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WO2022219969A1 - Adhesive composition and adhesive sheet - Google Patents

Adhesive composition and adhesive sheet Download PDF

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Publication number
WO2022219969A1
WO2022219969A1 PCT/JP2022/009805 JP2022009805W WO2022219969A1 WO 2022219969 A1 WO2022219969 A1 WO 2022219969A1 JP 2022009805 W JP2022009805 W JP 2022009805W WO 2022219969 A1 WO2022219969 A1 WO 2022219969A1
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WO
WIPO (PCT)
Prior art keywords
meth
sensitive adhesive
pressure
mass
adhesive composition
Prior art date
Application number
PCT/JP2022/009805
Other languages
French (fr)
Japanese (ja)
Inventor
雄也 米川
Original Assignee
綜研化学株式会社
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 綜研化学株式会社 filed Critical 綜研化学株式会社
Priority to CN202280026040.6A priority Critical patent/CN117120571A/en
Priority to JP2023514515A priority patent/JPWO2022219969A1/ja
Publication of WO2022219969A1 publication Critical patent/WO2022219969A1/en

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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
    • 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
    • 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
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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]

Definitions

  • the present invention relates to an adhesive composition and an adhesive sheet.
  • plastic materials have low polarity
  • versatile materials such as polypropylene, polyethylene, and cycloolefin resins are known to be difficult-to-adhere adherends. Therefore, pressure-sensitive adhesive sheets used for automotive applications and the like are required to have good adhesion to low-polarity adherends that are difficult to adhere to.
  • Patent Document 1 describes the use of an acrylic pressure-sensitive adhesive composition containing a nuclear hydrogenated terpene phenolic resin.
  • Patent Document 2 a (meth)acrylic polymer having a glass transition temperature of ⁇ 40° C. or lower, and 5 parts by weight or more and 40 parts by weight or less of tackifier with respect to 100 parts by weight of the (meth)acrylic polymer.
  • a resin composition containing a resin is described.
  • the present invention provides a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer exhibiting high adhesion to low-polar adherends such as polypropylene, polyethylene, and cycloolefin-based resins and having excellent heat resistance, and
  • An object of the present invention is to provide a pressure-sensitive adhesive sheet using the same.
  • a pressure-sensitive adhesive composition obtained by blending an acrylic polymer mainly composed of alkoxyalkyl (meth)acrylate with a tackifying resin having a high hydroxyl value has a low polarity.
  • the inventors have found that high adhesiveness is exhibited to an adherent, and have completed the present invention.
  • the (meth)acrylic polymer (A) contains 51 to 99.9% by mass of an alkoxyalkyl (meth)acrylate, 0.1 to 15% by mass of a carboxy group-containing monomer, and 0% of a hydroxyl group-containing monomer.
  • a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer having excellent adhesion to a low-polar adherend such as a polyolefin, and a low-polarity adherend.
  • a pressure-sensitive adhesive sheet having an excellent pressure-sensitive adhesive layer can be provided.
  • acryl and methacryl are also collectively referred to as “(meth)acryl”
  • acrylate and methacrylate are also collectively referred to as “(meth)acrylate”.
  • polymerization and copolymerization are collectively referred to as “polymerization”
  • polymers and copolymers are collectively referred to as “polymer”.
  • the pressure-sensitive adhesive composition comprises a specific (meth)acrylic polymer (A), a tackifying resin (B) having a hydroxyl value of 100 mgKOH/g or more, and a cross-linking agent (C).
  • A specific (meth)acrylic polymer
  • B tackifying resin
  • C cross-linking agent
  • the (meth)acrylic polymer (A) contained in the adhesive composition of the present invention contains 51 to 99.9% by mass of alkoxyalkyl (meth)acrylate and 0.1 to 15% by mass of a crosslinkable functional group-containing monomer. % of monomer component (a).
  • This monomer component (a) may be composed only of an alkoxyalkyl (meth)acrylate and a crosslinkable functional group-containing monomer, or may contain other monomers.
  • Alkoxyalkyl (meth)acrylate The number of carbon atoms in the alkoxyalkyl group in the alkoxyalkyl (meth)acrylate is usually 2-18, preferably 2-12, more preferably 2-10.
  • Alkoxyalkyl (meth)acrylates include, for example, methoxymethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl ( meth)acrylate, 4-methoxybutyl (meth)acrylate, 4-ethoxybutyl (meth)acrylate.
