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WO2018190355A1 - Adhesive sheet for decorative molding - Google Patents

Adhesive sheet for decorative molding Download PDF

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Publication number
WO2018190355A1
WO2018190355A1 PCT/JP2018/015155 JP2018015155W WO2018190355A1 WO 2018190355 A1 WO2018190355 A1 WO 2018190355A1 JP 2018015155 W JP2018015155 W JP 2018015155W WO 2018190355 A1 WO2018190355 A1 WO 2018190355A1
Authority
WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
adhesive layer
adhesive sheet
meth
Prior art date
Application number
PCT/JP2018/015155
Other languages
French (fr)
Japanese (ja)
Inventor
貴迪 山口
隼介 塩田
順 塩野
山本　真之
Original Assignee
王子ホールディングス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=63792634&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2018190355(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 王子ホールディングス株式会社 filed Critical 王子ホールディングス株式会社
Priority to JP2019512539A priority Critical patent/JP7115470B2/en
Priority to CN201880024761.7A priority patent/CN110506090B/en
Priority to KR1020197030660A priority patent/KR102542711B1/en
Publication of WO2018190355A1 publication Critical patent/WO2018190355A1/en

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    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid 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
    • 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
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • 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]
    • 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]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners

Definitions

  • the present invention relates to an adhesive sheet that can be used for decorative molding.
  • Three-dimensional surface decoration molding is a molding technology that decorates the surface of a substrate by bonding a film such as a decorative film to a three-dimensional member. Etc. are widely used.
  • 3D decorative molding for example, a decorative film (adhesive sheet for 3D decoration) to which a pressure-sensitive adhesive sheet is bonded is bonded to a member having a curved surface such as a spherical shape or an uneven shape and heated to about 140 ° C. Glue both together.
  • a curved surface portion having a large R (degree of curved surface) or the like since a high drawability is required for the 3D decorative adhesive sheet itself, selection of a material for forming the adhesive sheet is also important. Become.
  • the pressure-sensitive adhesive sheet for 3D decoration is mainly formed of a base material and a pressure-sensitive adhesive layer, and conventionally, polyvinyl chloride (PVC) has been used as the base material.
  • PVC polyvinyl chloride
  • PET polyethylene terephthalate
  • PE polyethylene
  • PP polypropylene
  • 3D addition of vinylidene fluoride resin excellent in flexibility and transparency is required to improve this point.
  • It has been proposed to be used as a base material for a decorative adhesive sheet see Patent Document 1).
  • blending monoalcohol with the isocyanate bridged type adhesive is also proposed (refer patent document 2 etc.). .
  • the method using a vinylidene fluoride resin has a problem that a toxic gas is generated when the vinylidene fluoride is combusted, which leaves a problem in terms of safety. It was. Moreover, even if it is a technique disclosed by patent document 2 etc., as long as PP or PE is used for a base material, the subject that transparency and a weather resistance are inferior could not be solved. In particular, in 3D decorative molding, a large stress and load are applied to the pressure-sensitive adhesive layer that is in close contact with the curved surface portion of the three-dimensional shaped member. There is also a problem. Moreover, when the base material of the adhesive sheet is a material such as PET, there is a problem that wrinkles and cracks occur in the adhesive sheet because the squeezability of the adhesive sheet is not sufficient.
  • the present invention has been made in view of the above, and an object of the present invention is to provide a decorative molding pressure-sensitive adhesive sheet that has excellent adhesion, is less likely to cause wrinkles and cracks after bonding, and is less likely to float and peel off.
  • the present inventors have used a base material containing polymethyl methacrylate and an adhesive layer containing a tackifier containing polymethyl methacrylate, The inventors have found that the above object can be achieved and have completed the present invention.
  • the present invention includes, for example, the inventions described in the following sections.
  • Item 1 Provided with a laminate in which a base material and an adhesive layer are laminated, The substrate contains polymethyl methacrylate;
  • the pressure-sensitive adhesive layer is a pressure-sensitive adhesive sheet for decorative molding, containing a tackifier containing polymethyl methacrylate.
  • Item 2. Item 2.
  • the decorative molding pressure-sensitive adhesive sheet according to Item 1, wherein the polymethyl methacrylate contained in the tackifier has a weight average molecular weight (Mw) of 500 to 50,000.
  • Mw weight average molecular weight
  • the pressure-sensitive adhesive layer includes a crosslinked structure of a base polymer (A) other than polymethyl methacrylate, Item 1 or 2 wherein the structural unit of the base polymer (A) contains a (meth) acrylic acid ester monomer unit (a1) and a (meth) acrylic monomer unit (a2) having a crosslinkable functional group.
  • the pressure-sensitive adhesive sheet for decorative molding described in 1. Item 4.
  • Item 4. The decorative molding pressure-sensitive adhesive sheet according to any one of items 1 to 3, wherein a water contact angle on a surface opposite to the pressure-sensitive adhesive layer side of the substrate is 40 ° to 95 °.
  • Item 5. The decorative molding pressure-sensitive adhesive sheet according to any one of Items 1 to 4, wherein a separator is bonded to a surface of the pressure-sensitive adhesive layer opposite to the substrate side.
  • the decorative molding pressure-sensitive adhesive sheet according to the present invention is excellent in adhesion, hardly causes wrinkles and cracks after being bonded, and is also less likely to float and peel off.
  • (A)-(d) is a schematic sectional drawing which shows an example of embodiment of the pressure-sensitive adhesive sheet for decorative molding according to the present invention.
  • the pressure-sensitive adhesive sheet for decorative molding of the present invention comprises a laminate in which a base material and a pressure-sensitive adhesive layer are laminated, the base material contains polymethyl methacrylate, and the pressure-sensitive adhesive layer contains polymethyl methacrylate. Contains a tackifier.
  • the pressure-sensitive adhesive sheet for decorative molding of the present invention may be abbreviated as “pressure-sensitive adhesive sheet”.
  • the base material is a member for supporting the pressure-sensitive adhesive layer.
  • PMMA1 polymethyl methacrylate
  • PMMA2 polymethyl methacrylate
  • the substrate may be composed of only PMMA1 as long as the 3D decoration is not impaired, or may be a copolymer or blend of PMMA1 and other materials. Good.
  • known materials used as a film substrate can be widely used.
  • acrylic resins other than PMMA, polystyrene, PE, PP, PET, polyamide, polyimide examples thereof include silicone resin, polycarbonate (PC), styrene rubber, isoprene rubber, isobutylene rubber, ethylene-propylene-diene rubber, and acrylic rubber.
  • the base material may be a laminated base material of PMMA1 and another material.
  • known materials used as a film substrate can be widely used.
  • the content of PMMA1 is 70% by mass or more, preferably 80% by mass or more, and 90% by mass or more with respect to the total mass of the substrate. It is more preferable that
  • the thickness ratio of PMMA1 and the other material is such that PMMA1 is 10% or more, preferably 15% or more, more preferably 20 with respect to the entire laminated substrate. % Or more.
  • PMMA1 used for a laminated base material may be comprised only by PMMA1, and the copolymer of PMMA1 and another material may be sufficient as it.
  • the base material has a water contact angle of 40 ° to 95 °, preferably 50 ° to 90 °, on the surface opposite to the surface to which the pressure-sensitive adhesive layer is bonded, that is, the surface to be decoratively molded. If the water contact angle is within the above range, excellent printability can be imparted.
  • a method for setting the water contact angle of the substrate in the above range a method of laminating a desired resin that falls within the range of the water contact angle, a method of providing a desired easy-adhesive layer that falls within the range of the contact angle, A method of corona irradiation so as to fall within the range is mentioned.
  • FIG.1 (c) is a pressure-sensitive adhesive sheet for decorative molding in the case where an easy-adhesion layer is provided on a single-layer base material (PMMA1).
  • the easy-adhesion layer includes the adhesive layer side of the base material and Is provided on the opposite surface.
  • FIG.1 (d) is a pressure-sensitive adhesive sheet for decorative molding when the base material is the laminated base material, and in this case, the easy-adhesion layer is on the surface opposite to the pressure-sensitive adhesive layer side of the laminated base material.
  • the kind of easily bonding layer is not specifically limited, For example, the well-known easily bonding layer which can be applied as an adhesive sheet and the easily bonding layer for providing printability can be applied widely.
  • the base material can be formed, for example, by molding a raw material containing PMMA1. Or a commercially available PMMA film can be used as a base material.
  • the molding method is not particularly limited, and a known molding method can be employed.
  • the kind of raw material containing PMMA 1 is not particularly limited.
  • the raw material containing PMMA 1 may be only PMMA, or may contain other materials described above in addition to PMMA.
  • the weight average molecular weight (Mw) of PMMA 1 is not particularly limited, and can be the same as that of a general PMMA film, for example.
  • the thickness of the substrate is not particularly limited and is, for example, 5 to 100 ⁇ m.
  • the base material is formed in a sheet shape or a film shape.
  • the surface of the base material can be flat and can have irregularities.
  • the substrate may have either a single layer structure or a multilayer structure.
  • the pressure-sensitive adhesive layer is a layer formed on the base material and is a layer for exerting adhesiveness.
  • the pressure-sensitive adhesive layer can be formed directly on the substrate, and other layers can be interposed between the substrate and the pressure-sensitive adhesive layer as long as the effects of the present invention are not impaired.
  • the pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition described later.
  • the pressure-sensitive adhesive composition contains a tackifier containing PMMA2.
  • the tackifier referred to in the present invention is a component that can act as an auxiliary agent for imparting tackiness to the pressure-sensitive adhesive layer, and is a component generally referred to as tackifier.
  • the content of the tackifier is 1 to 35 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight per 100 parts by weight of the base polymer (A) described later. it can.
  • the content ratio of PMMA2 contained in the tackifier is 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, based on the total mass of the tackifier. It is particularly preferably 99% by mass or more.
  • the content ratio of PMMA2 contained in the tackifier can be 100% by mass.
  • the type of polymethyl methacrylate (PMMA2) contained in the tackifier is not particularly limited as long as the compatibility with the base polymer is not inhibited.
  • PMMA2 can be widely adopted.
  • PMMA2 can use the material marketed, for example, or can also be manufactured by a well-known polymerization method, for example, radical polymerization.
  • PMMA2 may be a homopolymer of polymethyl methacrylate, or may be a copolymer of methyl methacrylate and another acrylic monomer as long as the effect as a tackifier is not inhibited. Good.
  • acrylic monomers include N-alkyl-substituted amino group-containing methacrylic acid esters such as dimethylaminoethyl methacrylate (DMAEMA).
  • the content of methyl methacrylate is 70% by mass or more based on the total mass of methyl methacrylate and other acrylic monomers. It is preferable that it is 80 mass% or more, and it is especially preferable that it is 90 mass% or more.
  • the weight average molecular weight (Mw) of PMMA2 is not particularly limited, and can be, for example, 500 to 50,000.
  • Mw weight average molecular weight
  • the adhesive performance of the pressure-sensitive adhesive sheet is further improved, and even after the pressure-sensitive adhesive sheet is bonded to a member for 3D decorative molding, wrinkles and cracks are less likely to occur, and further, floating and peeling are less likely to occur.
  • the tackifier can contain other components other than PMMA2 as long as the effects of the present invention are not impaired.
  • known tackifying resins and the like applied to the adhesive sheet can be widely used, and examples thereof include styrene resins, terpene resins, and rosin esters.
  • the adhesive layer contains components other than the tackifier.
  • the pressure-sensitive adhesive layer may contain a polymer that becomes a matrix component of the pressure-sensitive adhesive layer in addition to the tackifier.
  • the pressure-sensitive adhesive layer can contain a crosslinked structure of a base polymer (A) other than polymethyl methacrylate.
  • the structural unit of the base polymer (A) can contain a (meth) acrylic acid ester monomer unit (a1) and a (meth) acrylic monomer unit (a2) having a crosslinkable functional group.
  • the crosslinked structure of the base polymer (A) can be a matrix component of the pressure-sensitive adhesive layer.
  • the crosslinked structure of the base polymer (A) is formed, for example, by a reaction between a base polymer (A) other than PMMA and a crosslinking agent (B) described later.
  • the crosslinking agent (B) is a crosslinking agent that can react with the base polymer (A).
  • base polymer (A) other than PMMA means that the base polymer (A) is not a PMMA homopolymer. That is, when the base polymer (A) is a copolymer, a PMMA component can be included as a constituent component of the copolymer.
  • the (meth) acrylic acid ester monomer unit (a1) indicates a repeating structural unit formed when the (meth) acrylic acid ester monomer is polymerized, and does not indicate the monomer itself.
  • the (meth) acrylic monomer unit (a2) having a crosslinkable functional group indicates a repeating structural unit formed when a (meth) acrylic monomer having a crosslinkable functional group is polymerized. It does not indicate the monomer itself.
  • (meth) acryl means “acryl or methacryl” and “(meth) acryl” means “acryl or methacryl”.
  • (meth) acrylic acid is synonymous with the description “acrylic acid or methacrylic acid”.
  • (Meth) acrylate monomer unit (a1) can be formed of a (meth) acrylate monomer.
  • the (meth) acrylic acid ester monomer here is a monomer having no functional group that reacts with the crosslinking agent (B).
  • the type of the (meth) acrylate monomer is not particularly limited, and for example, a known (meth) acrylate monomer can be used.
  • Specific examples of the (meth) acrylic acid ester monomer include compounds having a hydrocarbon group having 1 to 20 carbon atoms in the ester moiety of the (meth) acrylic acid ester.
  • the hydrocarbon group may have a linear, branched, cyclic or cage structure. Further, the hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Furthermore, the hydrocarbon group may have a substituent.
  • the (meth) acrylate monomer examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) N-butyl acrylate, 2-ethylhexyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, ( Examples include n-octyl (meth) acrylate, isooctyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, and phenyl (meth) acrylate.
  • the base polymer (A) can contain only one type of (meth) acrylic acid ester monomer unit (a1), or can contain two or more types.
  • the (meth) acrylic monomer unit (a2) having a crosslinkable functional group can be formed of a (meth) acrylic monomer having a crosslinkable functional group.
  • the (meth) acrylic monomer having a crosslinkable functional group here is a (meth) acrylic monomer having a functional group that reacts with the crosslinker (B), and the (meth) acrylic acid ester monomer It is a monomer different from the body.
  • the crosslinkable functional group in the (meth) acrylic monomer having a crosslinkable functional group is not particularly limited as long as it is a functional group that reacts with the crosslinker (B), depending on the type of the crosslinker (B). Can be selected as appropriate.
  • examples of the crosslinkable functional group include a carboxyl group, a hydroxy group, an amino group, an amide group, a sulfo group, a sulfonic acid, an epoxy group, a chloro group, and a fluoro group.
  • the (meth) acrylic monomer having a crosslinkable functional group can have one crosslinkable functional group in one molecule, and can also have two or more crosslinkable functional groups.
  • the crosslinkable functional group may be the same or different.
  • the (meth) acrylic monomer having a crosslinkable functional group include (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, citraconic acid, 2- (meth) acryloyl. Roxyethylphthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxylethyl (meth) acrylate, carboxypolycaprolactone mono (meth) acrylate, (meth) acrylamide , Vinyl alcohol, hydroxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylamide and the like.
  • Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 2-hydroxy Butyl (meth) acrylate, 2,2-dimethyl 2-hydroxyethyl (meth) acrylate, 3-chloro 2-hydroxypropyl (meth) acrylate, 2-hydroxy 3-phenoxypropyl (meth) acrylate, 2-hydroxy 3-phenoxy Examples thereof include propyl (meth) acrylate and 8-hydroxyoctyl (meth) acrylate.
  • Examples of the hydroxyalkyl (meth) acrylamide include N-hydroxypropyl (meth) acrylamide.
  • the base polymer (A) can contain only one type of (meth) acrylic monomer unit (a2) having a crosslinkable functional group, or can contain two or more types.
  • the (meth) acrylate monomer unit (a1) is simply abbreviated as “monomer unit (a1)”.
  • the (meth) acrylic monomer unit (a2) having a crosslinkable functional group is simply abbreviated as “monomer unit (a2)”.
  • the base polymer (A) can contain other monomer units other than the monomer unit (a1) and the monomer unit (a2) as long as the effects of the present invention are not inhibited.
