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WO2018101372A1 - Composition adhésive, couche adhésive, et feuille adhésive - Google Patents

Composition adhésive, couche adhésive, et feuille adhésive Download PDF

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Publication number
WO2018101372A1
WO2018101372A1 PCT/JP2017/042927 JP2017042927W WO2018101372A1 WO 2018101372 A1 WO2018101372 A1 WO 2018101372A1 JP 2017042927 W JP2017042927 W JP 2017042927W WO 2018101372 A1 WO2018101372 A1 WO 2018101372A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
moisture
polymer
adhesive composition
Prior art date
Application number
PCT/JP2017/042927
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English (en)
Japanese (ja)
Inventor
佳子 吉良
賢輔 谷
量子 浅井
佳世 下川
岡田　研一
Original Assignee
日東電工株式会社
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
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to US16/465,475 priority Critical patent/US11560499B2/en
Priority to EP17876986.5A priority patent/EP3549994A4/fr
Priority to KR1020197015193A priority patent/KR20190086685A/ko
Priority to CN201780074035.1A priority patent/CN110023448B/zh
Priority claimed from JP2017229395A external-priority patent/JP7168315B2/ja
Publication of WO2018101372A1 publication Critical patent/WO2018101372A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J121/00—Adhesives based on unspecified rubbers
    • 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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • 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

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition, and a pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive layer.
  • Patent Document 1 describes that a coating composition obtained by mixing a specific resin composition and a specific moisture curable solution can be used as a primer composition having excellent adhesion to a wet surface. Has been.
  • Patent Document 2 discloses photopolymerization that can provide a moisture-curing adhesive having sufficient adhesive strength to an adherend having an uneven surface such as an inorganic material such as concrete or wood by photopolymerization. Composition and a moisture-curing adhesive sheet using the composition are described.
  • Patent Document 1 since the coating composition described in Patent Document 1 is used as a liquid primer composition and requires a coating operation and subsequent drying, there is a problem in terms of work efficiency.
  • Patent Document 2 Although the adhesive strength to an adherend having an uneven surface such as an inorganic material such as concrete or wood is examined, no consideration is given to the adhesive strength to a wet surface.
  • the present inventors have determined that the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer is moisture-reacted in an unreacted state.
  • the idea was to use a pressure-sensitive adhesive composition containing a sexual component. On that basis, in order to obtain good adhesion to the wet surface, it was found that it is important to keep the unreacted state of the moisture curable component high.
  • the present invention includes a pressure-sensitive adhesive composition that gives high adhesion to a wet surface by being excellent in storage stability of a moisture-curable component, a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition, and the pressure-sensitive adhesive layer. It is an object to provide an adhesive sheet.
  • One aspect of the present invention is a pressure-sensitive adhesive composition containing a base polymer and a moisture curable component, wherein the base polymer includes a polymer having no functional group that reacts with the moisture curable component, and The water content of the base polymer after storage for 24 hours at 25 ° C. and 50% RH is 0.1% by weight or less, and the pressure-sensitive adhesive composition contains the moisture-curable component in an unreacted state.
  • the base polymer may have a moisture permeability of 25 g / m 2 ⁇ 24 hr or less at 40 ° C. and 90% RH when a 100 ⁇ m thick layer is formed.
  • the base polymer may include a rubber polymer or an acrylic polymer.
  • the moisture curable component may be chemically bonded to the adherend.
  • the moisture curable component may be an aliphatic isocyanate or an alicyclic isocyanate.
  • the pressure-sensitive adhesive composition may further contain a water-absorbing material.
  • the water absorbing material may be a water absorbing polymer.
  • one embodiment of the present invention relates to a pressure-sensitive adhesive layer comprising the above pressure-sensitive adhesive composition.
  • one embodiment of the present invention relates to a pressure-sensitive adhesive sheet comprising the above pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer may be formed on a substrate.
  • a pressure-sensitive adhesive composition that gives high adhesive strength to a wet surface by being excellent in storage stability of a moisture-curable component, a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition, and the pressure-sensitive adhesive layer.
  • An adhesive sheet is provided.
  • the pressure-sensitive adhesive composition according to an embodiment of the present invention is a pressure-sensitive adhesive composition containing a base polymer and a moisture curable component, and the base polymer has a functional group that reacts with the moisture curable component.
  • the water content of the base polymer after storage for 24 hours at 25 ° C. and 50% RH is 0.1% by weight or less, and the moisture curable component is contained in an unreacted state. It is.
  • the pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition of the present embodiment or the pressure-sensitive adhesive sheet comprising the pressure-sensitive adhesive layer (hereinafter also referred to collectively as the pressure-sensitive adhesive sheet) is attached to the wet surface of the adherend
  • the pressure-sensitive adhesive composition The moisture-curable component contained in the (adhesive layer) in an unreacted state reacts with moisture such as moisture absorbed from the wet surface of the adherend and surrounding moisture and moisture to cure moisture. Adhesive strength to the adherend is improved. As a result, when affixed to the wet surface of the adherend, the adhesive strength increases with time, and high adhesive strength can be expressed.
  • the moisture curable component when the moisture curable component can be chemically bonded to the adherend, the moisture curable capable of being chemically bonded to the adherend contained in the pressure-sensitive adhesive composition (adhesive layer) in an unreacted state. Since the chemical bond between the component and the adherend surface proceeds, the adhesive force to the adherend surface is further improved, which is preferable.
  • the surrounding water moisture and moisture
  • the moisture-curable component is removed from the surrounding water (moisture and moisture) at the stage of storage of the product, preparation of the pressure-sensitive adhesive sheet from the pressure-sensitive adhesive composition, storage of the pressure-sensitive adhesive sheet, or before application of the pressure-sensitive adhesive sheet to the adherend. ) May cause moisture curing.
  • the production of the pressure-sensitive adhesive layer or the pressure-sensitive adhesive sheet from the pressure-sensitive adhesive composition and the sticking of the pressure-sensitive adhesive sheet to the adherend may be difficult, or a sufficient adhesive force may not be expressed after the sticking.
  • the water content of the base polymer after storage for 24 hours at 25 ° C. and 50% RH (hereinafter also simply referred to as water content) is 0.1 wt% or less (1000 ppm or less).
  • the adhesive composition is stored, the adhesive sheet is prepared from the adhesive composition, the adhesive sheet is stored, or the adhesive sheet is attached to the adherend. It is possible to sufficiently prevent or suppress ambient water (moisture or moisture) from accumulating in the pressure-sensitive adhesive composition (pressure-sensitive adhesive layer) at a stage prior to the operation.