  • alkoxyalkyl (meth)acrylate may be used alone, or two or more types may be used, but 2-methoxyethyl (meth)acrylate is preferred.
  • the amount of the alkoxyalkyl (meth)acrylate used in the total monomer component (a) is 51 to 99.9% by mass, preferably 71 to 99.9% by mass, more preferably 81 to 98% by mass. is.
  • crosslinkable functional group-containing monomer is preferably a monomer having at least one of a carboxy group and a hydroxyl group as a crosslinkable functional group, and at least one selected from a carboxy group-containing monomer and a hydroxyl group-containing monomer More preferably, it is a seed monomer.
  • carboxy group-containing monomer examples include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, itaconic acid, crotonic acid, and malein. Acids include fumaric acid and maleic anhydride, with (meth)acrylic acid being preferred.
  • carboxy group-containing monomer one type may be used alone, or two or more types may be used.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl ( meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, chloro-2-hydroxypropyl acrylate, diethylene glycol mono (meth) acrylate, allyl alcohol, 2-hydroxyethyl (meth) acrylate, 4-hydroxy Butyl (meth)acrylate is preferred.
  • the hydroxyl group-containing monomer one type may be used alone, or two or more types may be used.
  • At least part of the carboxyl groups and hydroxyl groups derived from the crosslinkable functional group-containing monomer becomes a crosslink point in the (meth)acrylic copolymer (A), and reacts with a crosslinker (C) described later to form a crosslinked structure. can be formed.
  • the crosslinkable functional group-containing monomer one type may be used alone, or two or more types may be used.
  • the amount of the crosslinkable functional group-containing monomer used in the total monomer component (a) is 0.1 to 15% by mass, preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass. is. In such a mode, a crosslinked structure of the (meth)acrylic polymer (A) is appropriately formed, and a pressure-sensitive adhesive layer having appropriate flexibility can be obtained.
  • Other monomers As other monomers that may be contained in the monomer component (a), monomers that can be copolymerized with the alkoxyalkyl (meth)acrylate and the crosslinkable functional group-containing monomer can be used without particular limitation.
  • (meth)acrylic acid alkyl esters alicyclic hydrocarbon group-containing (meth)acrylates, nitrogen atom-containing monomers, epoxy group-containing (meth)acrylates, acetoacetyl group-containing (meth)acrylates, aromatic ring-containing Monomers, methacryloxypropylmethoxysilane, vinyl acetate, vinyl chloride, (meth)acrylonitrile.
  • Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, iso -butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, n-heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate , iso-octyl (meth) acrylate, n-nonyl (meth) acrylate, iso-nonyl (meth) acrylate, n-decyl (meth) acrylate, iso-decyl (meth) acrylate, lauryl (meth
  • Examples of the alicyclic hydrocarbon group-containing (meth)acrylate include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate.
  • nitrogen atom-containing monomer examples include monomers having at least one functional group of an amide group and an amino group, specifically (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-isopropyl (meth) ) acrylamide, N,N-diethyl (meth)acrylamide, acryloylmorpholine, N-vinylacetamide, diacetone (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, vinylpyrrolidone, methylol (meth)acrylamide, methoxy Amide group-containing monomers such as ethyl (meth)acrylamide; N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, aminoethyl ( Amino group-containing monomers such as meth)acrylates
  • Examples of the epoxy group-containing (meth)acrylate include glycidyl (meth)acrylate.
  • Examples of the acetoacetyl group-containing (meth)acrylate include acetoacetoxyethyl (meth)acrylate.
  • aromatic ring-containing monomer examples include benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, methylstyrene, and vinyltoluene.
  • the other monomer is usually 30% by mass or less, preferably 0.1 to 30% by mass, in 100% by mass of the monomer component (a). , more preferably 0.2 to 25% by mass.
  • the other monomer it may be used individually by 1 type, or 2 or more types may be used.
  • the weight average molecular weight (Mw) of the (meth)acrylic polymer (A) by gel permeation chromatography (GPC) is usually 300,000 to 1,500,000. With such an aspect, it is possible to obtain a pressure-sensitive adhesive excellent in high-temperature durability. Moreover, the coating property of the pressure-sensitive adhesive composition is also excellent.
