粘着シートの剥離方法。 The pressure-sensitive adhesive sheet peeling method according to claim 5 or 6, wherein the pressure-reducing treatment is carried out after the pressure-sensitive adhesive layer is cured by irradiating the pressure-sensitive adhesive layer with an energy ray.
- 前記減圧処理を行ったのち、前記粘着剤層に対しエネルギー線を照射して前記粘着剤層を硬化させることを特徴とする請求項５または６に記載の粘着シートの剥離方法。 The pressure-sensitive adhesive sheet peeling method according to claim 5 or 6, wherein the pressure-sensitive adhesive layer is cured by irradiating the pressure-sensitive adhesive layer with an energy ray after the pressure reduction treatment.
- 前記粘着シートは、前記被着体の仮固定に用いられることを特徴とする請求項１～８のいずれか一項に記載の粘着シートの剥離方法。 The pressure-sensitive adhesive sheet peeling method according to any one of claims 1 to 8, wherein the pressure-sensitive adhesive sheet is used for temporarily fixing the adherend.
- 前記被着体は電子部材または光学部材であることを特徴とする請求項９に記載の粘着シートの剥離方法。 The pressure-sensitive adhesive sheet peeling method according to claim 9, wherein the adherend is an electronic member or an optical member.
- ワークを加工して得られる加工物の製造方法であって、
ワークと、少なくとも粘着剤層を備え、前記粘着剤層の内部に複数の独立した気室を有する粘着シートとを貼着する貼着工程と、
前記粘着シートに貼着された前記ワークを加工して加工物とする加工工程と、
少なくとも前記加工物が貼着された前記粘着シートを減圧環境に置いて前記気室中の気体を膨張させる減圧処理を行うことにより、前記粘着剤層の粘着力を低下させ、前記加工物と前記粘着シートとを剥離する剥離工程と
を備えることを特徴とする加工物の製造方法。 A method of manufacturing a workpiece obtained by processing a workpiece,
A pasting step of pasting a workpiece and at least a pressure-sensitive adhesive layer, and a pressure-sensitive adhesive sheet having a plurality of independent air chambers inside the pressure-sensitive adhesive layer;
A processing step of processing the workpiece adhered to the pressure-sensitive adhesive sheet into a processed product,
At least the pressure-sensitive adhesive sheet to which the workpiece is adhered is placed in a reduced-pressure environment to perform a pressure reduction treatment for expanding the gas in the air chamber, thereby reducing the adhesive strength of the pressure-sensitive adhesive layer, and the workpiece and the A process for producing a workpiece, comprising: a peeling step for peeling the pressure-sensitive adhesive sheet.
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