  • the water content is preferably 0.08% by weight or less, more preferably 0.05% by weight or less.
  • the one where the said moisture content is lower is preferable, and the lower limit is not specifically limited, For example, it is 0.01 weight%.
  • a base polymer contains the polymer which does not have a functional group which reacts with a moisture curable component.
  • a polymer having no functional group non-functional polymer
  • it may be a polymer having a functional group that does not react with the moisture curable component.
  • functional groups that react with the moisture curable component include carboxyl groups, hydroxyl groups, amide groups, amino groups, cyano groups, sulfonic acid groups, phosphoric acid groups, imide groups, isocyanate groups, alkoxy groups, silanol groups, and the like.
  • Examples include polar functional groups.
  • examples of the polymer include acrylic polymers, rubber polymers, silicone polymers, urethane polymers, and the like, and the moisture content is 0.1% by weight.
  • the following can be appropriately selected and used without a functional group that reacts with the moisture-curable component.
  • the functional group that can react with the moisture-curable component is a functional group that can also react with water, the affinity with water is high and the water content is high, which is not preferable.
  • an acrylic polymer and a rubber polymer are preferable from the viewpoint of adhesiveness, and a rubber polymer is more preferable from the viewpoint of moisture permeability.
  • Moisture permeability is related to the solubility and diffusibility of water in the polymer, and polymers with functional groups that can react with moisture-curable components increase the solubility of water in the polymer and lower the diffusivity. Is inappropriate.
  • examples of the rubber-based polymer include polyisobutylene (PIB), a copolymer of isobutylene and normal butylene, a copolymer of isobutylene and isoprene (for example, regular butyl rubber, chlorinated butyl rubber, brominated butyl rubber).
  • PIB polyisobutylene
  • isobutylene and normal butylene a copolymer of isobutylene and isoprene
  • regular butyl rubber for example, regular butyl rubber, chlorinated butyl rubber, brominated butyl rubber.
  • Butyl rubbers such as partially crosslinked butyl rubber), isobutylene polymers such as vulcanizates thereof; styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), isoprene Rubber (IR), Styrene-butadiene-styrene block copolymer (SBS), Styrene-ethylene-propylene-styrene block copolymer (SEPS, SIS hydrogenated product), Styrene-ethylene-propylene block copolymer (SEP) ,styrene Hydrogenated product of isoprene block copolymer), styrene thermoplastic elastomer such as styrene block copolymer such as styrene-isobutylene-styrene block copolymer (SIBS), styrene-but
  • PIB is more preferred because of its low water content.
  • these may be used individually by 1 type and may be used in combination of 2 or more type.
  • the polymer for the rubber modifier include aliphatic hydrocarbon resins such as 1,3-pentadiene polymers and polybutenes, dicyclopentadiene alicyclic hydrocarbon resins, petroleum softeners ( Low polar polymers such as paraffinic oils, naphthenic oils, and aromatic oils) may be used.
  • the acrylic polymer is a polymer having (meth) acrylic acid ester as a main monomer component, and has a (meth) acrylic acid alkyl ester (having a linear or branched alkyl group ( What contains (meth) acrylic-acid alkylester) as a main monomer component can be used suitably.
  • Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth ) Isobutyl acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate , Octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth
  • (meth) acrylic acid alkyl esters having an alkyl group having 1 to 14 carbon atoms are preferred, and (meth) acrylic acid alkyl esters having an alkyl group having 2 to 10 carbon atoms are more preferred.
  • the above “(meth) acrylic acid ester” represents “acrylic acid ester” and / or “methacrylic acid ester”, and the same applies to others.
  • Examples of (meth) acrylic acid esters other than the above (meth) acrylic acid alkyl esters include cycloaliphatic hydrocarbon groups such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
  • (Meth) acrylic acid ester having aromatic hydrocarbon groups such as (meth) acrylic acid ester and phenyl (meth) acrylate.
  • (meth) acrylic acid esters can be used alone or in combination of two or more. Moreover, as long as it is a monomer which does not have a polar functional group, you may copolymerize monomers other than an acrylic monomer with (meth) acrylic acid ester.
  • 80% by weight or more of the monomer component constituting the acrylic polymer is preferably (meth) acrylic acid alkyl ester, more preferably 90% by weight or more, and still more preferably 100%. % By weight.
  • a moisture curable component such as a polar group-containing monomer or a multifunctional monomer; It is important not to use monomers with functional groups that can react.
  • polar group-containing monomers examples include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and other carboxyl group-containing monomers or anhydrides thereof (maleic anhydride).
  • Hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; acrylamide, methacrylamide, N, Amide group-containing monomers such as N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide; aminoethyl (meth) acrylate, (Meth) dimethylaminoethyl acrylate, (meta Amino group-containing monomers such as t-butylaminoethyl acrylate; Glycidyl group monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; Monomers containing cyano groups such as acrylonitrile and me
  • polyfunctional monomer examples include hexanediol di (meth) acrylate, butanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, and (poly) propylene glycol di (meth).
  • neopentyl glycol di (meth) acrylate pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylol methanetri ( Examples include meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, and urethane acrylate.
  • the base polymer has a moisture permeability of 40 g and 90% RH (hereinafter also simply referred to as moisture permeability) when a layer having a thickness of 100 ⁇ m (also referred to as a polymer sheet or a polymer layer) is formed. m 2 ⁇ 24 hr or less is preferable. If the moisture permeability is 25 g / m 2 ⁇ 24 hr or less, the surrounding moisture and moisture should enter the pressure-sensitive adhesive composition (pressure-sensitive adhesive layer) at each stage before the pressure-sensitive adhesive sheet is attached to the adherend. Can be prevented or suppressed satisfactorily.
  • the moisture permeability is preferably 23 g / m 2 ⁇ 24 hr or less, and more preferably 20 g / m 2 ⁇ 24 hr or less.
  • the one where the said water vapor transmission rate is lower is preferable, and the lower limit is not specifically limited, For example, it is 10 g / m ⁇ 2 > * 24hr.
  • the moisture permeability at 40 ° C. and 90% RH when a base polymer layer having a thickness of 100 ⁇ m is formed can be measured by water vapor permeability (JIS K 7129: 2008). Specifically, for example, it can be measured by the measurement method described in the column of Examples described later.
  • the base polymer may be a polymer such as a modifier other than the above-described polymer having no functional group that reacts with the moisture-curable component (hereinafter also referred to as other polymer) within a range in which the effects of the present invention are not significantly inhibited. ) May be contained.