  • the content ratio of the monomer unit (a1) can be 50 to 99.9% by mass, preferably 60 to 99.5% by mass, more preferably all the structural units forming the base polymer (A). It can be 70 to 99.0% by mass.
  • the base polymer (A) can be a so-called random copolymer in which the monomer unit (a1), the monomer unit (a2) and the other monomer units are randomly arranged.
  • the base polymer (A) can have other structures such as a block polymer.
  • the crosslinking agent (B) is a component for crosslinking the base polymer (A).
  • the crosslinking agent (B) is a component capable of reacting with the crosslinkable functional group of the monomer unit (a2) in the base polymer (A).
  • the type of the crosslinking agent (B) is not particularly limited as long as it can react with the crosslinking functional group of the monomer unit (a2), and a wide variety of known crosslinking agents can be used.
  • crosslinking agent (B) examples include an epoxy crosslinking agent and an isocyanate crosslinking agent.
  • the type of the isocyanate crosslinking agent is not particularly limited, and a wide variety of known compounds can be used.
  • isocyanate crosslinking agents include tolylene diisocyanate, chlorophenylene diisocyanate, diphenylmethane diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and xylylene diisocyanate; cyclopentylene diisocyanate, cyclohexane And alicyclic isocyanates such as hexylene diisocyanate, and aromatic isocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4′-diphenylmethane diisocyanate.
  • An isocyanate crosslinking agent can be used individually or in mixture of 2 or more types. Further, it is more preferable to use a trifunctional derivative such as an adduct, a nurate or a burette obtained from the above-mentioned diisocyanate as an isocyanate crosslinking agent.
  • epoxy crosslinking agent examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol.
  • tetrafunctional N, N, N ′, N′-tetraglycidyl-m-xylenediamine and 1,3-bis (N, N-diglycidylaminomethyl) cyclohexanone exhibit a crosslinking effect with a small addition amount. Therefore, it is preferable.
  • the content of the cross-linked structure of the base polymer (A) contained in the pressure-sensitive adhesive layer and PMMA2 contained as a tackifier is not particularly limited.
  • the amount of PMMA2 contained as a tackifier is 1 to 35 parts by mass, preferably 5 to 30 parts by mass, and more preferably 10 to 25 parts by mass per 100 parts by mass of the crosslinked structure in the adhesive layer.
  • excellent adhesiveness can be imparted to the pressure-sensitive adhesive layer, and wrinkles and cracks are less likely to occur even after the pressure-sensitive adhesive sheet is bonded to the member to be 3D-decorated, and moreover, floating and peeling are more likely. Hard to happen.
  • the thickness of the pressure-sensitive adhesive layer is 5 to 50 ⁇ m, preferably 8 to 45 ⁇ m, more preferably 10 to 35 ⁇ m.
  • the pressure-sensitive adhesive layer can be formed on the entire surface of the substrate, but may not be formed on the entire surface of the substrate as long as the effect of the present invention is not hindered.
  • the method for forming the pressure-sensitive adhesive layer is not particularly limited.
  • it can be formed by a method comprising using a pressure-sensitive adhesive composition to form a pressure-sensitive adhesive layer (hereinafter referred to as “pressure-sensitive adhesive layer forming step”).
  • pressure-sensitive adhesive layer forming step for example, the pressure-sensitive adhesive layer is formed on the substrate by applying and curing the pressure-sensitive adhesive composition on the substrate. Thereby, the laminated body formed with a base material and an adhesive layer is obtained.
  • an adhesive composition contains the tackifier containing PMMA2 as an essential component.
  • a material containing the base polymer (A), the crosslinking agent (B), and the tackifier can be used.
  • the base polymer (A) can be obtained by a polymerization reaction of a raw material containing the (meth) acrylic acid ester monomer and the (meth) acrylic monomer having a crosslinkable functional group. This raw material is based on the total amount of the (meth) acrylic acid ester monomer and the (meth) acrylic monomer having a crosslinkable functional group.
  • the monomer for forming a1) can be contained in an amount of 50 to 99.9% by mass, preferably 60 to 99.5% by mass, more preferably 70 to 99.0% by mass.
  • a known polymerization initiator can be used.
  • the polymerization initiator include azobisisobutyronitrile, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 1,1′-azobis (cyclohexanecarbonitrile), Examples thereof include di-tert-butyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, ammonium persulfate, and a photopolymerization initiator (Irgacure (registered trademark) series, etc.).
  • the amount of the polymerization initiator used is not limited, and can be the same as the conditions for known polymerization methods.
  • a solvent can be used as necessary.
  • the kind of solvent is not specifically limited,
  • polymerization can be used widely.
  • ester compounds such as ethyl acetate and butyl acetate
  • ketones such as acetone and methyl ethyl ketone
  • aliphatic hydrocarbons such as hexane
  • aromatic compounds such as toluene, xylene, and benzene
  • the amount of the solvent used in the polymerization reaction is not particularly limited.
  • the polymerization reaction can be obtained by a known polymerization method.
  • this polymerization method for example, solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization and the like can be employed.
  • the polymerization reaction for example, can be performed under an inert gas atmosphere such as nitrogen.
  • the reaction time and reaction temperature of the polymerization reaction are not limited, and can be set as appropriate according to the type and amount of the monomer used.
  • the polymerization reaction can be performed under conditions of 20 to 100 ° C. and 1 to 24 hours.
  • the method for preparing the pressure-sensitive adhesive composition is not particularly limited, and the pressure-sensitive adhesive composition can be prepared by mixing the base polymer (A), the crosslinking agent (B), and the tackifier at a predetermined blending ratio.
  • the mixing method is not particularly limited, and for example, a commercially available mixer can be used.
  • the pressure-sensitive adhesive composition 0.001 to 5 parts by mass, preferably 0.005 to 3 parts by mass, more preferably 0.01 to 1 part by mass of the crosslinking agent (B) per 100 parts by mass of the base polymer (A). Parts can be contained.
  • the pressure-sensitive adhesive composition can contain other components as necessary in addition to the base polymer (A), the cross-linking agent (B), and the tackifier.
  • other components include silane coupling agents, crosslinking accelerators, antistatic agents, light stabilizers (absorption) agents, dispersion stabilizers, preservatives, viscosity modifiers, metal corrosion inhibitors, solvents, and the like.
  • the method for applying the pressure-sensitive adhesive composition onto the substrate is not particularly limited, and for example, a known coating method can be widely adopted.
  • the thickness of the coating film formed by applying the pressure-sensitive adhesive composition is not limited, and can be appropriately set according to the thickness of the pressure-sensitive adhesive layer of the target pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive layer forming step after the pressure-sensitive adhesive composition is applied on the substrate, the pressure-sensitive adhesive layer is formed by curing the coating film of the pressure-sensitive adhesive composition.
  • the curing method is not particularly limited, and for example, conventionally used curing methods for pressure-sensitive adhesive compositions can be widely employed.
  • the method of heating and hardening a coating film can be mentioned.
  • the temperature for heating can be, for example, 50 to 200 ° C., preferably 80 to 150 ° C.
  • the heating time may be set so that the solvent is volatilized and the residual solvent concentration of the pressure-sensitive adhesive layer is 1000 ppm or less. From the concentration of the pressure-sensitive adhesive composition, the desired thickness of the pressure-sensitive adhesive layer, etc. It is preferable to set appropriately within the time of about minutes.
  • the crosslinking agent (B) in the pressure-sensitive adhesive composition reacts with the crosslinkable functional group of the monomer unit (a2) in the base polymer (A), and the crosslinking reaction of the base polymer (A) proceeds. To do. Thereby, the adhesive layer containing the crosslinked structure of a base polymer (A) is formed.
  • This pressure-sensitive adhesive layer also contains PMMA2 as a tackifier.
  • the cured product can be aged in a predetermined environment as necessary.
  • the pressure-sensitive adhesive layer is formed by the above pressure-sensitive adhesive layer forming step.
  • the pressure-sensitive adhesive layer forming step by forming the pressure-sensitive adhesive layer on the substrate, the laminate contained in the pressure-sensitive adhesive sheet can be directly obtained by the pressure-sensitive adhesive layer forming step.
  • the adhesive sheet can also be provided with a separator.
  • a separator may be bonded to the surface of the pressure-sensitive adhesive layer opposite to the base material side.
  • This separator is a member for protecting the adhesive layer of the adhesive sheet.
  • the type of separator is not particularly limited, and a wide variety of known films that have been conventionally used as separators for adhesive sheets can be used.
  • a known release-treated polyester film can be used as the separator for the pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive sheet includes a separator
  • the pressure-sensitive adhesive sheet is formed by laminating the base material, the pressure-sensitive adhesive layer, and the separator in this order.
  • the pressure-sensitive adhesive sheet may be formed only of a base material and a pressure-sensitive adhesive layer (that is, a laminate), may be formed only of a layer consisting of a laminate and the separator, or the laminate and the above-described It can also have layers other than a separator.
  • a pressure-sensitive adhesive layer that is, a laminate
  • the manufacturing method of the adhesive sheet is not particularly limited.
  • a method including the pressure-sensitive adhesive layer forming step can be employed.
  • a laminate is formed by this pressure-sensitive adhesive layer forming step, and this can be obtained as a pressure-sensitive adhesive sheet.
  • the conditions of the pressure-sensitive adhesive layer forming step are the same as described above, and the pressure-sensitive adhesive composition to be used is as described above.
  • an adhesive sheet is equipped with a separator, for example, a laminated body is formed in advance by an adhesive layer forming step, and the adhesive layer side of the laminated body and the separator are bonded together so that the adhesive layer Can be obtained.
  • the method for bonding the surface of the laminate to the pressure-sensitive adhesive layer side and the separator is not particularly limited, and for example, known methods can be widely adopted.
  • the pressure-sensitive adhesive sheet includes a separator
  • a pressure-sensitive adhesive layer is formed on the separator by the pressure-sensitive adhesive layer forming step, and then a base material is bonded onto the pressure-sensitive adhesive layer.
  • a pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive layer is protected by the separator can be obtained.
  • the method for bonding the pressure-sensitive adhesive layer and the substrate is not particularly limited, and for example, known methods can be widely adopted.
  • the pressure-sensitive adhesive sheet of the present invention can be used as a pressure-sensitive adhesive sheet for three-dimensional surface decoration molding (3D decoration molding).
  • the pressure-sensitive adhesive sheet of the present invention has a substrate surface (the side opposite to the pressure-sensitive adhesive layer). Can be used as a decorative film.
  • the type of decorative printing is not particularly limited, and a known printing method can be adopted. For example, screen printing, ink-jet printing, painting, vacuum film formation, plating, transfer and bonding of decorative films, insert-molded metal patterns, etc., and black and other color-printed films were laminated. Examples include design films.
  • the decorative film provided with the pressure-sensitive adhesive sheet of the present invention can be used as a film for 3D decorative molding.
  • the surface of the decorative film on the pressure-sensitive adhesive layer side is bonded to a 3D-shaped member to be 3D-decorated, thereby imparting design properties to the 3D-shaped member.
  • the pressure-sensitive adhesive sheet includes a separator, the separator is peeled from the pressure-sensitive adhesive layer to expose the pressure-sensitive adhesive layer, and the surface of the pressure-sensitive adhesive layer is bonded to the three-dimensional member.
  • the pressure-sensitive adhesive sheet of the present invention contains PMMA in the base material, it has excellent drawability, so it has excellent adhesion to a three-dimensional member, and is less likely to cause wrinkles and cracks after being bonded. Excellent printability.
  • the pressure-sensitive adhesive sheet of the present invention contains PMMA (PMMA2) as a tackifier in the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer and the substrate have high affinity, and the glass of the pressure-sensitive adhesive layer as a whole.
  • the transition temperature can also be high. Thereby, even if it is high temperature, it becomes possible to maintain high adhesiveness, and even if 3D decorative molding is performed with the decorative film including the adhesive sheet of the present invention, the adhesive sheet is less likely to float and peel off. High reliability.
  • the compounding part number of a solution or a dispersion means a solid compounding quantity (mass part).
  • MMA methyl methacrylate
  • DMAEMA dimethylaminoethyl methacrylate
  • azobisisobutyronitrile a polymerization reaction was carried out for 5 hours while adding 1 part by mass of nitrile and refluxing.
  • Production Example 7 A pressure-sensitive adhesive composition was prepared in the same manner as in Production Example 1, except that a low-molecular weight polymer having a weight average molecular weight of 60,000 (denoted as C-4) was used as the tackifier (PMMA2).
  • Example 1 As a separator, a PET film having a thickness of 100 ⁇ m (manufactured by Oji F-Tex: 100RL-07 (2)) was prepared. On this separator, the pressure-sensitive adhesive composition obtained in Production Example 1 was applied so that the thickness after drying was 25 ⁇ m to form a coating film, which was dried at 100 ° C. for 3 minutes to form a coating film. Was cured to form an adhesive layer on the separator. Next, a PMMA film having a thickness of 75 ⁇ m (made by Kuraray Co., Ltd .: Parapure IT Grade # 75) formed of PMMA1 as a substrate was bonded to the surface of the pressure-sensitive adhesive layer. Thereby, the adhesive sheet was obtained. About the obtained adhesive sheet, curved-surface bonding suitability, that is, evaluation and reliability evaluation for 3D decorating properties, weather resistance evaluation, water contact angle, and print suitability evaluation were performed.
  • curved-surface bonding suitability that is, evaluation and reliability evaluation for 3D decorating properties, weather resistance evaluation, water contact
  • Example 2 Instead of using the pressure-sensitive adhesive composition obtained in Production Example 1, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition obtained in Production Example 3 was used. About the obtained adhesive sheet, evaluation similar to Example 1 was performed.
  • Example 3 Instead of using the pressure-sensitive adhesive composition obtained in Production Example 1, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition obtained in Production Example 4 was used. About the obtained adhesive sheet, evaluation similar to Example 1 was performed.
  • Example 4 Instead of using the pressure-sensitive adhesive composition obtained in Production Example 1, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition obtained in Production Example 5 was used. About the obtained adhesive sheet, evaluation similar to Example 1 was performed.
  • Example 5 instead of using the pressure-sensitive adhesive composition obtained in Production Example 1, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition obtained in Production Example 6 was used. About the obtained adhesive sheet, evaluation similar to Example 1 was performed.
  • Example 6 instead of using the pressure-sensitive adhesive composition obtained in Production Example 1, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition obtained in Production Example 7 was used. About the obtained adhesive sheet, evaluation similar to Example 1 was performed.
  • Example 1 About the obtained adhesive sheet, the adhesive sheet was obtained by the method similar to Example 1 except having changed the base material into the PET film (Toyobo Co., Ltd. Cosmo Shine A4300 # 75). About the obtained adhesive sheet, evaluation similar to Example 1 was performed.
  • Example 3 (Comparative Example 3) About the obtained adhesive sheet, the adhesive sheet was obtained by the method similar to Example 1 except having changed the base material into PP film. About the obtained adhesive sheet, evaluation similar to Example 1 was performed.
  • ⁇ Evaluation method> Weight average molecular weight
  • a GPC measurement device a high temperature GPC measuring machine with built-in differential refractometer (RI) “HLC-8121GPC-HT” manufactured by Tosoh Corporation is used, and three “TSKgel GMHHR-H (20) HT” manufactured by Tosoh Corporation are connected.
  • the weight average molecular weight was measured using a GPC column.
  • the column temperature was 140 ° C., trichlorobenzene was used as an eluent, and the flow rate was 1.0 ml / min.
  • a calibration curve was prepared using standard polystyrene.
  • ⁇ > Double-circle: There is no wrinkle of a film in a 3D glass curved surface part. ⁇ : Although the wrinkle of the film can be confirmed on the 3D glass curved surface portion, it cannot be confirmed by visual observation.
  • a wrinkle of the film can be visually confirmed on the curved surface portion of the 3D glass.
  • ⁇ Discount> Double-circle: There is no crack of a film in 3D glass curved-surface part.
  • X The crack of a film can be visually confirmed in a 3D glass curved-surface part.
  • ⁇ Floating and peeling> Double-circle: There is no floating and peeling at the interface of a film and an adhesive layer in a 3D glass curved surface part.
  • ⁇ Although floating and peeling at the interface between the film and the pressure-sensitive adhesive layer can be confirmed on the 3D glass curved surface portion, they can be confirmed by enlargement, but cannot be visually confirmed.