  • the (meth)acrylic polymer (A) is obtained by polymerizing the monomer component (a) by a conventionally known polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method and a suspension polymerization method. However, those produced by a solution polymerization method are preferred.
  • the (meth)acrylic polymer (A) may be obtained as a polymer solution containing the polymer and an organic solvent. Examples of the organic solvent that can be used for polymerization include organic solvents that will be described later as polymerization solvents used for solution polymerization.
  • a polymerization solvent and a monomer component (a) are charged into a reaction vessel, a polymerization initiator is added under an inert gas atmosphere such as nitrogen gas, and the reaction initiation temperature is usually 40 to 100° C., preferably 50 to The temperature is set to 90° C., and the reaction system is usually maintained at a temperature of 50 to 90° C., preferably 60 to 90° C., and reacted for 3 to 20 hours to obtain a (meth)acrylic polymer (A). .
  • polymerization initiators include peroxide polymerization initiators and azo initiators.
  • Peroxide-based polymerization initiators include, for example, t-butyl hydroperoxide, cumene hydroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-i-propylperoxydicarbonate.
  • azo initiators examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2- cyclopropylpropionitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane-1-carbo nitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis(2-amidinopropane) dihydrochloride, 2,2′- azobis(N,N'-dimethyleneisobutylamidine), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(isobutylamide) dihydrate, 4 , 4'
  • polymerization initiator may be used alone, or two or more types may be used. Moreover, it is not limited to adding the polymerization initiator multiple times during the polymerization.
  • the polymerization initiator is usually in the range of 0.001 to 5 parts by mass, preferably 0.005 to 3 parts by mass with respect to 100 parts by mass of the monomer component (a) forming the (meth)acrylic polymer (A). used in the amount of Moreover, a polymerization initiator, a chain transfer agent, a polymerizable monomer, and a polymerization solvent may be added as appropriate during the polymerization reaction.
  • polymerization solvent used for solution polymerization examples include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; cyclopentane, cyclohexane, cycloheptane, alicyclic hydrocarbons such as cyclooctane; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, Halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane, chlorobenzene; Esters such as ethyl acetate, propyl acetate, butyl acetate
  • ketones such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; sulfoxides such as dimethylsulfoxide and sulfolane;
  • Tackifying resin (B) The tackifier resin (B) contained in the pressure-sensitive adhesive composition of the present invention has a hydroxyl value of 100 mgKOH/g or more.
  • the hydroxyl value of the tackifier resin (B) is preferably 100 mgKOH/g or more, more preferably 110 mgKOH/g or more. Moreover, the hydroxyl value is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less.
  • the hydroxyl value of the tackifier resin (B) can be measured by potentiometric titration. When the hydroxyl value is within the above range, the compatibility with the (meth)acrylic polymer (A) is good, and the resulting pressure-sensitive adhesive sheet can have high adhesion to low-polar adherends. .
  • the tackifying resin (B) since the (meth)acrylic polymer (A) and the tackifying resin (B) have excellent compatibility, the tackifying resin (B) does not bleed out on the surface of the pressure-sensitive adhesive layer after the pressure-sensitive adhesive sheet is produced. is suppressed.
  • the acid value of the tackifying resin (B) is not particularly limited, but is usually 10 mgKOH/g or less, preferably 5 mgKOH/g or less, more preferably 3 mgKOH/g or less, and particularly preferably 0 to 1 mgKOH. /g.
  • the acid value of the tackifier resin (B) can be measured by potentiometric titration. When the acid value is within the above range, the compatibility with the (meth)acrylic polymer (A) is good, and the pressure-sensitive adhesive sheet obtained has excellent tackiness.
  • the softening point of the tackifying resin (B) can be appropriately selected depending on the desired adhesive property, and is not particularly limited, but is usually 90 to 180°C, preferably 95 to 170°C, more preferably 100 to 160°C. is. When the softening point is within the above range, the pressure-sensitive adhesive composition obtained can be suitably used for automobile applications where heat resistance is required.
  • the tackifying resin (B) may have a hydroxyl value of 100 mgKOH/g or more, and its structure is not particularly limited. , hydroxyl-modified resins, and resins obtained from (meth)acrylic low-molecular-weight substances having high hydroxyl groups. Among these, resins having a phenol skeleton are preferred because they are readily available, inexpensive, and economical. Examples of the resin having a phenol skeleton used as the tackifying resin (B) include resins having a hydroxyl value of 100 mgKOH/g or more and having a phenol skeleton in the main chain or side chain. Examples include phenol resins and resins in which a phenol skeleton is introduced by graft modification.