  • the content ratio of the other polymer with respect to the entire base polymer (100% by weight) is preferably 75% by weight or less, and more preferably 60% by weight or less.
  • the content of the polymer having no functional group that reacts with the moisture-curable component with respect to the entire base polymer (100% by weight) may be 100% by weight. 80% by weight or less, and more preferably 60% by weight or less.
  • the content of the polymer having no functional group that reacts with the moisture curable component is preferably 30% by weight or more, and preferably 40% by weight or more in order to exhibit the above-described effects satisfactorily. Is more preferable.
  • the moisture-curable component reacts with the moisture-curable component in the base polymer from the viewpoint of storage stability of the moisture-curable component before the pressure-sensitive adhesive sheet is attached to the wet surface of the adherend. It is preferred not to contain a polymer with possible functional groups.
  • functional groups that react with the moisture curable component include carboxyl groups, hydroxyl groups, amide groups, amino groups, cyano groups, sulfonic acid groups, phosphoric acid groups, imide groups, isocyanate groups, alkoxy groups, silanol groups, and the like. Examples include polar functional groups.
  • the content of the polymer having a functional group capable of reacting with the moisture-curable component is allowed as long as the content of the present invention is not significantly inhibited, for example, the content of the base polymer is 100% by weight or less. sell.
  • the pressure-sensitive adhesive composition contains a polymerization initiator
  • a curing reaction by heat or active energy rays using a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator (photoinitiator) can be used.
  • the said polymerization initiator can be used individually or in combination of 2 or more types.
  • the photopolymerization initiator is not particularly limited, and examples thereof include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, ⁇ -ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photopolymerization initiators.
  • An active oxime photopolymerization initiator, a benzoin photopolymerization initiator, a benzyl photopolymerization initiator, a benzophenone photopolymerization initiator, a ketal photopolymerization initiator, a thioxanthone photopolymerization initiator, and the like can be used.
  • examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane- Examples include 1-one and anisole methyl ether.
  • examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, and 4- (t-butyl). Examples include dichloroacetophenone.
  • Examples of the ⁇ -ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one, and the like.
  • Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride.
  • Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime.
  • the benzoin photopolymerization initiator includes, for example, benzoin.
  • Examples of the benzyl photopolymerization initiator include benzyl.
  • Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, ⁇ -hydroxycyclohexyl phenyl ketone, and the like.
  • Examples of the ketal photopolymerization initiator include benzyl dimethyl ketal.
  • thioxanthone photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.
  • the amount of the photopolymerization initiator used is not particularly limited.
  • the photopolymerization initiator is used in an amount of 0.01 to 5% by weight (preferably 0.1% to 100% by weight of all monomer components (or base polymer) for forming the base polymer). 05 to 3% by weight).
  • an active energy ray When activating the photopolymerization initiator, an active energy ray is irradiated.
  • active energy rays include ionizing radiation such as ⁇ rays, ⁇ rays, ⁇ rays, neutron rays, electron rays, and ultraviolet rays, and ultraviolet rays are particularly preferable.
  • the irradiation energy of the active energy ray, the irradiation time, etc. are not particularly limited as long as the photopolymerization initiator can be activated to cause the monomer component to react.
  • thermal polymerization initiator examples include azo polymerization initiators [for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis. (2-methylpropionic acid) dimethyl, 4,4′-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [ 2- (5-Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis (2-methylpropionamidine) disulfate, 2,2′-azobis (N, N′-di) Methyleneisobutylamidine) dihydrochloride], peroxide polymerization initiators (eg dibenzoyl peroxide, tert-butylpermaleate, etc.), Box-type polymerization initiators and the like. The amount of the thermal polymerization initiator used is
  • content of the said thermal-polymerization initiator is not specifically limited, For example, 0.001 weight% or more with respect to 100 weight% of all the monomer components (or base polymer) for forming a base polymer, Preferably it is 0.00. It is 05% by weight or more, 5% by weight or less, preferably 3% by weight or less.
  • the content of the base polymer in the pressure-sensitive adhesive composition according to this embodiment is not particularly limited, but from the viewpoint of the initial adhesive force, that is, the pressure-sensitive adhesive composition as a whole, excluding the solvent.
  • the total amount of components excluding the solvent of the agent composition is 100% by weight, preferably 5% by weight or more, more preferably 10% by weight or more, and further preferably 20% by weight or more.
  • the content of the base polymer is preferably 90% by weight or less, and 80% by weight or less, based on the entire component excluding the solvent of the pressure-sensitive adhesive composition, from the viewpoint of including a moisture curable component. More preferably, it is more preferably 70% by weight or less.
  • the moisture curable component is a component having a property (moisture curable) that causes a curing reaction in the presence of water (water or moisture).
  • a property moisture curable
  • hydrolyzable reactive groups or functional groups that start a reaction with water in the molecule, and resins and compounds that start curing with ambient water (water or moisture) such as in the air are included.
  • the moisture curable component used in the pressure-sensitive adhesive composition of the present embodiment has moisture curable properties.
  • the moisture curable component is contained in the pressure-sensitive adhesive composition in an unreacted state.
  • a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition of the present embodiment is attached to an adherend
  • the moisture curable component itself in an unreacted state is absorbed by moisture absorbed from the wet surface
  • Adhesion is further improved by curing with water such as moisture or moisture.
  • the moisture curable component is preferably a component that can be chemically bonded to the adherend to be attached. In such a case, the chemical bond proceeds between the unreacted moisture curable component and the adherend, whereby the adhesiveness is further improved.
  • moisture curable components used in this embodiment include isocyanate compounds, alkoxysilyl group-containing polymers, cyanoacrylate compounds, urethane compounds, and the like. Of these, an isocyanate compound and an alkoxysilyl group-containing polymer are preferable in terms of compatibility and curing speed.
  • a moisture hardening component may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the isocyanate compound (isocyanate) is hydrolyzed in the presence of water to become an amine, and is cured by reacting the isocyanate and the amine to form a urea bond. Further, a chemical bond can be formed with a hydroxyl group, an amino group, a carboxyl group or the like on the adherend surface.
  • isocyanate compound examples include aliphatic isocyanate, alicyclic isocyanate, and aromatic isocyanate. Of these, aliphatic isocyanates and alicyclic isocyanates are preferred because they have good compatibility with base polymers, particularly rubber polymers, and have low reactivity with moisture and moisture.
  • aliphatic isocyanate examples include ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMHMDI), dodecamethylene diisocyanate, lysine diisocyanate (LDI), and lysine triisocyanate (LTI). It is done.