  • delta The floating and peeling in the interface of a film and an adhesive layer can be slightly confirmed visually on a 3D glass curved surface part.
  • X The floating and peeling at the interface between the film and the pressure-sensitive adhesive layer can be visually confirmed on the curved surface portion of the 3D glass.
  • ⁇ Bubble> A There are no bubbles at the interface between the film and the pressure-sensitive adhesive layer on the curved surface of the 3D glass.
  • ⁇ Although bubbles can be confirmed at the interface between the film and the pressure-sensitive adhesive layer on the curved surface portion of the 3D glass, they can be confirmed, but cannot be visually confirmed.
  • delta A bubble can be slightly confirmed visually at the interface of a film and an adhesive layer in a 3D glass curved surface part.
  • X Air bubbles can be visually confirmed at the interface between the film and the pressure-sensitive adhesive layer on the curved surface portion of the 3D glass.
  • Transparency when the measured HAZE value (%) was less than 1.5 was accepted, and transparency when it was 1.5 or more was rejected.
  • the transparency when the measured HAZE value is less than 1.0 is “ ⁇ ”
  • the transparency when the measured HAZE value is 1.0 or more and less than 1.5 is “ ⁇ ”.
  • the transparency when the HAZE value was 1.5 or more was expressed as “x”.
  • the 3D glass curved surface has no floating, bubbles, or peeling at the interface between the film and the pressure-sensitive adhesive layer.
  • ⁇ Floating, air bubbles, and peeling at the interface between the film and the pressure-sensitive adhesive layer on the 3D glass curved surface can be confirmed if enlarged, but cannot be visually confirmed.
  • X The floating and peeling at the interface between the film and the pressure-sensitive adhesive layer can be visually confirmed on the curved surface portion of the 3D glass.
  • the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were manufactured by Kyowa Interface Chemical Co., Ltd. so that the base material surface (surface opposite to the pressure-sensitive adhesive layer) side was directed to the surface side and parallel to the ground.
  • An automatic contact angle meter DM-501 was set. 0.2 ⁇ L of ion exchange water was dropped on the set substrate surface and left for 0.5 seconds. Thereafter, the angle between the substrate and the dropped water droplet was measured.
  • Printability Ink A was prepared by mixing 100 parts by mass of ink (trade name: MRX HF-919 Black, Teikoku Ink Co., Ltd.) and 5 parts by weight of a curing agent (trade name: 210 curing agent, Teikoku Ink Co., Ltd.).
  • ink B 100 parts by mass of ink (trade name MRX HF-619 white, manufactured by Teikoku Ink) and 5 parts by mass of a curing agent (trade name 210 curing agent, manufactured by Teikoku Ink) were mixed to prepare ink B.
  • Cellophane tape (trade name CT28, manufactured by Nichiban Co., Ltd.) was peeled off after being brought into close contact with the printed layer as if pressed from above with a finger.
  • 100/100 is the case where the printed layer is not peeled off at all squares
  • 0/100 is the case where the printed layer is peeled off at all squares.
  • the ink adhesion was evaluated according to the following evaluation criteria, and “ ⁇ ” or “ ⁇ ” was set to a level satisfying printability.
  • the pressure-sensitive adhesive sheets obtained in the examples are excellent in curved portion bonding suitability because the base material is PMMA1 and the pressure-sensitive adhesive layer contains PMMA2 as a tackifier.
  • Example 6 since the molecular weight of PMMA2 was large, the transparency and reliability were inferior to those of Examples 1 to 5, but the suitability for bonding the curved surface portion was at a level with no practical problem.
  • Comparative Example 1 since the substrate was not PMMA 1 but PET, wrinkles and cracks were observed, and floating and peeling were also observed. Moreover, in the comparative example 2, since it did not contain PMMA as a tackifier, the remarkable float and peeling were seen.
  • Comparative Example 3 since the base material was PP instead of PMMA1, the occurrence of floating, peeling, and bubbles was observed, and the reliability, weather resistance, and printability were poor.
  • the pressure-sensitive adhesive sheet of the present invention is excellent in adhesion, hardly causes wrinkles and cracks after being bonded, and is less likely to float and peel off.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)

Abstract

Provided is an adhesive sheet for decorative molding, which exhibits excellent adhesiveness and is not susceptible to the occurrence of cracks and wrinkles after bonding, while being also not susceptible to the occurrence of loss of adhesion and separation of the sheet. An adhesive sheet for decorative molding according to the present invention is provided with a laminate in which a base material and an adhesive layer are laminated; and the base material contains a polymethyl methacrylate, while the adhesive layer contains a tackifying agent that contains a polymethyl methacrylate.

Description

加飾成型用粘着シートAdhesive sheet for decorative molding
　本発明は、加飾成型に用いることができる粘着シートに関する。 The present invention relates to an adhesive sheet that can be used for decorative molding.
　三次元表面加飾成型（３Ｄ加飾成型）は、三次元形状の部材に、加飾フィルム等のフィルムを貼り合せることで、基材の表面を加飾させる成型技術であり、近年、電子機材等に対して広く利用されている。３Ｄ加飾成型では、例えば、粘着シートが貼り合わされた加飾フィルム（３Ｄ加飾用粘着シート）を、球面形状又は凹凸形状等の曲面を有する部材に貼り合わせて、１４０℃程度に加熱しながら両者を接着する。この場合、Ｒ（曲面の度合い）の大きい曲面部等に対しては、３Ｄ加飾用粘着シート自体に高い絞り性が要求されることから、粘着シートを形成するための材料の選定も重要となる。 Three-dimensional surface decoration molding (3D decoration molding) is a molding technology that decorates the surface of a substrate by bonding a film such as a decorative film to a three-dimensional member. Etc. are widely used. In 3D decorative molding, for example, a decorative film (adhesive sheet for 3D decoration) to which a pressure-sensitive adhesive sheet is bonded is bonded to a member having a curved surface such as a spherical shape or an uneven shape and heated to about 140 ° C. Glue both together. In this case, for a curved surface portion having a large R (degree of curved surface) or the like, since a high drawability is required for the 3D decorative adhesive sheet itself, selection of a material for forming the adhesive sheet is also important. Become.
　３Ｄ加飾用粘着シートは、主に、基材と粘着剤層とで形成されており、従来はポリ塩化ビニル（ＰＶＣ）が基材として用いられていた。最近では、環境への負担を低減することを考慮して、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレン（ＰＥ）又はポリプロピレン（ＰＰ）基材が使用されることが多い。しかし、ＰＥ又はＰＰ基材は、透明性及び耐候性に劣り、粘着剤との密着性が悪かったことから、この点を改良すべく、柔軟性及び透明性に優れるフッ化ビニリデン樹脂を３Ｄ加飾用粘着シートの基材として使用することが提案されている（特許文献１等を参照）。また、ＰＥ又はＰＰ基材と粘着剤との密着性を改善するために、イソシアネート架橋型の粘着剤にモノアルコールを配合して形成した粘着シートも提案されている（特許文献２等を参照）。 The pressure-sensitive adhesive sheet for 3D decoration is mainly formed of a base material and a pressure-sensitive adhesive layer, and conventionally, polyvinyl chloride (PVC) has been used as the base material. Recently, in consideration of reducing the burden on the environment, a polyethylene terephthalate (PET), polyethylene (PE) or polypropylene (PP) substrate is often used. However, since PE or PP base material is inferior in transparency and weather resistance and has poor adhesion to the pressure-sensitive adhesive, 3D addition of vinylidene fluoride resin excellent in flexibility and transparency is required to improve this point. It has been proposed to be used as a base material for a decorative adhesive sheet (see Patent Document 1). Moreover, in order to improve the adhesiveness of PE or PP base material and an adhesive, the adhesive sheet formed by mix | blending monoalcohol with the isocyanate bridged type adhesive is also proposed (refer patent document 2 etc.). .
特開２００３－２３６９９８号公報JP 2003-236998 A 特開２０１６－１８００１９号公報JP 2016-180019 A
　しかしながら、特許文献１に開示の技術のように、フッ化ビニリデン樹脂を用いる方法では、フッ化ビニリデンが燃焼したときに有毒ガスが発生する問題があり、安全性の観点で課題を残すものであった。また、特許文献２等に開示の技術であっても、基材にＰＰ又はＰＥを用いる以上は、透明性や耐候性が劣るという課題は解決できていなかった。特に、３Ｄ加飾成型では、三次元形状の部材の曲面部に密着する粘着剤層に対しても大きな応力及び負荷がかかるので、十分な粘着性がない場合は、粘着シートの浮きが発生するという問題もある。また、粘着シートの基材がＰＥＴのような材料である場合は、粘着シートの絞り性が十分でないため、粘着シートに皺及び割れが発生する問題があった。 However, as in the technique disclosed in Patent Document 1, the method using a vinylidene fluoride resin has a problem that a toxic gas is generated when the vinylidene fluoride is combusted, which leaves a problem in terms of safety. It was. Moreover, even if it is a technique disclosed by patent document 2 etc., as long as PP or PE is used for a base material, the subject that transparency and a weather resistance are inferior could not be solved. In particular, in 3D decorative molding, a large stress and load are applied to the pressure-sensitive adhesive layer that is in close contact with the curved surface portion of the three-dimensional shaped member. There is also a problem. Moreover, when the base material of the adhesive sheet is a material such as PET, there is a problem that wrinkles and cracks occur in the adhesive sheet because the squeezability of the adhesive sheet is not sufficient.
　本発明は、上記に鑑みてなされたものであり、密着性に優れ、貼り合わせ後に皺及び割れが発生しにくく、しかも、浮き及び剥がれも起こりにくい加飾成型用粘着シートを提供することを目的とする。 The present invention has been made in view of the above, and an object of the present invention is to provide a decorative molding pressure-sensitive adhesive sheet that has excellent adhesion, is less likely to cause wrinkles and cracks after bonding, and is less likely to float and peel off. And
　本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、ポリメタクリル酸メチルを含む基材と、ポリメタクリル酸メチルを含む粘着付与剤を含有する粘着剤層とを用いることにより、上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have used a base material containing polymethyl methacrylate and an adhesive layer containing a tackifier containing polymethyl methacrylate, The inventors have found that the above object can be achieved and have completed the present invention.
　すなわち、本発明は、例えば、以下の項に記載の発明を包含する。
項１．基材及び粘着剤層が積層された積層体を備え、
　前記基材はポリメタクリル酸メチルを含有し、
　前記粘着剤層は、ポリメタクリル酸メチルを含む粘着付与剤を含有する、加飾成型用粘着シート。
項２．前記粘着付与剤に含まれるポリメタクリル酸メチルの重量平均分子量（Ｍｗ）が５００～５００００である、項１に記載の加飾成型用粘着シート。
項３．前記粘着剤層は、ポリメタクリル酸メチル以外のベースポリマー（Ａ）の架橋構造体を含み、
　前記ベースポリマー（Ａ）の構成単位は、（メタ）アクリル酸エステル単量体単位（ａ１）及び架橋性官能基を有する（メタ）アクリル単量体単位（ａ２）を含有する、項１又は２に記載の加飾成型用粘着シート。
項４．前記基材の粘着剤層側と逆の面の水接触角が４０°～９５°である、項１～３のいずれか１項に記載の加飾成型用粘着シート。
項５．前記粘着剤層の前記基材側と逆の面には、セパレータが貼り合わされている、項１～４のいずれか１項に記載の加飾成型用粘着シート。 That is, the present invention includes, for example, the inventions described in the following sections.
Item 1. Provided with a laminate in which a base material and an adhesive layer are laminated,
The substrate contains polymethyl methacrylate;
The pressure-sensitive adhesive layer is a pressure-sensitive adhesive sheet for decorative molding, containing a tackifier containing polymethyl methacrylate.
Item 2. Item 2. The decorative molding pressure-sensitive adhesive sheet according to Item 1, wherein the polymethyl methacrylate contained in the tackifier has a weight average molecular weight (Mw) of 500 to 50,000.
Item 3. The pressure-sensitive adhesive layer includes a crosslinked structure of a base polymer (A) other than polymethyl methacrylate,
Item 1 or 2 wherein the structural unit of the base polymer (A) contains a (meth) acrylic acid ester monomer unit (a1) and a (meth) acrylic monomer unit (a2) having a crosslinkable functional group. The pressure-sensitive adhesive sheet for decorative molding described in 1.
Item 4. Item 4. The decorative molding pressure-sensitive adhesive sheet according to any one of items 1 to 3, wherein a water contact angle on a surface opposite to the pressure-sensitive adhesive layer side of the substrate is 40 ° to 95 °.
Item 5. Item 5. The decorative molding pressure-sensitive adhesive sheet according to any one of Items 1 to 4, wherein a separator is bonded to a surface of the pressure-sensitive adhesive layer opposite to the substrate side.
　本発明に係る加飾成型用粘着シートは、密着性に優れ、貼り合わせ後に皺及び割れが発生しにくく、しかも、浮き及び剥がれも起こりにくい。 The decorative molding pressure-sensitive adhesive sheet according to the present invention is excellent in adhesion, hardly causes wrinkles and cracks after being bonded, and is also less likely to float and peel off.
（ａ）～（ｄ）はそれぞれ本発明に係る加飾成型用粘着シートの実施形態の一例を示す概略の断面図である。(A)-(d) is a schematic sectional drawing which shows an example of embodiment of the pressure-sensitive adhesive sheet for decorative molding according to the present invention.
　以下、本発明の実施形態について詳細に説明する。なお、本明細書中において、「含有」及び「含む」なる表現については、「含有」、「含む」、「実質的にからなる」及び「のみからなる」という概念を含む。 Hereinafter, embodiments of the present invention will be described in detail. In the present specification, the expressions “containing” and “including” include the concepts of “containing”, “including”, “consisting essentially of”, and “consisting only of”.
　本発明の加飾成型用粘着シートは、基材及び粘着剤層が積層された積層体を備え、前記基材はポリメタクリル酸メチルを含有し、前記粘着剤層は、ポリメタクリル酸メチルを含む粘着付与剤を含有する。なお、以下、本発明の加飾成型用粘着シートを「粘着シート」と略記することがある。 The pressure-sensitive adhesive sheet for decorative molding of the present invention comprises a laminate in which a base material and a pressure-sensitive adhesive layer are laminated, the base material contains polymethyl methacrylate, and the pressure-sensitive adhesive layer contains polymethyl methacrylate. Contains a tackifier. Hereinafter, the pressure-sensitive adhesive sheet for decorative molding of the present invention may be abbreviated as “pressure-sensitive adhesive sheet”.
　基材は、粘着剤層を支持するための部材である。 The base material is a member for supporting the pressure-sensitive adhesive layer.
　なお、以下においては、基材に含まれるポリメタクリル酸メチル（ＰＭＭＡ）と、粘着付与剤に含まれるＰＭＭＡとを区別するために、基材に含まれるＰＭＭＡを「ＰＭＭＡ１」、粘着付与剤に含まれるＰＭＭＡを「ＰＭＭＡ２」と表記する。 In the following, in order to distinguish between polymethyl methacrylate (PMMA) contained in the base material and PMMA contained in the tackifier, “PMMA1”, which is contained in the base material, is included in the tackifier. The PMMA to be displayed is expressed as “PMMA2”.