  • tackifying resin (B) examples include YS Polystar G125 (hydroxyl value 115 mgKOH/g, acid value 0 mgKOH/g, softening point 125° C.) manufactured by Yasuhara Chemical, YS Polystar G150 (hydroxyl value 115 mgKOH/g, acid value 0 mgKOH).
  • the amount of the tackifying resin (B) in the pressure-sensitive adhesive composition according to the present invention is usually 10 to 50 parts by mass, preferably 10 to 50 parts by mass, based on 100 parts by mass of the (meth)acrylic polymer (A). 40 parts by mass, more preferably 15 to 30 parts by mass.
  • amount of the tackifying resin (B) is within the above range, a pressure-sensitive adhesive sheet having excellent high-temperature properties can be obtained.
  • Crosslinking agent (C) The cross-linking agent (C) contained in the pressure-sensitive adhesive composition according to the present invention is not particularly limited as long as it can cross-link the (meth)acrylic polymer (A).
  • a cross-linking agent capable of reacting with the (meth)acrylic polymer (A) such as an isocyanate compound (C1), an epoxy compound (C2), a metal chelate compound (C3), etc., can be used. can.
  • the said crosslinking agent (C) may be used individually by 1 type, or may use 2 or more types.
  • isocyanate compound (C1) for example, an isocyanate compound having 2 or more isocyanate groups in one molecule is usually used, preferably 2 to 8, more preferably 3 to 6.
  • the number of isocyanate groups is within the above range, it is preferable from the viewpoint of efficiency of the cross-linking reaction between the (meth)acrylic polymer (A) and the isocyanate compound and the flexibility of the pressure-sensitive adhesive layer.
  • diisocyanate compounds having two isocyanate groups in one molecule include aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates.
  • Aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, 2,2,4-trimethyl Aliphatic diisocyanates having 4 to 30 carbon atoms such as -1,6-hexamethylene diisocyanate can be mentioned.
  • the alicyclic diisocyanate includes alicyclic compounds having 7 to 30 carbon atoms such as isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylene diisocyanate.
  • Diisocyanates can be mentioned.
  • aromatic diisocyanates include aromatic diisocyanates having 8 to 30 carbon atoms such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenylether diisocyanate, diphenylmethane diisocyanate and diphenylpropane diisocyanate.
  • isocyanate compounds having 3 or more isocyanate groups in one molecule include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Specific examples include 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, and 4,4',4''-triphenylmethane triisocyanate.
  • isocyanate compounds include polymers (e.g. dimers or trimers, biuret forms, isocyanurate forms) and derivatives (e.g., polyhydric alcohols and addition reaction products with diisocyanate compounds having two or more molecules) and polymers.
  • polyhydric alcohol in the derivative include low-molecular-weight polyhydric alcohols such as trimethylolpropane, glycerin, and pentaerythritol, and trihydric or higher alcohols.
  • High-molecular-weight polyhydric alcohols include, for example, polyether polyol, polyester polyols, acrylic polyols, polybutadiene polyols, and polyisoprene polyols.
  • isocyanate compounds include trimers of diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, biuret or isocyanurate of hexamethylene diisocyanate or tolylene diisocyanate, trimethylolpropane and tolylene diisocyanate or xylylene diisocyanate. (e.g. trimolecular adducts of tolylene diisocyanate or xylylene diisocyanate), reaction products of trimethylolpropane with hexamethylene diisocyanate (e.g. trimolecular adducts of hexamethylene diisocyanate), polyether polyisocyanates, Polyester polyisocyanates are mentioned.
  • xylylene diisocyanate-based and hexamethylene diisocyanate-based cross-linking agents are preferred from the viewpoint of resistance to yellowing, and tolylene diisocyanate-based cross-linking agents are preferred from the viewpoint of stress relaxation.
  • xylylene diisocyanate-based cross-linking agents include xylylene diisocyanate, polymers and derivatives thereof, and polymers.
  • hexamethylene diisocyanate-based cross-linking agents include hexamethylene diisocyanate, polymers and derivatives thereof, and polymers.