  • alicyclic isocyanate examples include isophorone diisocyanate (IPDI), cyclohexylene diisocyanate (CHDI), 4,4′-dicyclohexylmethane diisocyanate, hydrogenated XDI (H 6 XDI), hydrogenated MDI (H 12 MDI), norbornene diisocyanate ( NBDI) and the like.
  • IPDI isophorone diisocyanate
  • CHDI cyclohexylene diisocyanate
  • NBDI norbornene diisocyanate
  • aromatic isocyanate examples include diphenylmethane diisocyanate (MDI) such as 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate; crude diphenylmethane diisocyanate; polynuclear polyphenylene polymethyl polyisocyanate (polymeric MDI) ); Tolylene diisocyanate (TDI) such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate; naphthalene diisocyanate (NDI) such as 1,4-naphthalene diisocyanate and 1,5-naphthalene diisocyanate; 1,5-tetrahydro Naphthalene diisocyanate; 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-fluoro Phenylene diiso
  • the alkoxysilyl group-containing polymer is hydrolyzed in the presence of water to form silanol and is cured by condensation (crosslinking).
  • a strong chemical bond can be formed by a dehydration condensation reaction with a hydroxyl group on the surface of the adherend.
  • alkoxysilyl group-containing polymer examples include a linear dimethoxy group both-end type such as silylyl SAX220 and silylyl SAT350, a linear dimethoxy group single-ended type such as silyl SAT145, and silylyl SAX510 and silyl SAT580 manufactured by Kaneka Corporation.
  • a straight-chain trimethoxy group both-end type such as a branched dimethoxy group terminal type such as silyl SAT400
  • an acrylic-modified type such as silyl MA440, silyl MA903, and silyl MA904 can be used.
  • the content of the moisture curable component in the pressure-sensitive adhesive composition according to the present embodiment is not particularly limited, but from the viewpoint of obtaining high adhesive strength, the entire component excluding the solvent of the pressure-sensitive adhesive composition. That is, the total amount of components excluding the solvent of the pressure-sensitive adhesive composition is 100% by weight, preferably 0.1% by weight or more, preferably 0.5% by weight or more, and more preferably 1% by weight or more. Further, the content of the moisture curable component may be 50% by weight or less based on the entire component excluding the solvent of the pressure-sensitive adhesive composition, because the anchoring force with the substrate may be reduced due to excessive curing. Is desirably 40% by weight or less, particularly preferably 30% by weight or less.
  • the pressure-sensitive adhesive composition of this embodiment preferably further contains a water-absorbing material.
  • the water absorbing material represents a material that can absorb and retain moisture.
  • the pressure-sensitive adhesive composition contains a water-absorbing material
  • the pressure-sensitive adhesive sheet is affixed to the wet surface of the adherend, the water-absorbing material removes moisture on the wet surface that hinders adhesion between the pressure-sensitive adhesive sheet and the adherend.
  • the initial adhesive force to the adherend required for the pressure-sensitive adhesive sheet is satisfactorily expressed.
  • the pressure-sensitive adhesive sheet can follow the adherend having an uneven surface well. As a result, the adhesion to the wet surface can be improved more easily.
  • an organic water-absorbing material such as a water-absorbing polymer or an inorganic water-absorbing material can be used.
  • a water absorbing material may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the water-absorbing polymer include polyacrylic acids, water-soluble celluloses, polyvinyl alcohols, polyethylene oxides, starches, alginic acids, chitins, polysulfonic acids, polyhydroxymethacrylates, polyvinylpyrrolidones, polyacrylamides, Examples thereof include polyethyleneimines, polyallylamines, polyvinylamines, maleic anhydrides, and copolymers thereof.
  • a water absorbing polymer may be used individually by 1 type, and may be used in combination of 2 or more type.
  • polyacrylic acid sodium salt, maleic anhydride and polyisobutylene copolymer are preferable, and maleic anhydride and polyisobutylene copolymer are more preferable.
  • a commercially available product may be used as the water-absorbing polymer.
  • Commercially available water-absorbing polymers include, for example, KC Flock (cellulose powder, manufactured by Nippon Paper Chemicals Co., Ltd.), Sunrose (carboxymethylcellulose, manufactured by Nippon Paper Chemicals Co., Ltd.), Aquaric CA (acrylic acid polymer partial sodium salt) Cross-linked product, Nippon Shokubai Co., Ltd.), Acryhope (acrylic acid polymer partial sodium salt cross-linked product, Nippon Shokubai Co., Ltd.), Sunwet (Polyacrylate cross-linked product, Sundia Polymer Co., Ltd.), Aqua Pearl Acrylate cross-linked product, manufactured by Sundia Polymer Co., Ltd., Aqua Keep (acrylic acid polymer partial sodium salt cross-linked product, manufactured by Sumitomo Seika Co., Ltd.), Aqua Coke (modified polyalkylene oxide, manufactured by Sumitomo Seika Co., Ltd.), KI gel (cross-linked product of iso
  • inorganic water-absorbing materials examples include silica gel and inorganic polymers such as smecton SA manufactured by Kunimine Kogyo Co., Ltd.
  • the content of the water-absorbing material in the case of further containing a water-absorbing material is not particularly limited, but the moisture absorption and removability of the adherend to the wet surface is not limited. From the viewpoint of improving adhesiveness, it is preferably 0.5% by weight or more with respect to the entire component excluding the solvent of the pressure-sensitive adhesive composition, that is, the total amount of the component excluding the solvent of the pressure-sensitive adhesive composition is 100% by weight. It is more preferably 1% by weight or more, and further preferably 2% by weight or more.
  • the content of the water-absorbing material is preferably 50% by weight or less, more preferably 40% by weight or less, based on the entire component excluding the solvent of the pressure-sensitive adhesive composition, from the viewpoint of adhesive strength after moisture curing. 30% by weight or less is particularly preferable.
  • the pressure-sensitive adhesive composition according to the present embodiment may contain a tackifier (tackifier) for the purpose of adjusting the elastic modulus and giving tack during initial adhesion.
  • tackifiers include polybutenes, rosin resins, terpene resins, petroleum resins (for example, petroleum aliphatic hydrocarbon resins, petroleum aromatic hydrocarbon resins, petroleum aliphatic / aromatic copolymerization carbonization).
  • Examples thereof include hydrogen resins, petroleum alicyclic hydrocarbon resins (hydrogenated aromatic hydrocarbon resins), coumarone resins, and the like. In terms of compatibility, a petroleum resin and a rosin resin are preferable.
  • a tackifier may be used alone or in combination of two or more.