　図１（ａ）～（ｄ）は、本発明の加飾成型用粘着シートの基材及び粘着剤層の積層構造の一例を示す断面図である。図１（ａ）の形態のように、基材は、３Ｄ加飾性を損なわない限り、ＰＭＭＡ１のみで構成されてもよいし、ＰＭＭＡ１と他の材料との共重合体もしくはブレンドであってもよい。該共重合体もしくはブレンド基材における他の材料としては、フィルム基材として使用される公知の材料を広く使用でき、例えば、ＰＭＭＡ以外のアクリル樹脂、ポリスチレン、ＰＥ、ＰＰ、ＰＥＴ、ポリアミド、ポリイミド、シリコーン樹脂、ポリカーボネート（ＰＣ）、スチレンゴム、イソプレンゴム、イソブチレンゴム、エチレン－プロピレン－ジエンゴム、アクリルゴム等が例示される。また、図１（ｂ）に示すように、基材は、ＰＭＭＡ１と他の材料との積層基材であってもよい。該積層基材における他の材料としては、フィルムの基材として使用されている公知の材料を広く使用でき、例えば、ＰＭＭＡ以外のアクリル樹脂、ポリスチレン、ＰＥ、ＰＰ、ＰＥＴ、ポリアミド、ポリイミド、シリコーン樹脂、ポリカーボネート（ＰＣ）等が例示される。 1 (a) to 1 (d) are cross-sectional views showing an example of a laminated structure of a base material and a pressure-sensitive adhesive layer of the decorative molding pressure-sensitive adhesive sheet of the present invention. As shown in FIG. 1 (a), the substrate may be composed of only PMMA1 as long as the 3D decoration is not impaired, or may be a copolymer or blend of PMMA1 and other materials. Good. As other materials in the copolymer or blend substrate, known materials used as a film substrate can be widely used. For example, acrylic resins other than PMMA, polystyrene, PE, PP, PET, polyamide, polyimide, Examples thereof include silicone resin, polycarbonate (PC), styrene rubber, isoprene rubber, isobutylene rubber, ethylene-propylene-diene rubber, and acrylic rubber. Moreover, as shown in FIG.1 (b), the base material may be a laminated base material of PMMA1 and another material. As other materials in the laminated substrate, known materials used as a film substrate can be widely used. For example, acrylic resins other than PMMA, polystyrene, PE, PP, PET, polyamide, polyimide, silicone resin And polycarbonate (PC).
　ＰＭＭＡ１と他の材料とを共重合もしくはブレンドする場合、ＰＭＭＡ１の含有量は、基材の全質量に対して、７０質量％以上であり、８０質量％以上であることが好ましく、９０質量％以上であることがより好ましい。 When PMMA1 and other materials are copolymerized or blended, the content of PMMA1 is 70% by mass or more, preferably 80% by mass or more, and 90% by mass or more with respect to the total mass of the substrate. It is more preferable that
　基材がＰＭＭＡ１と他の材料との積層基材である場合、ＰＭＭＡ１と他の材料との厚み比は、積層基材全体に対しＰＭＭＡ１が１０％以上、好ましくは１５％以上、より好ましくは２０％以上である。なお、積層基材に用いられるＰＭＭＡ１は、ＰＭＭＡ１のみで構成されてもよいし、ＰＭＭＡ１と他の材料との共重合体であってもよい。 When the substrate is a laminated substrate of PMMA1 and another material, the thickness ratio of PMMA1 and the other material is such that PMMA1 is 10% or more, preferably 15% or more, more preferably 20 with respect to the entire laminated substrate. % Or more. In addition, PMMA1 used for a laminated base material may be comprised only by PMMA1, and the copolymer of PMMA1 and another material may be sufficient as it.
　基材は、粘着剤層が貼合される面とは逆側の面、つまり加飾成型される面の水接触角が４０°～９５°、好ましくは５０°～９０°である。水接触角が前記範囲内であれば、優れた印刷適性を付与できる。基材の水接触角を上記範囲にする方法としては、上記水接触角の範囲に入る所望の樹脂を積層する方法、上記接触角の範囲に入る所望の易接着層を設ける方法、上記接触角の範囲に入るようにコロナ照射をする方法等があげられる。 The base material has a water contact angle of 40 ° to 95 °, preferably 50 ° to 90 °, on the surface opposite to the surface to which the pressure-sensitive adhesive layer is bonded, that is, the surface to be decoratively molded. If the water contact angle is within the above range, excellent printability can be imparted. As a method for setting the water contact angle of the substrate in the above range, a method of laminating a desired resin that falls within the range of the water contact angle, a method of providing a desired easy-adhesive layer that falls within the range of the contact angle, A method of corona irradiation so as to fall within the range is mentioned.
　図１（ｃ）は、単層の基材（ＰＭＭＡ１）に易接着層が設けられた場合の加飾成型用粘着シートであり、この場合、易接着層は、基材の粘着剤層側とは逆側の面に設けられる。図１（ｄ）は、基材が前記積層基材である場合の加飾成型用粘着シートであり、この場合も易接着層は、積層基材の粘着剤層側とは逆側の面に設けられる。易接着層の種類は特に限定されず、例えば、粘着シートとして適用され得る公知の易接着層や印刷適性を付与するための易接着層を広く適用することができる。 FIG.1 (c) is a pressure-sensitive adhesive sheet for decorative molding in the case where an easy-adhesion layer is provided on a single-layer base material (PMMA1). In this case, the easy-adhesion layer includes the adhesive layer side of the base material and Is provided on the opposite surface. FIG.1 (d) is a pressure-sensitive adhesive sheet for decorative molding when the base material is the laminated base material, and in this case, the easy-adhesion layer is on the surface opposite to the pressure-sensitive adhesive layer side of the laminated base material. Provided. The kind of easily bonding layer is not specifically limited, For example, the well-known easily bonding layer which can be applied as an adhesive sheet and the easily bonding layer for providing printability can be applied widely.
　基材は、例えば、ＰＭＭＡ１を含む原料を成型することで形成することができる。あるいは、市販のＰＭＭＡフィルムを基材として使用することができる。ＰＭＭＡ１を含む原料を用いて基材を成型する場合、その成型方法は特に限定されず、公知の成型方法を採用することができる。ＰＭＭＡ１を含む原料の種類も特に限定されない。ＰＭＭＡ１を含む原料は、ＰＭＭＡのみであってもよいし、あるいは、ＰＭＭＡに加えて前述の他の材料を含むことができる。 The base material can be formed, for example, by molding a raw material containing PMMA1. Or a commercially available PMMA film can be used as a base material. When a base material is molded using a raw material containing PMMA 1, the molding method is not particularly limited, and a known molding method can be employed. The kind of raw material containing PMMA 1 is not particularly limited. The raw material containing PMMA 1 may be only PMMA, or may contain other materials described above in addition to PMMA.
　ＰＭＭＡ１の重量平均分子量（Ｍｗ）は特に限定されず、例えば、一般のＰＭＭＡフィルムと同様とすることができる。 The weight average molecular weight (Mw) of PMMA 1 is not particularly limited, and can be the same as that of a general PMMA film, for example.
　基材の厚みは特に限定されず、例えば、５～１００μｍである。 The thickness of the substrate is not particularly limited and is, for example, 5 to 100 μm.
　基材は、シート状又はフィルム状に形成される。基材の表面は平坦とすることができ、また、凹凸を有することもできる。基材は、単層構造及び多層構造のいずれの構造を有していてもよい。 The base material is formed in a sheet shape or a film shape. The surface of the base material can be flat and can have irregularities. The substrate may have either a single layer structure or a multilayer structure.
　粘着剤層は、基材上に形成される層であり、粘着性を発揮させるための層である。粘着剤層は、基材上に直接形成することができ、また、本発明の効果が阻害されない限りは、基材と粘着剤層との間に他の層を介在させることができる。 The pressure-sensitive adhesive layer is a layer formed on the base material and is a layer for exerting adhesiveness. The pressure-sensitive adhesive layer can be formed directly on the substrate, and other layers can be interposed between the substrate and the pressure-sensitive adhesive layer as long as the effects of the present invention are not impaired.
　粘着剤層は後記粘着剤組成物を用いて形成することができる。該粘着剤組成物は、ＰＭＭＡ２を含む粘着付与剤を含有する。本発明でいう粘着付与剤は、粘着剤層に対して粘着性を付与するための助剤として作用することができる成分であり、一般的にタッキファイヤと称される成分である。粘着剤層において、粘着付与剤の含有量は、後記ベースポリマー（Ａ）１００質量部あたり、１～３５質量部、好ましくは５～３０質量部、さらに好ましくは１０～２５質量部とすることができる。この場合、粘着剤層に対して優れた粘着性を付与でき、また、３Ｄ加飾成型させる部材に粘着シートを貼り合わせ後においても皺及び割れがより発生しにくく、しかも、浮き及び剥がれもより起こりにくい。 The pressure-sensitive adhesive layer can be formed using a pressure-sensitive adhesive composition described later. The pressure-sensitive adhesive composition contains a tackifier containing PMMA2. The tackifier referred to in the present invention is a component that can act as an auxiliary agent for imparting tackiness to the pressure-sensitive adhesive layer, and is a component generally referred to as tackifier. In the pressure-sensitive adhesive layer, the content of the tackifier is 1 to 35 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight per 100 parts by weight of the base polymer (A) described later. it can. In this case, excellent adhesiveness can be imparted to the pressure-sensitive adhesive layer, and wrinkles and cracks are less likely to occur even after the pressure-sensitive adhesive sheet is bonded to the member to be 3D-decorated, and moreover, floating and peeling are more likely. Hard to happen.
　粘着付与剤に含まれるＰＭＭＡ２の含有割合は、粘着付与剤の全質量に対して、５０質量％以上であり、８０質量％以上であることが好ましく、９０質量％以上であることがより好ましく、９９質量％以上であることが特に好ましい。粘着付与剤に含まれるＰＭＭＡ２の含有割合は、１００質量％とすることができる。 The content ratio of PMMA2 contained in the tackifier is 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, based on the total mass of the tackifier. It is particularly preferably 99% by mass or more. The content ratio of PMMA2 contained in the tackifier can be 100% by mass.
　粘着付与剤に含まれるポリメタクリル酸メチル（ＰＭＭＡ２）の種類は、ベースポリマーとの相溶性を阻害しない限り、特に限定されず、例えば、公知のＰＭＭＡを広く採用することができる。ＰＭＭＡ２は、例えば、市販されている材料を使用することができ、あるいは、公知の重合法、例えば、ラジカル重合によって製造することもできる。 The type of polymethyl methacrylate (PMMA2) contained in the tackifier is not particularly limited as long as the compatibility with the base polymer is not inhibited. For example, known PMMA can be widely adopted. PMMA2 can use the material marketed, for example, or can also be manufactured by a well-known polymerization method, for example, radical polymerization.
　ＰＭＭＡ２は、ポリメタクリル酸メチルのホモポリマーであってもよいし、あるいは、粘着付与剤としての効果が阻害されない限りは、メタクリル酸メチルと他のアクリル単量体との共重合体であってもよい。他のアクリル単量体としては、例えば、メタクリル酸ジメチルアミノエチル（ＤＭＡＥＭＡ）等のＮ－アルキル置換アミノ基含有メタクリル酸エステルを挙げることができる。 PMMA2 may be a homopolymer of polymethyl methacrylate, or may be a copolymer of methyl methacrylate and another acrylic monomer as long as the effect as a tackifier is not inhibited. Good. Examples of other acrylic monomers include N-alkyl-substituted amino group-containing methacrylic acid esters such as dimethylaminoethyl methacrylate (DMAEMA).
　ＰＭＭＡ２がメタクリル酸メチルと他のアクリル単量体との共重合体である場合、メタクリル酸メチルの含有量は、メタクリル酸メチル及び他のアクリル単量体の全質量に対して、７０質量％以上とすることができ、８０質量％以上であることが好ましく、９０質量％以上であることが特に好ましい。 When PMMA2 is a copolymer of methyl methacrylate and another acrylic monomer, the content of methyl methacrylate is 70% by mass or more based on the total mass of methyl methacrylate and other acrylic monomers. It is preferable that it is 80 mass% or more, and it is especially preferable that it is 90 mass% or more.
　ＰＭＭＡ２の重量平均分子量（Ｍｗ）は、特に限定されず、例えば、５００～５００００とすることができる。この場合、粘着シートの粘着性能がさらに優れ、また、粘着シートを３Ｄ加飾成型させる部材に貼り合わせ後でも、皺及び割れがより発生しにくく、しかも、浮き及び剥がれもより起こりにくい。 The weight average molecular weight (Mw) of PMMA2 is not particularly limited, and can be, for example, 500 to 50,000. In this case, the adhesive performance of the pressure-sensitive adhesive sheet is further improved, and even after the pressure-sensitive adhesive sheet is bonded to a member for 3D decorative molding, wrinkles and cracks are less likely to occur, and further, floating and peeling are less likely to occur.
　粘着付与剤は、本発明の効果が阻害されない限りは、ＰＭＭＡ２以外の他の成分を含むことができる。他の成分としては、粘着用のシートに適用されている公知の粘着付与樹脂等を広く使用でき、例えば、スチレン樹脂、テルペン樹脂、ロジンエステル等が挙げられる。 The tackifier can contain other components other than PMMA2 as long as the effects of the present invention are not impaired. As other components, known tackifying resins and the like applied to the adhesive sheet can be widely used, and examples thereof include styrene resins, terpene resins, and rosin esters.
　粘着剤層には、粘着付与剤以外の成分が含まれる。例えば、粘着剤層には、粘着付与剤以外に、粘着剤層のマトリックス成分となるポリマーが含まれ得る。 The adhesive layer contains components other than the tackifier. For example, the pressure-sensitive adhesive layer may contain a polymer that becomes a matrix component of the pressure-sensitive adhesive layer in addition to the tackifier.
　具体的に粘着剤層は、ポリメタクリル酸メチル以外のベースポリマー（Ａ）の架橋構造体を含むことができる。前記ベースポリマー（Ａ）の構成単位は、（メタ）アクリル酸エステル単量体単位（ａ１）及び架橋性官能基を有する（メタ）アクリル単量体単位（ａ２）を含有することができる。ベースポリマー（Ａ）の架橋構造は、粘着剤層のマトリックス成分となり得る。 Specifically, the pressure-sensitive adhesive layer can contain a crosslinked structure of a base polymer (A) other than polymethyl methacrylate. The structural unit of the base polymer (A) can contain a (meth) acrylic acid ester monomer unit (a1) and a (meth) acrylic monomer unit (a2) having a crosslinkable functional group. The crosslinked structure of the base polymer (A) can be a matrix component of the pressure-sensitive adhesive layer.
　ベースポリマー（Ａ）の架橋構造体は、例えば、ＰＭＭＡ以外のベースポリマー（Ａ）と、後記する架橋剤（Ｂ）との反応で形成される。架橋剤（Ｂ）は、ベースポリマー（Ａ）と反応することができる架橋剤である。 The crosslinked structure of the base polymer (A) is formed, for example, by a reaction between a base polymer (A) other than PMMA and a crosslinking agent (B) described later. The crosslinking agent (B) is a crosslinking agent that can react with the base polymer (A).
　ここでいう「ＰＭＭＡ以外のベースポリマー（Ａ）」とは、ベースポリマー（Ａ）がＰＭＭＡホモポリマーでないことを意味する。つまり、ベースポリマー（Ａ）が共重合体である場合は、共重合体の構成成分としてＰＭＭＡ成分を含むことができる。 Here, “base polymer (A) other than PMMA” means that the base polymer (A) is not a PMMA homopolymer. That is, when the base polymer (A) is a copolymer, a PMMA component can be included as a constituent component of the copolymer.
　前記（メタ）アクリル酸エステル単量体単位（ａ１）とは、（メタ）アクリル酸エステル単量体が重合された場合に形成される繰り返し構造単位を示し、単量体そのものを示すわけではない。同様に、架橋性官能基を有する（メタ）アクリル単量体単位（ａ２）とは、架橋性官能基を有する（メタ）アクリル単量体が重合された場合に形成される繰り返し構造単位を示し、単量体そのものを示すわけではない。 The (meth) acrylic acid ester monomer unit (a1) indicates a repeating structural unit formed when the (meth) acrylic acid ester monomer is polymerized, and does not indicate the monomer itself. . Similarly, the (meth) acrylic monomer unit (a2) having a crosslinkable functional group indicates a repeating structural unit formed when a (meth) acrylic monomer having a crosslinkable functional group is polymerized. It does not indicate the monomer itself.
　なお、本明細書では「（メタ）アクリル」とは「アクリルもしくはメタクリル」を意味し、「（メタ）アクリ」は、「アクリもしくはメタクリ」を意味する。例えば、「（メタ）アクリル酸」との記載は「アクリル酸もしくはメタクリル酸」との記載と同義である。 In this specification, “(meth) acryl” means “acryl or methacryl” and “(meth) acryl” means “acryl or methacryl”. For example, the description “(meth) acrylic acid” is synonymous with the description “acrylic acid or methacrylic acid”.
　（メタ）アクリル酸エステル単量体単位（ａ１）は、（メタ）アクリル酸エステル単量体で形成することができる。ここでいう（メタ）アクリル酸エステル単量体は、架橋剤（Ｂ）と反応する官能基を有していない単量体である。 (Meth) acrylate monomer unit (a1) can be formed of a (meth) acrylate monomer. The (meth) acrylic acid ester monomer here is a monomer having no functional group that reacts with the crosslinking agent (B).
　（メタ）アクリル酸エステル単量体の種類は特に限定されず、例えば、公知の（メタ）アクリル酸エステル単量体を使用することができる。（メタ）アクリル酸エステル単量体の具体例としては、（メタ）アクリル酸エステルのエステル部位の炭素数が１～２０である炭化水素基である化合物を挙げることができる。炭化水素基は、直鎖状、分岐状、環状及び籠状のいずれの構造であってもよい。また、炭化水素基は、飽和炭化水素基及び不飽和炭化水素基のいずれの基であってもよい。さらに炭化水素基は、置換基を有していてもよい。 The type of the (meth) acrylate monomer is not particularly limited, and for example, a known (meth) acrylate monomer can be used. Specific examples of the (meth) acrylic acid ester monomer include compounds having a hydrocarbon group having 1 to 20 carbon atoms in the ester moiety of the (meth) acrylic acid ester. The hydrocarbon group may have a linear, branched, cyclic or cage structure. Further, the hydrocarbon group may be either a saturated hydrocarbon group or an unsaturated hydrocarbon group. Furthermore, the hydrocarbon group may have a substituent.
　（メタ）アクリル酸エステル単量体のより詳しい具体例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸ｉ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ｎ－ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸イソボルニル、（メタ）アクリル酸アダマンチル、（メタ）アクリル酸フェニル等を挙げることができる。 Specific examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) N-butyl acrylate, 2-ethylhexyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, ( Examples include n-octyl (meth) acrylate, isooctyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, and phenyl (meth) acrylate.
　ベースポリマー（Ａ）は、（メタ）アクリル酸エステル単量体単位（ａ１）を１種のみ含むことができるし、あるいは、２種以上を含むことができる。 The base polymer (A) can contain only one type of (meth) acrylic acid ester monomer unit (a1), or can contain two or more types.
　架橋性官能基を有する（メタ）アクリル単量体単位（ａ２）は、架橋性官能基を有する（メタ）アクリル単量体で形成することができる。ここでいう架橋性官能基を有する（メタ）アクリル単量体は、架橋剤（Ｂ）と反応する官能基を有する（メタ）アクリル単量体であって、前記（メタ）アクリル酸エステル単量体とは異なる単量体である。 The (meth) acrylic monomer unit (a2) having a crosslinkable functional group can be formed of a (meth) acrylic monomer having a crosslinkable functional group. The (meth) acrylic monomer having a crosslinkable functional group here is a (meth) acrylic monomer having a functional group that reacts with the crosslinker (B), and the (meth) acrylic acid ester monomer It is a monomer different from the body.
　架橋性官能基を有する（メタ）アクリル単量体における架橋性官能基としては、架橋剤（Ｂ）と反応する官能基である限りは、特に限定されず、架橋剤（Ｂ）の種類に応じて適宜選択することができる。例えば、架橋性官能基としては、カルボキシル基、ヒドロキシ基、アミノ基、アミド基、スルホ基、スルホン酸、エポキシ基、クロロ基、フルオロ基等を挙げることができる。 The crosslinkable functional group in the (meth) acrylic monomer having a crosslinkable functional group is not particularly limited as long as it is a functional group that reacts with the crosslinker (B), depending on the type of the crosslinker (B). Can be selected as appropriate. For example, examples of the crosslinkable functional group include a carboxyl group, a hydroxy group, an amino group, an amide group, a sulfo group, a sulfonic acid, an epoxy group, a chloro group, and a fluoro group.
　架橋性官能基を有する（メタ）アクリル単量体は、１分子中に架橋性官能基を一つ有することができ、また、架橋性官能基を二つ以上有することもできる。架橋性官能基を有する（メタ）アクリル単量体は、１分子中に架橋性官能基を二つ以上有する場合、架橋性官能基は同種及び異種のいずれであってもよい。 The (meth) acrylic monomer having a crosslinkable functional group can have one crosslinkable functional group in one molecule, and can also have two or more crosslinkable functional groups. When the (meth) acrylic monomer having a crosslinkable functional group has two or more crosslinkable functional groups in one molecule, the crosslinkable functional group may be the same or different.
　架橋性官能基を有する（メタ）アクリル単量体のより詳しい具体例としては、（メタ）アクリル酸、マレイン酸、無水マレイン酸、イタコン酸、フマル酸、シトラコン酸、２－（メタ）アクリロイロキシエチルフタル酸、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルマレイン酸、（メタ）アクリル酸カルボキシルエチル、カルボキシポリカプロラクトンモノ（メタ）アクリレート、（メタ）アクリルアミド、ビニルアルコール、（メタ）アクリル酸ヒドロキシアルキル、ヒドロキシアルキル（メタ）アクリルアミド等が挙げられる。 Specific examples of the (meth) acrylic monomer having a crosslinkable functional group include (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, citraconic acid, 2- (meth) acryloyl. Roxyethylphthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxylethyl (meth) acrylate, carboxypolycaprolactone mono (meth) acrylate, (meth) acrylamide , Vinyl alcohol, hydroxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylamide and the like.
　前記（メタ）アクリル酸ヒドロキシアルキルとしては、２－ヒドロキシエチル（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、６－ヒドロキシヘキシル（メタ）アクリレート、５－ヒドロキシペンチル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、２，２－ジメチル２－ヒドロキシエチル（メタ）アクリレート、３－クロロ２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシ３－フェノキシプロピル（メタ）アクリレート、２－ヒドロキシ３－フェノキシプロピル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート等が挙げられる。前記ヒドロキシアルキル（メタ）アクリルアミドとしては、Ｎ－ヒドロキシプロピル（メタ）アクリルアミド等が挙げられる。 Examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 2-hydroxy Butyl (meth) acrylate, 2,2-dimethyl 2-hydroxyethyl (meth) acrylate, 3-chloro 2-hydroxypropyl (meth) acrylate, 2-hydroxy 3-phenoxypropyl (meth) acrylate, 2-hydroxy 3-phenoxy Examples thereof include propyl (meth) acrylate and 8-hydroxyoctyl (meth) acrylate. Examples of the hydroxyalkyl (meth) acrylamide include N-hydroxypropyl (meth) acrylamide.
　ベースポリマー（Ａ）は、架橋性官能基を有する（メタ）アクリル単量体単位（ａ２）を１種のみ含むことができるし、あるいは、２種以上を含むことができる。 The base polymer (A) can contain only one type of (meth) acrylic monomer unit (a2) having a crosslinkable functional group, or can contain two or more types.
　なお、以下では（メタ）アクリル酸エステル単量体単位（ａ１）を単に「単量体単位（ａ１）」と略記する。また、架橋性官能基を有する（メタ）アクリル単量体単位（ａ２）を単に「単量体単位（ａ２）」と略記する。 In the following, the (meth) acrylate monomer unit (a1) is simply abbreviated as “monomer unit (a1)”. The (meth) acrylic monomer unit (a2) having a crosslinkable functional group is simply abbreviated as “monomer unit (a2)”.
　ベースポリマー（Ａ）は、本発明の効果が阻害されない限りは、単量体単位（ａ１）及び単量体単位（ａ２）以外のその他単量体単位を含有することができる。 The base polymer (A) can contain other monomer units other than the monomer unit (a1) and the monomer unit (a2) as long as the effects of the present invention are not inhibited.
　ベースポリマー（Ａ）を形成する全構成単位あたり、単量体単位（ａ１）の含有割合を５０～９９．９質量％とすることができ、好ましくは６０～９９．５質量％、さらに好ましくは７０～９９.０質量％とすることができる。 The content ratio of the monomer unit (a1) can be 50 to 99.9% by mass, preferably 60 to 99.5% by mass, more preferably all the structural units forming the base polymer (A). It can be 70 to 99.0% by mass.
　ベースポリマー（Ａ）は、単量体単位（ａ１）、単量体単位（ａ２）及び前記その他単量体単位がランダムに配列したいわゆるランダム共重合体とすることができる。あるいは、ベースポリマー（Ａ）は、ブロックポリマー等、その他の構造を有することもできる。 The base polymer (A) can be a so-called random copolymer in which the monomer unit (a1), the monomer unit (a2) and the other monomer units are randomly arranged. Alternatively, the base polymer (A) can have other structures such as a block polymer.
　架橋剤（Ｂ）は、ベースポリマー（Ａ）を架橋させるための成分である。特に、架橋剤（Ｂ）は、ベースポリマー（Ａ）中の単量体単位（ａ２）の架橋性官能基と反応することができる成分である。 The crosslinking agent (B) is a component for crosslinking the base polymer (A). In particular, the crosslinking agent (B) is a component capable of reacting with the crosslinkable functional group of the monomer unit (a2) in the base polymer (A).
　架橋剤（Ｂ）は、単量体単位（ａ２）の架橋性官能基と反応することができる限りは、その種類は特に限定されず、公知の架橋剤を広く用いることができる。 The type of the crosslinking agent (B) is not particularly limited as long as it can react with the crosslinking functional group of the monomer unit (a2), and a wide variety of known crosslinking agents can be used.
　架橋剤（Ｂ）としては、例えば、エポキシ架橋剤、イソシアネート架橋剤等を挙げることができる。 Examples of the crosslinking agent (B) include an epoxy crosslinking agent and an isocyanate crosslinking agent.
　イソシアネート架橋剤の種類は特に限定されず、公知の化合物を広く使用できる。このようなイソシアネート架橋剤としては、トリレンジイソシアネート、クロロフェニ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、ブチレンジイソシアネート、ヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、水添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ポリイソシアネート；シクロペンチレンジイソシアネート、シクロへキシレンジイソシアネート等の脂環族イソシアネート類、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート等の芳香族イソシアネート；が例示される。イソシアネート架橋剤は、単独又は異なる２種以上を混合して使用することができる。また、上述したジイソシアネートから得られるアダクト体、ヌレート体、ビュレット体等の３官能の誘導体をイソシアネート架橋剤として用いることがより好ましい。 The type of the isocyanate crosslinking agent is not particularly limited, and a wide variety of known compounds can be used. Examples of such isocyanate crosslinking agents include tolylene diisocyanate, chlorophenylene diisocyanate, diphenylmethane diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and xylylene diisocyanate; cyclopentylene diisocyanate, cyclohexane And alicyclic isocyanates such as hexylene diisocyanate, and aromatic isocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4′-diphenylmethane diisocyanate. An isocyanate crosslinking agent can be used individually or in mixture of 2 or more types. Further, it is more preferable to use a trifunctional derivative such as an adduct, a nurate or a burette obtained from the above-mentioned diisocyanate as an isocyanate crosslinking agent.
　エポキシ架橋剤としては、例えば、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、ネオペンチル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、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミン、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサノン、トリメチロールプロパンポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル等が挙げられる。 Examples of the epoxy crosslinking agent include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol. Diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexanone, trimethylolpropane polyglycidyl ether, diglycerol polyglycidyl Examples include ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, and the like.
　中でも４官能であるＮ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミン、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサノンは少量の添加量で架橋効果が発現するため好ましい。 Among these, tetrafunctional N, N, N ′, N′-tetraglycidyl-m-xylenediamine and 1,3-bis (N, N-diglycidylaminomethyl) cyclohexanone exhibit a crosslinking effect with a small addition amount. Therefore, it is preferable.
　粘着剤層に含まれるベースポリマー（Ａ）の架橋構造体、及び、粘着付与剤として含まれるＰＭＭＡ２の含有量は特に限定されない。例えば、粘着剤層中の前記架橋構造体１００質量部あたり、粘着付与剤として含まれるＰＭＭＡ２を１～３５質量部、好ましくは５～３０質量部、さらに好ましくは１０～２５質量部である。この場合、粘着剤層に対して優れた粘着性を付与でき、また、３Ｄ加飾成型させる部材に粘着シートを貼り合わせ後においても皺及び割れがより発生しにくく、しかも、浮き及び剥がれもより起こりにくい。 The content of the cross-linked structure of the base polymer (A) contained in the pressure-sensitive adhesive layer and PMMA2 contained as a tackifier is not particularly limited. For example, the amount of PMMA2 contained as a tackifier is 1 to 35 parts by mass, preferably 5 to 30 parts by mass, and more preferably 10 to 25 parts by mass per 100 parts by mass of the crosslinked structure in the adhesive layer. In this case, excellent adhesiveness can be imparted to the pressure-sensitive adhesive layer, and wrinkles and cracks are less likely to occur even after the pressure-sensitive adhesive sheet is bonded to the member to be 3D-decorated, and moreover, floating and peeling are more likely. Hard to happen.
　粘着剤層の厚みは５～５０μｍ、好ましくは８～４５μｍ、より好ましくは１０～３５μｍである。 The thickness of the pressure-sensitive adhesive layer is 5 to 50 μm, preferably 8 to 45 μm, more preferably 10 to 35 μm.
　粘着剤層は、基材の全面に形成され得るが、本発明の効果が阻害されない程度であれば、基材の全面に形成されていなくてもよい。 The pressure-sensitive adhesive layer can be formed on the entire surface of the substrate, but may not be formed on the entire surface of the substrate as long as the effect of the present invention is not hindered.
　粘着剤層の形成方法は特に限定されない。例えば、粘着剤組成物を使用して、粘着剤層を形成する工程（以下、「粘着剤層形成工程」という）を具備する方法によって形成することができる。粘着剤層形成工程では、例えば、粘着剤組成物を基材上に塗布し、硬化させることで、基材上に粘着剤層が形成される。これにより、基材及び粘着剤層で形成される積層体が得られる。 The method for forming the pressure-sensitive adhesive layer is not particularly limited. For example, it can be formed by a method comprising using a pressure-sensitive adhesive composition to form a pressure-sensitive adhesive layer (hereinafter referred to as “pressure-sensitive adhesive layer forming step”). In the pressure-sensitive adhesive layer forming step, for example, the pressure-sensitive adhesive layer is formed on the substrate by applying and curing the pressure-sensitive adhesive composition on the substrate. Thereby, the laminated body formed with a base material and an adhesive layer is obtained.
　粘着剤組成物を使用して粘着剤層を形成する場合は、粘着剤組成物は、ＰＭＭＡ２を含む粘着付与剤を必須成分として含む。粘着剤組成物としては、例えば、前記ベースポリマー（Ａ）と、前記架橋剤（Ｂ）と、前記粘着付与剤とを含有する材料を使用することができる。 When forming an adhesive layer using an adhesive composition, an adhesive composition contains the tackifier containing PMMA2 as an essential component. As the pressure-sensitive adhesive composition, for example, a material containing the base polymer (A), the crosslinking agent (B), and the tackifier can be used.
　ベースポリマー（Ａ）は、前記（メタ）アクリル酸エステル単量体及び前記架橋性官能基を有する（メタ）アクリル単量体を含む原料の重合反応により得ることができる。この原料は、（メタ）アクリル酸エステル単量体及び架橋性官能基を有する（メタ）アクリル単量体の総量に対して、（メタ）アクリル酸エステル単量体（すなわち、単量体単位（ａ１）を形成するための単量体）を５０～９９．９質量％、好ましくは６０～９９．５質量％、さらに好ましくは７０～９９．０質量％含有することができる。 The base polymer (A) can be obtained by a polymerization reaction of a raw material containing the (meth) acrylic acid ester monomer and the (meth) acrylic monomer having a crosslinkable functional group. This raw material is based on the total amount of the (meth) acrylic acid ester monomer and the (meth) acrylic monomer having a crosslinkable functional group. The monomer for forming a1) can be contained in an amount of 50 to 99.9% by mass, preferably 60 to 99.5% by mass, more preferably 70 to 99.0% by mass.
　前記重合反応では、例えば、公知の重合開始剤を使用することができる。重合開始剤としては、例えば、アゾビスイソブチロニトリル、２，２’－アゾビス［２－（２－イミダゾリン－２－イル）プロパン］ジヒドロクロライド、１，１’－アゾビス（シクロヘキサンカルボニトリル）、ジ－ｔｅｒｔ－ブチルペルオキシド、ｔｅｒｔ－ブチルヒドロペルオキシド、過酸化ベンゾイル、過硫酸アンモニウム、光重合開始剤（イルガキュア（登録商標）シリーズ等）等が挙げられる。重合開始剤の使用量も限定されず、公知の重合方法の条件と同様とすることができる。 In the polymerization reaction, for example, a known polymerization initiator can be used. Examples of the polymerization initiator include azobisisobutyronitrile, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 1,1′-azobis (cyclohexanecarbonitrile), Examples thereof include di-tert-butyl peroxide, tert-butyl hydroperoxide, benzoyl peroxide, ammonium persulfate, and a photopolymerization initiator (Irgacure (registered trademark) series, etc.). The amount of the polymerization initiator used is not limited, and can be the same as the conditions for known polymerization methods.