  • the content when the tackifier is included in the pressure-sensitive adhesive composition is relative to the whole component excluding the solvent of the pressure-sensitive adhesive composition, that is, the component excluding the solvent of the pressure-sensitive adhesive composition.
  • the total amount is 100% by weight, preferably 10% by weight or more, more preferably 15% by weight or more, and further preferably 20% by weight or more.
  • the content of the tackifier is preferably 80% by weight or less, and 70% by weight with respect to the entire component excluding the solvent of the pressure-sensitive adhesive composition, from the viewpoint of giving the pressure-sensitive adhesive a suitable cohesive force. More preferably, it is more preferably 60% by weight or less.
  • the pressure-sensitive adhesive composition of the present embodiment includes a viscosity modifier, a release modifier, a plasticizer, a softener, a filler, a colorant (pigment, dye, etc.), and aging, as long as the effects of the present invention are not impaired.
  • the filler include inorganic fillers such as talc, titanium oxide, calcium oxide, magnesium oxide, zinc oxide, titanium oxide, calcium carbonate, carbon, silica, clay, mica, barium sulfate, whisker, and magnesium hydroxide. It is done.
  • the content of the filler is preferably 80% by weight or less, and more preferably 70% by weight or less, based on the entire component excluding the solvent of the pressure-sensitive adhesive composition, from the viewpoint of rough surface adhesion. .
  • various common solvents can be used as the solvent (solvent) used in the pressure-sensitive adhesive composition.
  • the solvent include esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as toluene and benzene; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane and methylcyclohexane Organic solvents such as ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • the said solvent may be used individually or in combination of 2 or more types.
  • the elastic modulus (initial elastic modulus) of the pressure-sensitive adhesive layer (before moisture curing) when the pressure-sensitive adhesive layer is formed is preferably 400 kPa or less, and is 300 kPa or less. Is more preferable, and it is further more preferable that it is 200 kPa or less.
  • the initial elastic modulus is 400 kPa or less, good followability can be exhibited even for an adherend having an uneven surface.
  • the water absorption of the water absorbent material is satisfactorily exhibited without impeding the swelling when the water absorbent material absorbs moisture on the wet surface of the adherend.
  • the initial elastic modulus is preferably 0.1 kPa or more.
  • the initial elastic modulus of the pressure-sensitive adhesive layer when the pressure-sensitive adhesive layer was formed was prepared by preparing a sample obtained by rolling the pressure-sensitive adhesive layer into a string, and using a tensile tester (AG-IS manufactured by Shimadzu Corporation). Can be calculated from a stress-strain curve measured when pulled at a speed of 50 mm / min.
  • the pressure-sensitive adhesive layer of this embodiment is formed using the above pressure-sensitive adhesive composition.
  • the forming method is not particularly limited, and a known method can be adopted, but it can be performed according to the following method for producing a pressure-sensitive adhesive sheet.
  • the preferable range of each component amount in an adhesive layer is the same as the preferable range of each component amount except the solvent in an adhesive composition.
  • the pressure-sensitive adhesive layer can be obtained, for example, in the form of a pressure-sensitive adhesive sheet by applying the pressure-sensitive adhesive composition to a substrate described later using a known coating method and drying it. Also, after the pressure-sensitive adhesive composition is applied to a surface having peelability and dried or cured to form a pressure-sensitive adhesive layer on the surface, the pressure-sensitive adhesive layer is bonded to a non-peelable substrate and transferred. You may let them.
  • the method for applying the adhesive composition to the substrate is not particularly limited. For example, a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater, fountain die coater, closed An edge die coater or the like can be used. Further, a solventless coating method such as rolling or extrusion may be applied.
  • the pressure-sensitive adhesive layer may be formed by applying the pressure-sensitive adhesive composition to a release sheet (or a sheet-like substrate having a release surface).
  • the thickness of the pressure-sensitive adhesive layer after drying is not particularly limited, but is preferably 5 to 1000 ⁇ m, preferably 10 to 500 ⁇ m from the viewpoint of exhibiting good followability to an adherend having an uneven surface. Is more preferable.
  • the drying temperature can be, for example, 50 to 150 ° C.
  • the surface of the pressure-sensitive adhesive layer to be adhered to the adherend (the surface to be adhered) is 0.5 to It is preferably exposed at 80% (more preferably 1 to 70%). If the ratio of the water-absorbing material to the surface area of the adhesive surface of the pressure-sensitive adhesive layer is 0.5% or more, the moisture on the wet surface of the adherend can be absorbed well. Moreover, if the ratio of the water absorbing material to the surface area of the sticking surface of the pressure-sensitive adhesive layer is 80% or less, the pressure-sensitive adhesive layer can be favorably bonded to the adherend.
  • the pressure-sensitive adhesive sheet of this embodiment has the above-mentioned pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive sheet of the present embodiment may be a pressure-sensitive adhesive sheet with a substrate having a pressure-sensitive adhesive layer on one or both sides of a sheet-like substrate (support), and the pressure-sensitive adhesive layer is held on a release sheet. It may be a baseless adhesive sheet such as.
  • the concept of the pressure-sensitive adhesive sheet herein may include what are called pressure-sensitive adhesive tapes, pressure-sensitive adhesive labels, pressure-sensitive adhesive films and the like.
  • the pressure-sensitive adhesive layer is typically formed continuously, but is not limited to such a form.
  • the pressure-sensitive adhesive layer is formed in a regular or random pattern such as a dot shape or a stripe shape. It may be.
  • the pressure-sensitive adhesive sheet of the present embodiment may be in a roll shape or a single wafer shape. Or the adhesive sheet of the form processed into various shapes may be sufficient.
  • the material for forming the base material examples include polyolefin films such as polyethylene, polypropylene, and ethylene / propylene copolymers; polyester films such as polyethylene terephthalate; plastic films such as polyvinyl chloride; paper such as kraft paper and Japanese paper Kinds: Cloths such as cotton cloth and soft cloth; woven cloths such as polyester non-woven cloth and vinylon cloth woven cloth; metal foil.
  • the thickness of a base material is not specifically limited.
  • the plastic films may be non-stretched films or stretched (uniaxially stretched or biaxially stretched) films.
  • the surface of the substrate on which the pressure-sensitive adhesive layer is provided may be subjected to a surface treatment such as application of a primer and corona discharge treatment.
  • the adhesive sheet may be perforated to provide a through hole.
  • the moisture on the wet surface of the adherend can escape to the back side of the pressure-sensitive adhesive sheet (opposite to the sticking surface) through the through hole. More moisture on the wet surface of the adherend can be removed.
  • the pressure-sensitive adhesive layer may be protected by a release liner (separator, release film) until use.