　前記重合反応では、必要に応じて溶媒を使用することができる。溶媒の種類は特に限定されず、例えば、重合で使用されている公知の有機溶媒を広く使用することができる。例えば、酢酸エチル、酢酸ブチル等のエステル化合物；アセトン、メチルエチルケトン等のケトン；ヘキサン等の脂肪族炭化水素；トルエン、キシレン、ベンゼン等の芳香族化合物；を挙げることができる。前記重合反応で使用する溶媒の使用量は特に限定されない。 In the polymerization reaction, a solvent can be used as necessary. The kind of solvent is not specifically limited, For example, the well-known organic solvent currently used by superposition | polymerization can be used widely. For example, ester compounds such as ethyl acetate and butyl acetate; ketones such as acetone and methyl ethyl ketone; aliphatic hydrocarbons such as hexane; aromatic compounds such as toluene, xylene, and benzene; The amount of the solvent used in the polymerization reaction is not particularly limited.
　前記重合反応は、公知の重合方法によって得ることができる。この重合方法としては、例えば、溶液重合、バルク重合、懸濁重合、乳化重合等を採用できる。 The polymerization reaction can be obtained by a known polymerization method. As this polymerization method, for example, solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization and the like can be employed.
　前記重合反応では、例えば、窒素等の不活性ガス雰囲気下で重合反応を行うことができる。 In the polymerization reaction, for example, the polymerization reaction can be performed under an inert gas atmosphere such as nitrogen.
　重合反応の反応時間及び反応温度も限定されず、使用する単量体の種類及び使用量に応じて、適宜設定することができる。例えば、２０～１００℃、１～２４時間の条件で重合反応を行うことができる。 The reaction time and reaction temperature of the polymerization reaction are not limited, and can be set as appropriate according to the type and amount of the monomer used. For example, the polymerization reaction can be performed under conditions of 20 to 100 ° C. and 1 to 24 hours.
　粘着剤組成物の調製方法は特に限定されず、前記ベースポリマー（Ａ）と、前記架橋剤（Ｂ）と、前記粘着付与剤とを所定の配合割合で混合することで調製することができる。混合方法も特に限定されず、例えば、市販の混合機を使用できる。 The method for preparing the pressure-sensitive adhesive composition is not particularly limited, and the pressure-sensitive adhesive composition can be prepared by mixing the base polymer (A), the crosslinking agent (B), and the tackifier at a predetermined blending ratio. The mixing method is not particularly limited, and for example, a commercially available mixer can be used.
　粘着剤組成物は、ベースポリマー（Ａ）１００質量部あたり、前記架橋剤（Ｂ）を０．００１～５質量部、好ましくは０．００５～３質量部、より好ましくは０．０１～１質量部含有することができる。 In the pressure-sensitive adhesive composition, 0.001 to 5 parts by mass, preferably 0.005 to 3 parts by mass, more preferably 0.01 to 1 part by mass of the crosslinking agent (B) per 100 parts by mass of the base polymer (A). Parts can be contained.
　粘着剤組成物は、前記ベースポリマー（Ａ）、前記架橋剤（Ｂ）、前記粘着付与剤の他、必要に応じてその他の成分を含有することができる。その他の成分としては、例えば、シランカップリング剤、架橋促進剤、帯電防止剤、光安定（吸収）剤、分散安定剤、防腐剤、粘度調整剤、金属腐食防止剤、溶剤等が挙げられる。 The pressure-sensitive adhesive composition can contain other components as necessary in addition to the base polymer (A), the cross-linking agent (B), and the tackifier. Examples of other components include silane coupling agents, crosslinking accelerators, antistatic agents, light stabilizers (absorption) agents, dispersion stabilizers, preservatives, viscosity modifiers, metal corrosion inhibitors, solvents, and the like.
　粘着剤層形成工程において、粘着剤組成物を基材上に塗布する方法は特に限定されず、例えば、公知の塗布方法を広く採用することができる。粘着剤組成物を塗布し形成される塗膜の厚みも限定されず、目的の粘着シートの粘着剤層の厚みに応じて適宜設定することができる。 In the pressure-sensitive adhesive layer forming step, the method for applying the pressure-sensitive adhesive composition onto the substrate is not particularly limited, and for example, a known coating method can be widely adopted. The thickness of the coating film formed by applying the pressure-sensitive adhesive composition is not limited, and can be appropriately set according to the thickness of the pressure-sensitive adhesive layer of the target pressure-sensitive adhesive sheet.
　粘着剤層形成工程において、粘着剤組成物を基材上に塗布した後、粘着剤組成物の塗膜を硬化することで、粘着剤層が形成される。硬化方法は特に限定されず、例えば、従来から行われている粘着剤組成物の硬化方法を広く採用することができる。例えば、塗膜を加熱して硬化する方法を挙げることができる。加熱する場合の温度は、例えば、５０～２００℃、好ましくは８０℃～１５０℃とすることができる。加熱時間は溶剤が揮発し、粘着剤層の残留溶剤濃度が１０００ｐｐｍ以下になるように設定すればよく、粘着剤組成物の濃度、所望する粘着剤層の厚み等から上記温度範囲で１～３０分程度の時間内で適宜設定することが好ましい。 In the pressure-sensitive adhesive layer forming step, after the pressure-sensitive adhesive composition is applied on the substrate, the pressure-sensitive adhesive layer is formed by curing the coating film of the pressure-sensitive adhesive composition. The curing method is not particularly limited, and for example, conventionally used curing methods for pressure-sensitive adhesive compositions can be widely employed. For example, the method of heating and hardening a coating film can be mentioned. The temperature for heating can be, for example, 50 to 200 ° C., preferably 80 to 150 ° C. The heating time may be set so that the solvent is volatilized and the residual solvent concentration of the pressure-sensitive adhesive layer is 1000 ppm or less. From the concentration of the pressure-sensitive adhesive composition, the desired thickness of the pressure-sensitive adhesive layer, etc. It is preferable to set appropriately within the time of about minutes.
　前記硬化によって、粘着剤組成物中の架橋剤（Ｂ）が、ベースポリマー（Ａ）中の単量体単位（ａ２）の架橋性官能基と反応し、ベースポリマー（Ａ）の架橋反応が進行する。これにより、ベースポリマー（Ａ）の架橋構造体を含む粘着剤層が形成される。この粘着剤層には、粘着付与剤としてのＰＭＭＡ２も含まれる。 By the curing, the crosslinking agent (B) in the pressure-sensitive adhesive composition reacts with the crosslinkable functional group of the monomer unit (a2) in the base polymer (A), and the crosslinking reaction of the base polymer (A) proceeds. To do. Thereby, the adhesive layer containing the crosslinked structure of a base polymer (A) is formed. This pressure-sensitive adhesive layer also contains PMMA2 as a tackifier.
　前記塗膜を硬化した後は、必要に応じて、硬化物を所定の環境下で熟成処理を行うことができる。 After the coating film is cured, the cured product can be aged in a predetermined environment as necessary.
　以上の粘着剤層形成工程によって、粘着剤層が形成される。粘着剤層形成工程において、粘着剤層を基材上に形成することにより、粘着剤層形成工程によって、粘着シートに含まれる積層体を直接得ることができる。 The pressure-sensitive adhesive layer is formed by the above pressure-sensitive adhesive layer forming step. In the pressure-sensitive adhesive layer forming step, by forming the pressure-sensitive adhesive layer on the substrate, the laminate contained in the pressure-sensitive adhesive sheet can be directly obtained by the pressure-sensitive adhesive layer forming step.
　粘着シートはセパレータを備えることもできる。 The adhesive sheet can also be provided with a separator.
　例えば、粘着シートは、前記粘着剤層の前記基材側と逆の面には、セパレータが貼り合わされていてもよい。このセパレータは、粘着シートの粘着剤層を保護するための部材である。 For example, in the pressure-sensitive adhesive sheet, a separator may be bonded to the surface of the pressure-sensitive adhesive layer opposite to the base material side. This separator is a member for protecting the adhesive layer of the adhesive sheet.
　セパレータの種類は特に限定されず、従来から粘着シートのセパレータとして使用されている公知のフィルムを広く採用できる。例えば、公知の剥離処理されたポリエステルフィルムを粘着シートのセパレータとして採用できる。 The type of separator is not particularly limited, and a wide variety of known films that have been conventionally used as separators for adhesive sheets can be used. For example, a known release-treated polyester film can be used as the separator for the pressure-sensitive adhesive sheet.
　粘着シートがセパレータを備える場合、基材、粘着剤層及びセパレータがこの順に積層することで粘着シートが形成される。 When the pressure-sensitive adhesive sheet includes a separator, the pressure-sensitive adhesive sheet is formed by laminating the base material, the pressure-sensitive adhesive layer, and the separator in this order.
　粘着シートは、基材及び粘着剤層（つまり、積層体）のみで形成されていてもよいし、積層体と前記セパレータからなる層のみで形成されていてもよいし、あるいは、積層体と前記セパレータ以外の層をさらに有することもできる。 The pressure-sensitive adhesive sheet may be formed only of a base material and a pressure-sensitive adhesive layer (that is, a laminate), may be formed only of a layer consisting of a laminate and the separator, or the laminate and the above-described It can also have layers other than a separator.
　粘着シートの製造方法は特に限定されない。例えば、前記粘着剤層形成工程を備える方法を採用することができる。この粘着剤層形成工程によって積層体が形成され、これを粘着シートとして得ることができる。粘着剤層形成工程の条件は前記と同様であり、使用する粘着剤組成物も前記のとおりである。 The manufacturing method of the adhesive sheet is not particularly limited. For example, a method including the pressure-sensitive adhesive layer forming step can be employed. A laminate is formed by this pressure-sensitive adhesive layer forming step, and this can be obtained as a pressure-sensitive adhesive sheet. The conditions of the pressure-sensitive adhesive layer forming step are the same as described above, and the pressure-sensitive adhesive composition to be used is as described above.
　また、粘着シートがセパレータを備える場合は、例えば、あらかじめ積層体を粘着剤層形成工程によって形成し、この積層体の粘着剤層側の面とセパレータとを貼り合わせることで、セパレータで粘着剤層が保護された粘着シートを得ることができる。積層体の粘着剤層側の面とセパレータとを張り合わせる方法は特に限定されず、例えば公知の方法を広く採用することができる。 Moreover, when an adhesive sheet is equipped with a separator, for example, a laminated body is formed in advance by an adhesive layer forming step, and the adhesive layer side of the laminated body and the separator are bonded together so that the adhesive layer Can be obtained. The method for bonding the surface of the laminate to the pressure-sensitive adhesive layer side and the separator is not particularly limited, and for example, known methods can be widely adopted.
　また、別の態様として、粘着シートがセパレータを備える場合は、まずセパレータに、前記粘着剤層形成工程によって粘着剤層を形成し、次いで、該粘着剤層上に基材を貼り合わせることで、セパレータで粘着剤層が保護された粘着シートを得ることができる。粘着剤層と基材とを張り合わせる方法は特に限定されず、例えば公知の方法を広く採用することができる。 Moreover, as another aspect, when the pressure-sensitive adhesive sheet includes a separator, first, a pressure-sensitive adhesive layer is formed on the separator by the pressure-sensitive adhesive layer forming step, and then a base material is bonded onto the pressure-sensitive adhesive layer. A pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive layer is protected by the separator can be obtained. The method for bonding the pressure-sensitive adhesive layer and the substrate is not particularly limited, and for example, known methods can be widely adopted.
　本発明の粘着シートは、三次元表面加飾成型（３Ｄ加飾成型）のための粘着シートとして使用することができ、例えば、本発明の粘着シートは、基材面（粘着剤層と逆側の面）に加飾印刷をして、加飾フィルムとして使用することができる。 The pressure-sensitive adhesive sheet of the present invention can be used as a pressure-sensitive adhesive sheet for three-dimensional surface decoration molding (3D decoration molding). For example, the pressure-sensitive adhesive sheet of the present invention has a substrate surface (the side opposite to the pressure-sensitive adhesive layer). Can be used as a decorative film.
　加飾印刷の種類は特に限定されず、公知の印刷方法を採用できる。例えば、スクリーン印刷、インクジェット印刷、塗装、真空製膜、めっき、加飾フィルムの転写及び貼合、インサート成型金属柄等に印刷されたフィルムと、黒色等のカラー印刷されたフィルムとが積層された意匠フィルム等が挙げられる。 The type of decorative printing is not particularly limited, and a known printing method can be adopted. For example, screen printing, ink-jet printing, painting, vacuum film formation, plating, transfer and bonding of decorative films, insert-molded metal patterns, etc., and black and other color-printed films were laminated. Examples include design films.
　本発明の粘着シートを備える加飾フィルムは、３Ｄ加飾成型用のフィルムとして使用できる。加飾フィルムの粘着剤層側の面が、３Ｄ加飾成型させる三次元形状の部材に貼り合わされ、これにより、三次元形状部材に意匠性が付与される。粘着シートがセパレータを備える場合は、セパレータを粘着剤層から剥離して粘着剤層を露出させ、この粘着剤層の面を前記三次元形状の部材に貼り合わせる。 The decorative film provided with the pressure-sensitive adhesive sheet of the present invention can be used as a film for 3D decorative molding. The surface of the decorative film on the pressure-sensitive adhesive layer side is bonded to a 3D-shaped member to be 3D-decorated, thereby imparting design properties to the 3D-shaped member. When the pressure-sensitive adhesive sheet includes a separator, the separator is peeled from the pressure-sensitive adhesive layer to expose the pressure-sensitive adhesive layer, and the surface of the pressure-sensitive adhesive layer is bonded to the three-dimensional member.
　本発明の粘着シートは、基材にＰＭＭＡが含まれることから、絞り性に優れるため、三次元形状の部材に対して密着性が優れ、貼り合わせ後に皺及び割れも発生しにくく、その上、印刷適性にも優れる。 Since the pressure-sensitive adhesive sheet of the present invention contains PMMA in the base material, it has excellent drawability, so it has excellent adhesion to a three-dimensional member, and is less likely to cause wrinkles and cracks after being bonded. Excellent printability.
　しかも、本発明の粘着シートは、粘着剤層中にも粘着付与剤としてＰＭＭＡ（ＰＭＭＡ２）が含まれることから、粘着剤層と基材との親和性も高く、また、粘着剤層全体のガラス転移温度も高く成り得る。これにより、高温であっても高い粘着性を維持することが可能となり、本発明の粘着シートを備える加飾フィルムで３Ｄ加飾成型をしたとしても、粘着シートの浮き及び剥がれの発生も起こりにくく、高い信頼性を有する。 Moreover, since the pressure-sensitive adhesive sheet of the present invention contains PMMA (PMMA2) as a tackifier in the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer and the substrate have high affinity, and the glass of the pressure-sensitive adhesive layer as a whole. The transition temperature can also be high. Thereby, even if it is high temperature, it becomes possible to maintain high adhesiveness, and even if 3D decorative molding is performed with the decorative film including the adhesive sheet of the present invention, the adhesive sheet is less likely to float and peel off. High reliability.
　以下、実施例により本発明をより具体的に説明するが、本発明はこれら実施例の態様に限定されるものではない。また、特に断りが無い場合、溶液又は分散液の配合部数は固形配合量（質量部）を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the embodiments. Moreover, when there is no notice in particular, the compounding part number of a solution or a dispersion means a solid compounding quantity (mass part).
　（製造例１）
　攪拌機、窒素ガス導入管、温度計及び還流冷却管を備えた反応容器に、アクリル酸ｎ－ブチル８０質量部及びアクリル酸メチル１７質量部からなる単量体（ａ１）と、アクリル酸３質量部からなる単量体（ａ２）と、酢酸エチル（ＥｔＡｃ）１５０質量部と、メチルエチルケトン（ＭＥＫ）２０質量部とを仕込み、窒素ガスを導入しながら７０℃に昇温した。次いで、重合開始剤アゾビスイソブチロニトリル（ＡＩＢＮ）を０．０５質量部加え、窒素雰囲気下、７０℃で８時間重合反応を行った。反応終了後、固形分濃度が２５質量％になるよう酢酸エチル（ＥｔＡｃ）にて希釈し、ベースポリマー（Ａ）の溶液を得た。 (Production Example 1)
In a reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser, a monomer (a1) composed of 80 parts by mass of n-butyl acrylate and 17 parts by mass of methyl acrylate, and 3 parts by mass of acrylic acid The monomer (a2) consisting of 150 parts by mass of ethyl acetate (EtAc) and 20 parts by mass of methyl ethyl ketone (MEK) were charged, and the temperature was raised to 70 ° C. while introducing nitrogen gas. Next, 0.05 part by mass of a polymerization initiator azobisisobutyronitrile (AIBN) was added, and a polymerization reaction was performed at 70 ° C. for 8 hours in a nitrogen atmosphere. After completion of the reaction, the solution was diluted with ethyl acetate (EtAc) so that the solid content concentration was 25% by mass to obtain a solution of the base polymer (A).
　一方、撹拌機、窒素ガス導入管、温度計及び還流冷却器を備えた反応容器に、トルエン１００質量部を仕込み、窒素ガスを導入しながら９０℃に昇温した。次いで、メタクリル酸メチル（ＭＭＡ）９９質量部、メタクリル酸ジメチルアミノエチル（ＤＭＡＥＭＡ）１質量部、アゾビスイソブチロニトリル１質量部を滴下ロートより、２時間かけて滴下し、さらにアゾビスイソブチロニトリル１質量部を追加して還流させながら５時間重合反応を行った。反応終了後、固形分濃度が４５質量％になるようトルエンにて希釈し、重量平均分子量２万の低分子量ポリマー（ＰＭＭＡ２）の溶液を得た。この低分子量ポリマー（ＰＭＭＡ２）を（Ｃ－１）と表記した。 Meanwhile, 100 parts by mass of toluene was charged into a reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux condenser, and the temperature was raised to 90 ° C. while introducing nitrogen gas. Next, 99 parts by weight of methyl methacrylate (MMA), 1 part by weight of dimethylaminoethyl methacrylate (DMAEMA) and 1 part by weight of azobisisobutyronitrile were dropped from the dropping funnel over 2 hours, and further azobisisobutyrate. A polymerization reaction was carried out for 5 hours while adding 1 part by mass of nitrile and refluxing. After completion of the reaction, the solution was diluted with toluene so that the solid content concentration was 45% by mass, and a solution of a low molecular weight polymer (PMMA2) having a weight average molecular weight of 20,000 was obtained. This low molecular weight polymer (PMMA2) was represented as (C-1).
　得られたベースポリマー（Ａ）１００質量部と、架橋剤（Ｂ）としてエポキシ系架橋剤であるＮ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミン（三菱ガス化学（株）製：テトラッドＸ）を０．０６質量部と、粘着付与剤（タッキファイヤ）として前記低分子量ポリマー（Ｃ－１）を１５質量部とを混合し、酢酸エチルにて固形分濃度が２０％の溶液となるように希釈撹拌して、粘着剤組成物（ベースポリマー（Ａ）１００質量部に対して粘着付与剤であるＰＭＭＡ２成分を１５質量部含有）を調製した。 100 parts by mass of the obtained base polymer (A) and N, N, N ′, N′-tetraglycidyl-m-xylenediamine (Mitsubishi Gas Chemical Co., Ltd.) which is an epoxy-based crosslinking agent as the crosslinking agent (B) : Tetrad X) is mixed with 0.06 parts by mass and 15 parts by mass of the low molecular weight polymer (C-1) as a tackifier (tackifier), and a solution having a solid content concentration of 20% in ethyl acetate The mixture was diluted and stirred so as to prepare an adhesive composition (containing 15 parts by mass of PMMA2 component as a tackifier with respect to 100 parts by mass of the base polymer (A)).
　（製造例２）
　粘着付与剤を使用しなかったこと以外は製造例１と同様の方法で粘着剤組成物（ベースポリマー（Ａ）１００質量部に対して粘着付与剤であるＰＭＭＡ２成分を０質量部含有）を調製した。 (Production Example 2)
A pressure-sensitive adhesive composition (containing 0 part by mass of PMMA 2 component as a tackifier with respect to 100 parts by mass of the base polymer (A)) was prepared in the same manner as in Production Example 1 except that no tackifier was used. did.
　（製造例３）
　Ｃ－１（ＰＭＭＡ２）の配合量を１５質量部から１０質量部に変更した以外は製造例１と同様の方法で粘着剤組成物（ベースポリマー（Ａ）１００質量部に対して粘着付与剤であるＰＭＭＡ２成分を１０質量部含有）を調製した。 (Production Example 3)
Except for changing the blending amount of C-1 (PMMA2) from 15 parts by mass to 10 parts by mass, the pressure-sensitive adhesive composition (base polymer (A) 100 parts by mass with a tackifier) was used in the same manner as in Production Example 1. 10 parts by mass of a PMMA2 component) was prepared.
　（製造例４）
　Ｃ-１（ＰＭＭＡ２）の配合量を１５質量部から２５質量部に変更した以外は製造例１と同様の方法で粘着剤組成物（ベースポリマー（Ａ）１００質量部に対して粘着付与剤であるＰＭＭＡ２成分を２５質量部含有）を調製した。 (Production Example 4)
Except for changing the blending amount of C-1 (PMMA2) from 15 parts by mass to 25 parts by mass, the pressure-sensitive adhesive composition (base polymer (A) is 100 parts by mass with a tackifier in the same manner as in Production Example 1. 25 parts by mass of a certain PMMA2 component) was prepared.
　（製造例５）
　粘着付与剤（ＰＭＭＡ２）として重量平均分子量１０００の低分子量ポリマー（Ｃ－２と表記）を使用した以外は製造例１と同様の方法で粘着剤組成物を調製した。 (Production Example 5)
A pressure-sensitive adhesive composition was prepared in the same manner as in Production Example 1 except that a low molecular weight polymer having a weight average molecular weight of 1000 (denoted as C-2) was used as the tackifier (PMMA2).
　（製造例６）
　粘着付与剤（ＰＭＭＡ２）として重量平均分子量４．５万の低分子量ポリマー（Ｃ－３と表記）を使用した以外は製造例１と同様の方法で粘着剤組成物を調製した。 (Production Example 6)
A pressure-sensitive adhesive composition was prepared in the same manner as in Production Example 1 except that a low molecular weight polymer (denoted as C-3) having a weight average molecular weight of 45,000 was used as the tackifier (PMMA2).
　（製造例７）
　粘着付与剤（ＰＭＭＡ２）として重量平均分子量６万の低分子量ポリマー（Ｃ－４と表記）を使用した以外は製造例１と同様の方法で粘着剤組成物を調製した。 (Production Example 7)
A pressure-sensitive adhesive composition was prepared in the same manner as in Production Example 1, except that a low-molecular weight polymer having a weight average molecular weight of 60,000 (denoted as C-4) was used as the tackifier (PMMA2).
　（実施例１）
　セパレータとして、厚み１００μｍのＰＥＴフィルム（王子エフテックス社製：１００ＲＬ－０７（２））を準備した。このセパレータ上に、製造例１で得られた粘着剤組成物を、乾燥後の厚みが２５μｍとなるように塗工して塗膜を形成し、これを１００℃で３分間乾燥して塗膜を硬化させ、セパレータ上に粘着剤層を形成した。次いで、該粘着剤層の表面に、基材としてＰＭＭＡ１で形成される厚み７５μｍのＰＭＭＡフィルム（クラレ社製：パラピュアＩＴグレード＃７５）を貼合した。これにより、粘着シートが得られた。得られた粘着シートについて、曲面部貼合適性、つまり、３Ｄ加飾性についての評価及び信頼性評価、耐候性評価、水接触角並びに印刷適性評価を行った。 Example 1
As a separator, a PET film having a thickness of 100 μm (manufactured by Oji F-Tex: 100RL-07 (2)) was prepared. On this separator, the pressure-sensitive adhesive composition obtained in Production Example 1 was applied so that the thickness after drying was 25 μm to form a coating film, which was dried at 100 ° C. for 3 minutes to form a coating film. Was cured to form an adhesive layer on the separator. Next, a PMMA film having a thickness of 75 μm (made by Kuraray Co., Ltd .: Parapure IT Grade # 75) formed of PMMA1 as a substrate was bonded to the surface of the pressure-sensitive adhesive layer. Thereby, the adhesive sheet was obtained. About the obtained adhesive sheet, curved-surface bonding suitability, that is, evaluation and reliability evaluation for 3D decorating properties, weather resistance evaluation, water contact angle, and print suitability evaluation were performed.
　（実施例２）
　製造例１で得られた粘着剤組成物を使用する代わりに、製造例３で得られた粘着剤組成物を使用したこと以外は実施例１と同様の方法で粘着シートを得た。得られた粘着シートについて、実施例１と同様の評価を行った。 (Example 2)
Instead of using the pressure-sensitive adhesive composition obtained in Production Example 1, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition obtained in Production Example 3 was used. About the obtained adhesive sheet, evaluation similar to Example 1 was performed.
　（実施例３）
　製造例１で得られた粘着剤組成物を使用する代わりに、製造例４で得られた粘着剤組成物を使用したこと以外は実施例１と同様の方法で粘着シートを得た。得られた粘着シートについて、実施例１と同様の評価を行った。 (Example 3)
Instead of using the pressure-sensitive adhesive composition obtained in Production Example 1, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition obtained in Production Example 4 was used. About the obtained adhesive sheet, evaluation similar to Example 1 was performed.
　（実施例４）
　製造例１で得られた粘着剤組成物を使用する代わりに、製造例５で得られた粘着剤組成物を使用したこと以外は実施例１と同様の方法で粘着シートを得た。得られた粘着シートについて、実施例１と同様の評価を行った。 Example 4
Instead of using the pressure-sensitive adhesive composition obtained in Production Example 1, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition obtained in Production Example 5 was used. About the obtained adhesive sheet, evaluation similar to Example 1 was performed.
　（実施例５）
　製造例１で得られた粘着剤組成物を使用する代わりに、製造例６で得られた粘着剤組成物を使用したこと以外は実施例１と同様の方法で粘着シートを得た。得られた粘着シートについて、実施例１と同様の評価を行った。 (Example 5)
Instead of using the pressure-sensitive adhesive composition obtained in Production Example 1, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition obtained in Production Example 6 was used. About the obtained adhesive sheet, evaluation similar to Example 1 was performed.
　（実施例６）
　製造例１で得られた粘着剤組成物を使用する代わりに、製造例７で得られた粘着剤組成物を使用したこと以外は実施例１と同様の方法で粘着シートを得た。得られた粘着シートについて、実施例１と同様の評価を行った。 (Example 6)
Instead of using the pressure-sensitive adhesive composition obtained in Production Example 1, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition obtained in Production Example 7 was used. About the obtained adhesive sheet, evaluation similar to Example 1 was performed.
　（比較例１）
　得られた粘着シートについて、基材をＰＥＴフィルム（東洋紡社製：コスモシャインＡ４３００＃７５）に変更したこと以外は実施例１と同様の方法で粘着シートを得た。得られた粘着シートについて、実施例１と同様の評価を行った。 (Comparative Example 1)
About the obtained adhesive sheet, the adhesive sheet was obtained by the method similar to Example 1 except having changed the base material into the PET film (Toyobo Co., Ltd. Cosmo Shine A4300 # 75). About the obtained adhesive sheet, evaluation similar to Example 1 was performed.
　（比較例２）
　製造例１で得られた粘着剤組成物を使用する代わりに、製造例２で得られた粘着剤組成物を使用したこと以外は実施例１と同様の方法で粘着シートを得た。得られた粘着シートについて、実施例１と同様の評価を行った。 (Comparative Example 2)
Instead of using the pressure-sensitive adhesive composition obtained in Production Example 1, a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive composition obtained in Production Example 2 was used. About the obtained adhesive sheet, evaluation similar to Example 1 was performed.
　（比較例３）
　得られた粘着シートについて、基材をＰＰフィルムに変更したこと以外は実施例１と同様の方法で粘着シートを得た。得られた粘着シートについて、実施例１と同様の評価を行った。 (Comparative Example 3)
About the obtained adhesive sheet, the adhesive sheet was obtained by the method similar to Example 1 except having changed the base material into PP film. About the obtained adhesive sheet, evaluation similar to Example 1 was performed.
　＜評価方法＞
　（重量平均分子量）
　ＧＰＣ測定装置として、東ソー株式会社製示差屈折計（ＲＩ）内蔵型高温ＧＰＣ測定機「ＨＬＣ－８１２１ＧＰＣ－ＨＴ」を使用し、東ソー株式会社製「ＴＳＫｇｅｌ ＧＭＨＨＲ－Ｈ（２０）ＨＴ」を３本連結させたＧＰＣカラムを使用して、重量平均分子量を測定した。カラム温度は１４０℃、溶離液としてトリクロロベンゼンを用い、流速１．０ｍｌ／分にて測定した。測定には、標準ポリスチレンを用いて検量線を作製した。 <Evaluation method>
(Weight average molecular weight)
As a GPC measurement device, a high temperature GPC measuring machine with built-in differential refractometer (RI) “HLC-8121GPC-HT” manufactured by Tosoh Corporation is used, and three “TSKgel GMHHR-H (20) HT” manufactured by Tosoh Corporation are connected. The weight average molecular weight was measured using a GPC column. The column temperature was 140 ° C., trichlorobenzene was used as an eluent, and the flow rate was 1.0 ml / min. For the measurement, a calibration curve was prepared using standard polystyrene.
　（曲面部貼合適性）
　セパレータを剥離した後、粘着シートをＲ＝３．６の曲面部を有するガラス（以下、３Ｄガラスと記載）に１４０℃で真空圧着させた。その後、ガラス貼合サンプルを２３℃５０ＲＨ％で１時間放置し、曲面部を観察し、下記評価基準で皺、割、浮き及び剥がれ、並びに、気泡の状態を判定した。
＜皺＞
◎：３Ｄガラス曲面部にフィルムの皺が全くない。
○：３Ｄガラス曲面部にフィルムの皺が、拡大すれば確認できるものの、目視では確認できない。
×：３Ｄガラス曲面部にフィルムの皺が目視で確認できる。
＜割＞
◎：３Ｄガラス曲面部にフィルムの割れが全くない。
○：３Ｄガラス曲面部にフィルムの割れが、拡大すれば確認できるものの、目視では確認できない。
×：３Ｄガラス曲面部にフィルムの割れが目視で確認できる。
＜浮き及び剥がれ＞
◎：３Ｄガラス曲面部にフィルムと粘着剤層の界面に浮き及び剥がれが全くない。
○：３Ｄガラス曲面部にフィルムと粘着剤層の界面に浮き及び剥がれが、拡大すれば確認できるものの、目視では確認できない。
△：３Ｄガラス曲面部にフィルムと粘着剤層の界面に浮き及び剥がれが目視でわずかに確認できる。
×：３Ｄガラス曲面部にフィルムと粘着剤層の界面に浮き及び剥がれが目視で確認できる。
＜気泡＞
◎：３Ｄガラス曲面部にフィルムと粘着剤層の界面に気泡が全くない。
○：３Ｄガラス曲面部にフィルムと粘着剤層の界面に気泡が、拡大すれば確認できるものの、目視では確認できない。
△：３Ｄガラス曲面部にフィルムと粘着剤層の界面に気泡が目視でわずかに確認できる。
×：３Ｄガラス曲面部にフィルムと粘着剤層の界面に気泡が目視で確認できる。 (Adaptability for curved surface bonding)
After peeling off the separator, the pressure-sensitive adhesive sheet was vacuum-bonded at 140 ° C. to glass having a curved surface portion with R = 3.6 (hereinafter referred to as 3D glass). Thereafter, the glass-bonded sample was allowed to stand at 23 ° C. and 50 RH% for 1 hour, the curved surface portion was observed, and wrinkles, splits, floats and peeling, and the state of bubbles were determined according to the following evaluation criteria.