  • the protection by the release liner is also useful for maintaining the unreacted state of the unreacted moisture-curable component in the pressure-sensitive adhesive layer.
  • a conventional release paper or the like can be used, and is not particularly limited.
  • a substrate having a release treatment layer, a low adhesive substrate made of a fluoropolymer, and a low adhesive substrate made of a nonpolar polymer. Etc. can be used.
  • the substrate having a release treatment layer include plastic films and papers surface-treated with a release treatment agent such as silicone, long chain alkyl, fluorine, and molybdenum sulfide.
  • fluorine-based polymer of a low-adhesive substrate made of a fluorine-based polymer examples include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymer, chloro Examples include fluoroethylene / vinylidene fluoride copolymers.
  • nonpolar polymer of the low-adhesive substrate made of a nonpolar polymer include olefin resins (for example, polyethylene and polypropylene).
  • the release liner can be formed by a known or common method. Further, the thickness of the release liner is not particularly limited.
  • the moisture curable component is contained in an unreacted state.
  • the unreacted state represents a state in which no curing reaction is caused by water (water or moisture).
  • the retention rate (residual rate) of the moisture-curable component in the pressure-sensitive adhesive composition after being stored at 25 ° C. and 50% RH for 24 hours is 30% or more. Preferably, it is 40% or more, more preferably 50% or more.
  • the maintenance ratio can be measured as follows. First, the ratio between the absorbance at 2275 cm ⁇ 1 derived from isocyanate groups and the absorbance at 2250-2255 cm ⁇ 1 derived from methylene groups of the base polymer obtained from infrared spectroscopic measurement of the pressure-sensitive adhesive sheet (adhesive layer) immediately after production is calculated.
  • the absorbance ratio is the ratio of the absorbance derived from the isocyanate group to the absorbance derived from the methylene group (absorbance derived from the isocyanate group / absorbance derived from the methylene group).
  • the absorbance ratio obtained from the infrared spectroscopic measurement of the pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) after being stored for 24 hours in an environment of 25 ° C. and 50% RH was calculated in the same manner.
  • the maintenance factor of the sex component (isocyanate compound) is calculated. Specifically, it is calculated from the following relational expression.
  • Moisture curable component (isocyanate compound) retention rate (%) ⁇ (absorbance ratio of adhesive sheet after 24 hours storage at 25 ° C., 50% RH) / (absorbance ratio of adhesive sheet immediately after preparation) ⁇ ⁇ 100
  • the retention rate of the moisture curable component is determined from the rate of change in the absorbance ratio at the wave number at which a representative peak derived from the moisture curable component appears in infrared spectroscopy. Can be calculated.
  • the pressure-sensitive adhesive composition, pressure-sensitive adhesive layer and pressure-sensitive adhesive sheet (pressure-sensitive adhesive composition etc.) of the present embodiment are used in order to maintain the unreacted moisture-curable component in the pressure-sensitive adhesive composition and the like in an unreacted state. It is preferable to reduce or block the influence of surrounding water (moisture and humidity).
  • the pressure-sensitive adhesive sheet of this embodiment may be packaged with an appropriate package. Examples of the material of the package include aluminum moisture-proof bags, but are not limited thereto.
  • the atmosphere inside the package may be air, but may be replaced with an inert gas such as nitrogen or argon.
  • the adherend to which the pressure-sensitive adhesive sheet of this embodiment is affixed is not particularly limited, but is preferably one that can be chemically bonded to an unreacted moisture-curable component in the pressure-sensitive adhesive composition (pressure-sensitive adhesive layer).
  • Examples include concrete, mortar, asphalt, metal, wood, tiles, plastic materials such as paint film surfaces and bathroom inner walls, skin, bones, teeth, and living body interiors.
  • Example 1 After dissolving styrene-isoprene-styrene block copolymer (SIS) (Quintac QTC3520 manufactured by Nippon Zeon Co., Ltd.) and isoprene rubber (LIR-30 manufactured by Kuraray Co., Ltd.) as a base polymer in toluene as a solvent.
  • SIS styrene-isoprene-styrene block copolymer
  • LIR-30 isoprene rubber
  • hexamethylene diisocyanate (HDI) as a moisture curable component (Basonut HA2000 manufactured by BASF), isobutylene / maleic anhydride copolymer (KI gel manufactured by Kuraray Trading Co., Ltd.) as a water-absorbing material, Ratio of each component ratio of liquid fully hydrogenated rosin methyl ester resin (M-HDR manufactured by Maruzen Petrochemical Co., Ltd.) as a tackifier, with respect to the total amount of the components excluding the solvent in the adhesive composition.
  • the pressure-sensitive adhesive composition of Example 1 was prepared.
  • Example 2 A pressure-sensitive adhesive composition of Example 2 was prepared in the same manner as in Example 1 except that the moisture curable component was changed to Takenate D-101E (tolylene diisocyanate, TDI) manufactured by Mitsui Chemicals.
  • D-101E tolylene diisocyanate, TDI
  • Example 3 A pressure-sensitive adhesive composition of Example 3 was produced in the same manner as in Example 1 except that the moisture curable component was changed to Takenate D-120N (hydrogenated xylene diisocyanate, H 6 XDI) manufactured by Mitsui Chemicals.
  • Example 4 A pressure-sensitive adhesive composition of Example 4 was produced in the same manner as in Example 4 except that the moisture curable component was changed to Takenate D-140N (isophorone diisocyanate, IPDI) manufactured by Mitsui Chemicals.
  • the moisture curable component was changed to Takenate D-140N (isophorone diisocyanate, IPDI) manufactured by Mitsui Chemicals.
  • Example 5 High molecular weight polyisobutylene polymer as base polymer (OPanol N80 manufactured by BASF), low molecular weight polyisobutylene polymer (Tetrax 5T manufactured by JXTG Energy Co., Ltd.), liquid polybutene (HV-300 manufactured by JXTG Energy Co., Ltd.) was dissolved in toluene as a solvent, and then this solution was mixed with hexamethylene diisocyanate (HDI) as a moisture-curing component (Basonut HA2000 manufactured by BASF), isobutylene / maleic anhydride copolymer as a water-absorbing material ( Kuraray Trading Co., Ltd.
  • HDI hexamethylene diisocyanate
  • Example 6 In Example 5, a modified acrylic polymer (Aquaric CS-6S manufactured by Nippon Shokubai Co., Ltd.) as a water-absorbing material, an alkoxysilyl group-containing polymer (Syryl SAX510 manufactured by Kaneka Corporation) as a moisture curable component, It was changed to use another alkoxysilyl group-containing polymer (Silyl SAT145 manufactured by Kaneka Corporation) and hexamethylene diisocyanate (HDI) (Basonut HI2000 manufactured by BASF), and the solvent in the pressure-sensitive adhesive composition was changed.