<皺>
(Double-circle): There is no wrinkle of a film in a 3D glass curved surface part.
○: Although the wrinkle of the film can be confirmed on the 3D glass curved surface portion, it cannot be confirmed by visual observation.
X: A wrinkle of the film can be visually confirmed on the curved surface portion of the 3D glass.
<Discount>
(Double-circle): There is no crack of a film in 3D glass curved-surface part.
○: Although the crack of the film can be confirmed on the 3D glass curved surface portion, it cannot be confirmed visually.
X: The crack of a film can be visually confirmed in a 3D glass curved-surface part.
<Floating and peeling>
(Double-circle): There is no floating and peeling at the interface of a film and an adhesive layer in a 3D glass curved surface part.
○: Although floating and peeling at the interface between the film and the pressure-sensitive adhesive layer can be confirmed on the 3D glass curved surface portion, they can be confirmed by enlargement, but cannot be visually confirmed.
(Triangle | delta): The floating and peeling in the interface of a film and an adhesive layer can be slightly confirmed visually on a 3D glass curved surface part.
X: The floating and peeling at the interface between the film and the pressure-sensitive adhesive layer can be visually confirmed on the curved surface portion of the 3D glass.
<Bubble>
A: There are no bubbles at the interface between the film and the pressure-sensitive adhesive layer on the curved surface of the 3D glass.
○: Although bubbles can be confirmed at the interface between the film and the pressure-sensitive adhesive layer on the curved surface portion of the 3D glass, they can be confirmed, but cannot be visually confirmed.
(Triangle | delta): A bubble can be slightly confirmed visually at the interface of a film and an adhesive layer in a 3D glass curved surface part.
X: Air bubbles can be visually confirmed at the interface between the film and the pressure-sensitive adhesive layer on the curved surface portion of the 3D glass.
　（信頼性）
　３Ｄガラス貼合サンプルを８５℃ｄｒｙ環境下に１００時間放置し、その後の曲面部を観察した。
◎：３Ｄガラス曲面部にフィルムと粘着剤層の界面に浮き・気泡、剥がれが全くない
○：３Ｄガラス曲面部にフィルムと粘着剤層の界面に浮き・気泡、剥がれが、拡大すれば確認できるものの、目視では確認できない。
△：３Ｄガラス曲面部にフィルムと粘着剤層の界面に浮き及び剥がれが目視でわずかに確認できる。
×：３Ｄガラス曲面部にフィルムと粘着剤層の界面に浮き・気泡、剥がれが目視で確認できる。 (reliability)
The 3D glass-bonded sample was left in an 85 ° C. dry environment for 100 hours, and the subsequent curved surface portion was observed.
：: No floating / bubbles / peeling at the interface between the film and the pressure-sensitive adhesive layer on the curved surface of the 3D glass. ○: Floating / bubbles / peeling at the interface between the film and the pressure-sensitive adhesive layer on the curved surface of the 3D glass can be confirmed by enlargement. However, it cannot be confirmed visually.
(Triangle | delta): The floating and peeling in the interface of a film and an adhesive layer can be slightly confirmed visually on a 3D glass curved surface part.
X: Floating, air bubbles, and peeling at the interface between the film and the pressure-sensitive adhesive layer can be visually confirmed on the curved surface portion of the 3D glass.
　（ＨＡＺＥ及び透明性）
　実施例及び比較例で得た粘着シートの一方の粘着面を松浪ガラス社製のスライドガラス（品番：Ｓ９１１２）に貼合してサンプルを作製し、続いて、貼合時に混入した微細な空気等の影響を排除するために、前記サンプルに対し、０．５ＭＰａ、４０℃の条件で３０分間オートクレーブ（加圧脱泡）処理を実施した。その後、光の照射方向から見て基材、粘着剤層及びガラスの順になるように日本電色工業（株）製のＮＤＨ４０００に前記サンプルを設置し、ヘイズを測定した。測定したＨＡＺＥ値（％）が１．５未満であった場合の透明性を合格、１．５以上であった場合の透明性を不合格とした。特に、測定したＨＡＺＥ値が１．０未満であった場合の透明性を「◎」、測定したＨＡＺＥ値が１．０以上１．５未満であった場合の透明性を「○」とし、測定したＨＡＺＥ値が１．５以上であった場合の透明性を「×」と表記した。 (HAZE and transparency)
One of the pressure-sensitive adhesive sheets of the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples was bonded to a slide glass (product number: S9112) manufactured by Matsunami Glass Co., Ltd., followed by fine air mixed during bonding. In order to eliminate the influence of the above, the sample was subjected to an autoclave (pressure defoaming) treatment under conditions of 0.5 MPa and 40 ° C. for 30 minutes. Then, the said sample was installed in NDH4000 by Nippon Denshoku Industries Co., Ltd. so that it might become the order of a base material, an adhesive layer, and glass seeing from the irradiation direction of light, and the haze was measured. Transparency when the measured HAZE value (%) was less than 1.5 was accepted, and transparency when it was 1.5 or more was rejected. In particular, the transparency when the measured HAZE value is less than 1.0 is “◎”, and the transparency when the measured HAZE value is 1.0 or more and less than 1.5 is “◯”. The transparency when the HAZE value was 1.5 or more was expressed as “x”.
　（耐候性）
　実施例及び比較例で得た粘着シートの一方の粘着面を松浪ガラス社製のスライドガラス（品番：Ｓ９１１２）に貼合してサンプルを作製し、続いて、貼合時に混入した微細な空気等の影響を排除するために、前記サンプルに対し、０．５ＭＰａ、４０℃の条件で３０分間オートクレーブ（加圧脱泡）処理を実施した。その後、光の照射方向から見て基材、粘着剤層及びガラスの順になるように、スガ試験機（株）製のサンシャイン・キセノンウェザーメーターＳ８０－Ｘ７５に前記サンプルを設置し、１００時間処理し（処理条件：ＢＰＴ温度＝６３℃、照射量：１６２［Ｗ／ｍ２］）、その後、取り出したサンプルの外観を観察、下記判定基準で評価した。
◎：３Ｄガラス曲面部にフィルムと粘着剤層の界面に浮き及び気泡、剥がれが全くない。○：３Ｄガラス曲面部にフィルムと粘着剤層の界面に浮き及び気泡、剥がれが、拡大すれば確認できるものの、目視では確認できない。
×：３Ｄガラス曲面部にフィルムと粘着剤層の界面に浮き及び剥がれが目視で確認できる。 (Weatherability)
One of the pressure-sensitive adhesive sheets of the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples was bonded to a slide glass (product number: S9112) manufactured by Matsunami Glass Co., Ltd., followed by fine air mixed during bonding. In order to eliminate the influence of the above, the sample was subjected to an autoclave (pressure defoaming) treatment under conditions of 0.5 MPa and 40 ° C. for 30 minutes. After that, the sample is placed on a sunshine / xenon weather meter S80-X75 manufactured by Suga Test Instruments Co., Ltd. in the order of the base material, the adhesive layer, and the glass as viewed from the direction of light irradiation, and processed for 100 hours. (Processing conditions: BPT temperature = 63 ° C., irradiation amount: 162 [W / m 2 ]), and then the appearance of the sample taken out was observed and evaluated according to the following criteria.
A: The 3D glass curved surface has no floating, bubbles, or peeling at the interface between the film and the pressure-sensitive adhesive layer. ○: Floating, air bubbles, and peeling at the interface between the film and the pressure-sensitive adhesive layer on the 3D glass curved surface can be confirmed if enlarged, but cannot be visually confirmed.
X: The floating and peeling at the interface between the film and the pressure-sensitive adhesive layer can be visually confirmed on the curved surface portion of the 3D glass.
　（水接触角）
　実施例及び比較例で得た粘着シートを、基材面（粘着剤層と逆側の面）側が表面側を向くように、かつ、地面に対し平行になるよう協和界面化学（株）製の自動接触角計ＤＭ－５０１にセットした。セットした基材面にイオン交換水を０．２μＬ滴下し、０．５秒放置した。その後、基材と滴下した水滴との角度を測定した。 (Water contact angle)
The pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples were manufactured by Kyowa Interface Chemical Co., Ltd. so that the base material surface (surface opposite to the pressure-sensitive adhesive layer) side was directed to the surface side and parallel to the ground. An automatic contact angle meter DM-501 was set. 0.2 μL of ion exchange water was dropped on the set substrate surface and left for 0.5 seconds. Thereafter, the angle between the substrate and the dropped water droplet was measured.
　（印刷適性）
　インキ（商品名ＭＲＸ　ＨＦ－９１９墨、帝国インキ社製）１００質量部と、硬化剤（商品名２１０硬化剤、帝国インキ社製）５質量部とを混合し、インキＡを調製した。 (Printability)
Ink A was prepared by mixing 100 parts by mass of ink (trade name: MRX HF-919 Black, Teikoku Ink Co., Ltd.) and 5 parts by weight of a curing agent (trade name: 210 curing agent, Teikoku Ink Co., Ltd.).
　別途、インキ（商品名ＭＲＸ　ＨＦ－６１９白、帝国インキ社製）１００質量部と、硬化剤（商品名２１０硬化剤、帝国インキ社製）５質量部とを混合し、インキＢを調製した。 Separately, 100 parts by mass of ink (trade name MRX HF-619 white, manufactured by Teikoku Ink) and 5 parts by mass of a curing agent (trade name 210 curing agent, manufactured by Teikoku Ink) were mixed to prepare ink B.
　インキＡ及びインキＢをそれぞれ用いて、実施例及び比較例で得た粘着シートの基材表面（粘着剤層と逆側の面）にスクリーン印刷し、８０℃で１時間乾燥させて粘着シートの基材表面上に膜厚１５μｍの印刷層を形成した。ＪＩＳ　Ｋ　５６００－５－６に準拠し、以下のようにして碁盤目密着試験を行った。 Using each of ink A and ink B, screen-printed on the base material surface (surface opposite to the pressure-sensitive adhesive layer) of the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples, and dried at 80 ° C. for 1 hour. A printed layer having a thickness of 15 μm was formed on the substrate surface. In accordance with JIS K 5600-5-6, a cross-cut adhesion test was performed as follows.
　セロハンテープ（商品名ＣＴ２８、ニチバン社製）を、指で上から押し付けるようにして印刷層に密着させた後に剥離した。１００マスの内、印刷層が全てのマス目で剥離していない場合を１００／１００、全てのマス目で剥離している場合を０／１００とし、印刷層が剥離していないマス目を数え、以下の評価基準にてインキの密着性を評価し、「◎」、又は「○」を印刷適性として満足できる水準とした。
◎：９６／１００～１００／１００
○：７５／１００～９５／１００
×：０／１００～７４／１００ Cellophane tape (trade name CT28, manufactured by Nichiban Co., Ltd.) was peeled off after being brought into close contact with the printed layer as if pressed from above with a finger. Of 100 squares, 100/100 is the case where the printed layer is not peeled off at all squares, and 0/100 is the case where the printed layer is peeled off at all squares. The ink adhesion was evaluated according to the following evaluation criteria, and “◎” or “◯” was set to a level satisfying printability.
A: 96/100 to 100/100
○: 75/100 to 95/100
×: 0/100 to 74/100
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示す結果から、実施例で得た粘着シートは、基材がＰＭＭＡ１であり、かつ、粘着剤層が粘着付与剤としてＰＭＭＡ２を含有することから、曲面部貼合適性に優れていることがわかる。実施例６ではＰＭＭＡ２の分子量が大きいので透明性及び信頼性が実施例１～５よりも劣るものの、曲面部貼合適性は実用上問題ない水準であった。これに対し、比較例１では、基材がＰＭＭＡ１ではなくＰＥＴであることから、皺及び割れが観察され、しかも、浮き及び剥がれも見られた。また、比較例２では、粘着付与剤としてＰＭＭＡを含有しないことから、顕著な浮き及び剥がれが見られた。比較例３では、基材がＰＭＭＡ１ではなくＰＰであることから、浮き、剥がれ及び気泡の発生が観察され、しかも、信頼性及び耐候性、並びに印刷適性が悪かった。 From the results shown in Table 1, the pressure-sensitive adhesive sheets obtained in the examples are excellent in curved portion bonding suitability because the base material is PMMA1 and the pressure-sensitive adhesive layer contains PMMA2 as a tackifier. I understand. In Example 6, since the molecular weight of PMMA2 was large, the transparency and reliability were inferior to those of Examples 1 to 5, but the suitability for bonding the curved surface portion was at a level with no practical problem. On the other hand, in Comparative Example 1, since the substrate was not PMMA 1 but PET, wrinkles and cracks were observed, and floating and peeling were also observed. Moreover, in the comparative example 2, since it did not contain PMMA as a tackifier, the remarkable float and peeling were seen. In Comparative Example 3, since the base material was PP instead of PMMA1, the occurrence of floating, peeling, and bubbles was observed, and the reliability, weather resistance, and printability were poor.
　以上より、本発明の粘着シートは、密着性に優れ、貼り合わせ後に皺及び割れが発生しにくく、しかも、浮き及び剥がれも起こりにくいことが示された。 From the above, it was shown that the pressure-sensitive adhesive sheet of the present invention is excellent in adhesion, hardly causes wrinkles and cracks after being bonded, and is less likely to float and peel off.

Claims (5)

  1. 　基材及び粘着剤層が積層された積層体を備え、
    　前記基材はポリメタクリル酸メチルを含有し、
    　前記粘着剤層は、ポリメタクリル酸メチルを含む粘着付与剤を含有する、加飾成型用粘着シート。     Provided with a laminate in which a base material and an adhesive layer are laminated,
    The substrate contains polymethyl methacrylate;
    The pressure-sensitive adhesive layer is a pressure-sensitive adhesive sheet for decorative molding, containing a tackifier containing polymethyl methacrylate.
  2. 　前記粘着付与剤に含まれるポリメタクリル酸メチルの重量平均分子量（Ｍｗ）が５００～５００００である、請求項１に記載の加飾成型用粘着シート。 The pressure-sensitive adhesive sheet for decorative molding according to claim 1, wherein the polymethyl methacrylate contained in the tackifier has a weight average molecular weight (Mw) of 500 to 50,000.
  3. 　前記粘着剤層は、ポリメタクリル酸メチル以外のベースポリマー（Ａ）の架橋構造体を含み、
    　前記ベースポリマー（Ａ）の構成単位は、（メタ）アクリル酸エステル単量体単位（ａ１）及び架橋性官能基を有する（メタ）アクリル単量体単位（ａ２）を含有する、請求項１又は２に記載の加飾成型用粘着シート。     The pressure-sensitive adhesive layer includes a crosslinked structure of a base polymer (A) other than polymethyl methacrylate,
    The constituent unit of the base polymer (A) contains a (meth) acrylic acid ester monomer unit (a1) and a (meth) acrylic monomer unit (a2) having a crosslinkable functional group. 2. The decorative molding pressure-sensitive adhesive sheet according to 2.
  4. 　前記基材の粘着剤層側と逆の面の水接触角が４０°～９５°である、請求項１～３のいずれか１項に記載の加飾成型用粘着シート。 The pressure-sensitive adhesive sheet for decorative molding according to any one of claims 1 to 3, wherein a water contact angle on a surface opposite to the pressure-sensitive adhesive layer side of the substrate is 40 ° to 95 °.
  5. 　前記粘着剤層の前記基材側と逆の面には、セパレータが貼り合わされている、請求項１～４のいずれか１項に記載の加飾成型用粘着シート。 The pressure-sensitive adhesive sheet for decorative molding according to any one of claims 1 to 4, wherein a separator is bonded to a surface of the pressure-sensitive adhesive layer opposite to the substrate side.
PCT/JP2018/015155 2017-04-13 2018-04-11 Adhesive sheet for decorative molding WO2018190355A1 (en)

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JP7427855B1 (en) 2023-09-01 2024-02-06 ａｒｔｉｅｎｃｅ株式会社 Adhesive composition for decorative sheet, decorative sheet, decorative structure and manufacturing method thereof
US12031128B2 (en) 2021-04-07 2024-07-09 Battelle Memorial Institute Rapid design, build, test, and learn technologies for identifying and using non-viral carriers
US12109223B2 (en) 2020-12-03 2024-10-08 Battelle Memorial Institute Polymer nanoparticle and DNA nanostructure compositions and methods for non-viral delivery

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