  • the pressure-sensitive adhesive composition of Example 6 was prepared by blending so that the ratio of each component to the total amount of components to be removed would be the ratio described in Table 2.
  • Example 7 In a reaction vessel equipped with a stirrer, thermometer, nitrogen gas inlet tube, reflux condenser and dropping funnel, butyl acrylate (BA) as a monomer component: 100 parts by weight and toluene as a polymerization solvent: 190 parts by weight The mixture was stirred and stirred for 2 hours while introducing nitrogen gas. After removing oxygen in the polymerization system in this way, 0.3 part by weight of 2,2′-azobisisobutyronitrile was added as a polymerization initiator, and solution polymerization was carried out at 60 ° C. for 6 hours to butyl acrylate. A solution of the polymer (BA) (acrylic polymer 1) was obtained.
  • BA butyl acrylate
  • hexamethylene diisocyanate (HDI) as a moisture-curing component (Basonut HA2000 manufactured by BASF), KI gel manufactured by Kuraray Trading Co., Ltd. as a water-absorbing material, liquid fully hydrogenated rosin methyl ester as a tackifier
  • the resin M-HDR manufactured by Maruzen Petrochemical Co., Ltd. was blended so that the ratio of each component to the total amount of the components excluding the solvent in the adhesive composition would be the ratio described in Table 2.
  • An agent composition was prepared.
  • a solution of 100 parts by weight of butyl (BA) and 10 parts by weight of acrylic acid (AA) (acrylic polymer solution 2) was obtained.
  • tolylene diisocyanate (TDI) as a moisture curable component (Coronate L manufactured by Tosoh Corporation)
  • KI gel manufactured by Kuraray Trading Co., Ltd. as a water absorbing material
  • liquid fully hydrogenated rosin methyl as a tackifier
  • An ester resin (M-HDR manufactured by Maruzen Petrochemical Co., Ltd.) was blended so that the ratio of each component relative to the total amount of the components excluding the solvent in the adhesive composition would be the ratio described in Table 2.
  • An agent composition was prepared.
  • the water content of the base polymer after storage at 25 ° C. and 50% RH was measured as follows. The results are shown in Tables 1-2.
  • a polyester release film (trade name “Diafoil MRF”, thickness 38 ⁇ m, manufactured by Mitsubishi Polyester Co., Ltd.) was prepared.
  • the base polymer solution according to each example was applied to the release surface of the release liner and dried at 130 ° C. for 5 minutes to form a polymer sheet (polymer layer) having a thickness of 20 ⁇ m.
  • the other surface of the polymer layer formed on the above release liner was bonded to the release surface of the same release liner as the already bonded release liner to prepare a polymer sheet having both surfaces protected by the release liner.
  • the other side of the polymer sheet formed on the release liner was bonded to a PET film having a thickness of 25 ⁇ m (Lumirror S-10 manufactured by Toray Industries, Inc., moisture permeability: 24 g / m 2 ⁇ 24 hr).
  • the release liner was peeled from the produced laminated film.
  • the moisture permeability T of the laminated film was changed from one room at 25 ° C. and 50% RH to two rooms at 40 ° C. and 90% RH using a MOCON water vapor permeability measuring device manufactured by Hitachi High-Tech Science Co., Ltd.
  • the moisture permeability R (g / m 2 ⁇ 24 hr) of only the polymer sheet was calculated by the following formula.
  • R 1 / (1 / T-1 / 24)
  • the absorbance ratio is the ratio of the absorbance derived from the isocyanate group to the absorbance derived from the methylene group (absorbance derived from the isocyanate group / absorbance derived from the methylene group).
  • Moisture curable component (isocyanate compound) retention rate (%) ⁇ (absorbance ratio of polymer sheet after 24 hours storage at 25 ° C., 50% RH) / (absorbance ratio of polymer sheet immediately after preparation) ⁇ ⁇ 100
  • a polyester release film (trade name “Diafoil MRF”, thickness 38 ⁇ m, manufactured by Mitsubishi Polyester Co., Ltd.) was prepared.
  • the pressure-sensitive adhesive composition according to each example was applied to the release surface of this release liner, dried at 80 ° C. for 5 minutes, and then further dried at 130 ° C. for 30 minutes to form a pressure-sensitive adhesive layer having a thickness of 300 ⁇ m.
  • the other surface of the pressure-sensitive adhesive layer formed on the release liner was bonded to the release surface of a paper release film (manufactured by Oji F-Tex Co., Ltd.) to produce a pressure-sensitive adhesive sheet whose both surfaces were protected by the release liner. .
  • a paper release film manufactured by Oji F-Tex Co., Ltd.
  • the retention rate of the moisture-curable component after open storage was calculated as follows. The results are shown in Table 3.
  • the absorbance at 2275 cm ⁇ 1 derived from the isocyanate group and 2250 derived from the methylene group of the base polymer obtained from infrared spectroscopic measurement (using 3100 FT-IR manufactured by Varian) of the pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) immediately after production.
  • the ratio of absorbance at ⁇ 2255 cm ⁇ 1 was calculated.
  • the absorbance ratio is the ratio of the absorbance derived from the isocyanate group to the absorbance derived from the methylene group (absorbance derived from the isocyanate group / absorbance derived from the methylene group).
  • the absorbance ratio obtained from the infrared spectroscopic measurement of the pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) after being stored for 24 hours in an environment of 25 ° C. and 50% RH was calculated in the same manner.
  • the maintenance factor of the sex component (isocyanate compound) was calculated. Specifically, it was calculated from the following relational expression.
  • Moisture curable component (isocyanate compound) retention rate (%) ⁇ (absorbance ratio of adhesive sheet after 24 hours storage at 25 ° C., 50% RH) / (absorbance ratio of adhesive sheet immediately after preparation) ⁇ ⁇ 100
  • a polyester release film (trade name “Diafoil MRF”, thickness 38 ⁇ m, manufactured by Mitsubishi Polyester Co., Ltd.) was prepared.
  • a solution of the pressure-sensitive adhesive composition according to each example was applied to the release surface of this release liner, dried at 80 ° C. for 10 minutes, and then dried at 130 ° C. for another 30 minutes to form a pressure-sensitive adhesive layer having a thickness of 300 ⁇ m. Formed.
  • the other surface of the pressure-sensitive adhesive layer formed on the release liner was bonded to a base film having a thickness of 25 ⁇ m to produce a single-sided pressure-sensitive adhesive sheet.
  • a PET film resin film manufactured by Toray Industries, Inc. and a trade name “Lumirror S-10” were used.
  • the pressure-sensitive adhesive sheet thus prepared was cut so as to have a width of 20 mm and a length of 10 cm, and an adhesive force measurement described later was performed.
  • the prepared pressure-sensitive adhesive sheet was sealed in a moisture-proof bag made of aluminum together with a desiccant (silica gel) before measuring the adhesive strength in order to maintain the unreacted state of the moisture-curable component.
  • a slate standard plate manufactured by Nippon Test Panel Co., Ltd., having a product name “JIS A5430 (FB)” (hereinafter also referred to as a slate plate) having a thickness of 3 mm, a width of 30 mm, and a length of 125 mm was prepared.
  • the glossy surface of this slate plate was used.
  • the slate plate was dried at 130 ° C. for 1 hour, and the weight of the slate plate at this time was measured and defined as “weight of the slate plate before being immersed in water”.
  • the agent composition and the pressure-sensitive adhesive sheet had high storage stability and exhibited high adhesive force on the wet surface.
  • the pressure-sensitive adhesive compositions and pressure-sensitive adhesive sheets of Comparative Examples 1 and 2 each having a moisture content exceeding the range specified in the present invention and the base polymer having a functional group that reacts with the moisture-curable component are storage stability.
  • the adhesive strength to the wet surface was low. The higher the water content, the more the water is retained in the polymer, so that it is less likely to diffuse and release from the polymer.
  • the reaction of the moisture curable component with water in the polymer can be promoted.
  • the polar functional group capable of reacting with the moisture-curable component is highly hydrophilic, it not only reacts with the moisture-curable component itself but also promotes the reaction with water. It is considered inappropriate from the point of view.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne : une composition adhésive contenant un polymère de base et un constituant durcissant à l'humidité, le polymère de base contenant un polymère ne présentant pas de groupe fonctionnel qui réagit avec le constituant durcissant à l'humidité, la teneur en eau du polymère de base après avoir été stocké à 25 °C et 50 % d'humidité relative durant 24 heures est de 0,1 % en pds ou moins, et le constituant durcissant à l'humidité est contenu sous un état non réagi ; une couche adhésive comprenant la composition adhésive ; et une feuille adhésive ayant la couche adhésive.
PCT/JP2017/042927 2016-11-30 2017-11-29 Composition adhésive, couche adhésive, et feuille adhésive WO2018101372A1 (fr)

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US16/465,475 US11560499B2 (en) 2016-11-30 2017-11-29 Adhesive composition, adhesive layer and adhesive sheet
EP17876986.5A EP3549994A4 (fr) 2016-11-30 2017-11-29 Composition adhésive, couche adhésive, et feuille adhésive
KR1020197015193A KR20190086685A (ko) 2016-11-30 2017-11-29 점착제 조성물, 점착제층 및 점착 시트
CN201780074035.1A CN110023448B (zh) 2016-11-30 2017-11-29 粘合剂组合物、粘合剂层及粘合片材

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58171460A (ja) * 1982-03-31 1983-10-08 Nitto Electric Ind Co Ltd 吸湿硬化型感圧接着剤
JPH0211688A (ja) * 1988-06-29 1990-01-16 Eidai Co Ltd 木材の接着方法
JPH09316228A (ja) * 1996-06-03 1997-12-09 Kanegafuchi Chem Ind Co Ltd 熱可塑性樹脂発泡体およびその製造法
JP2000273418A (ja) 1999-03-25 2000-10-03 Sekisui Chem Co Ltd 光重合性組成物、湿気硬化型粘接着性シート、及び部材の接合方法
JP2001354749A (ja) 2000-06-09 2001-12-25 Nippon Shokubai Co Ltd 樹脂組成物、湿気硬化性溶液、被覆材組成物及びその施工方法
JP2002188071A (ja) * 2000-12-21 2002-07-05 Asahi Built Kogyo Kk 粘着性湿気硬化形ホットメルト接着剤およびこれを用いた貼り付け施工方法
JP2008163502A (ja) * 2006-12-27 2008-07-17 Nicca Chemical Co Ltd ポリエステル繊維布帛の面ファスナーによる擦過に対する耐性を向上させる方法、及び車輌内装材の製造方法
JP2009144068A (ja) * 2007-12-14 2009-07-02 Nitomuzu:Kk 延伸剥離テープ
WO2014115521A1 (fr) * 2013-01-22 2014-07-31 東洋インキＳｃホールディングス株式会社 Composition adhésive, et stratifié et procédé de fabrication correspondant
JP2014231586A (ja) * 2013-05-30 2014-12-11 大日本印刷株式会社 粘着剤組成物およびそれを用いた粘着シート

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58171460A (ja) * 1982-03-31 1983-10-08 Nitto Electric Ind Co Ltd 吸湿硬化型感圧接着剤
JPH0211688A (ja) * 1988-06-29 1990-01-16 Eidai Co Ltd 木材の接着方法
JPH09316228A (ja) * 1996-06-03 1997-12-09 Kanegafuchi Chem Ind Co Ltd 熱可塑性樹脂発泡体およびその製造法
JP2000273418A (ja) 1999-03-25 2000-10-03 Sekisui Chem Co Ltd 光重合性組成物、湿気硬化型粘接着性シート、及び部材の接合方法
JP2001354749A (ja) 2000-06-09 2001-12-25 Nippon Shokubai Co Ltd 樹脂組成物、湿気硬化性溶液、被覆材組成物及びその施工方法
JP2002188071A (ja) * 2000-12-21 2002-07-05 Asahi Built Kogyo Kk 粘着性湿気硬化形ホットメルト接着剤およびこれを用いた貼り付け施工方法
JP2008163502A (ja) * 2006-12-27 2008-07-17 Nicca Chemical Co Ltd ポリエステル繊維布帛の面ファスナーによる擦過に対する耐性を向上させる方法、及び車輌内装材の製造方法
JP2009144068A (ja) * 2007-12-14 2009-07-02 Nitomuzu:Kk 延伸剥離テープ
WO2014115521A1 (fr) * 2013-01-22 2014-07-31 東洋インキＳｃホールディングス株式会社 Composition adhésive, et stratifié et procédé de fabrication correspondant
JP2014231586A (ja) * 2013-05-30 2014-12-11 大日本印刷株式会社 粘着剤組成物およびそれを用いた粘着シート

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3549994A4 *

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