  • tolylene diisocyanate-based cross-linking agents include tolylene diisocyanate, its multimers, derivatives, and polymers.
  • Epoxy compound (C2) examples include compounds having two or more epoxy groups in the molecule, such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis( N,N'-diamineglycidylaminomethyl).
  • Metal chelate compound (C3) examples include polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium, and alkoxides, acetylacetone, ethyl acetoacetate, and the like. Coordinated compounds are included. Specific examples include aluminum isopropylate, aluminum secondary butyrate, aluminum ethylacetoacetate/diisopropylate, aluminum trisethylacetoacetate, and aluminum trisacetylacetonate.
  • the amount of the cross-linking agent (C) in the pressure-sensitive adhesive composition is usually 0.01 to 10 parts by mass, preferably 0.01 to 10 parts by mass, per 100 parts by mass of the (meth)acrylic polymer (A). 02 to 5 parts by mass, more preferably 0.03 to 2.5 parts by mass. In such a mode, a sufficiently and moderately crosslinked structure is formed, a cohesive force is high, and a pressure-sensitive adhesive having excellent balance of adhesive physical properties and excellent durability can be obtained.
  • Organic solvent (D) The pressure-sensitive adhesive composition of the present invention may contain an organic solvent (D) in order to adjust coatability.
  • organic solvent (D) include the organic solvents listed in the production conditions for the (meth)acrylic polymer (A) described above.
  • the organic solvent used in the production of the (meth)acrylic polymer (A) and the organic solvent (D) contained in the pressure-sensitive adhesive composition may be the same organic solvent or different organic solvents. good.
  • As the organic solvent one type may be used alone, or two or more types may be used.
  • the adhesive composition contains the organic solvent (D), it is usually 30 to 90% by mass, preferably 40 to 90% by mass, based on 100% by mass of the adhesive composition.
  • Additive (E) The pressure-sensitive adhesive composition of the present invention may contain an additive (E) in addition to the components (A) to (D) as long as the effects of the present invention are not impaired.
  • the additive (E) includes, for example, a tackifying resin other than the tackifying resin (B), a silane coupling agent, an antistatic agent, an antioxidant, a light stabilizer, a metal corrosion inhibitor, a plasticizer, and a cross-linking accelerator. and rework agents.
  • a tackifying resin other than the tackifying resin (B) e.g., a silane coupling agent, an antistatic agent, an antioxidant, a light stabilizer, a metal corrosion inhibitor, a plasticizer, and a cross-linking accelerator. and rework agents.
  • the additive (E) one type may be used alone, or two or more types may be used.
  • the amount varies depending on the type of the additive (E) and is not particularly limited. 0.01 to 10 mass %, preferably 0.1 to 5 mass %.
  • the pressure-sensitive adhesive composition of the present invention can be prepared, for example, by mixing the components described above by a conventionally known method. For example, by mixing a solution containing a (meth)acrylic polymer (A), a tackifying resin (B), a cross-linking agent (C), and optionally other components such as additives, , an adhesive composition can be prepared.
  • the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition comprising the (meth)acrylic polymer (A), the tackifying resin (B), and the cross-linking agent (C) has a haze of 5.0 at a thickness of 25 ⁇ m. It is preferably 0% or less, more preferably 0.5 to 4.5%, even more preferably 1.0 to 2.5%.
  • the fact that the haze is in the above range indicates that the (meth)acrylic polymer (A) and the tackifying resin (B) are appropriately compatible, and the obtained pressure-sensitive adhesive sheet has low polarity adhesion. It exhibits high adhesiveness to the body.
  • the pressure-sensitive adhesive composition may contain additives that inhibit transparency such as fillers and pigments. It is preferable that the haze of the pressure-sensitive adhesive layer with a thickness of 25 ⁇ m consisting of the combination (A), the tackifying resin (B) and the cross-linking agent (C) is within the above range.
  • the contact angle between the surface of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention and liquid paraffin is preferably less than 40°, more preferably 10 to 35°.
  • a contact angle within the above range indicates that the tackifying resin (B) is appropriately present on the surface of the pressure-sensitive adhesive layer that contacts the adherend.
  • the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition exhibits the above properties, for example, polyethylene (PE), polypropylene (PP), various polyolefins such as cycloolefin resin (COP), etc. It also exhibits high adhesiveness to the body.
  • PE polyethylene
  • PP polypropylene
  • COP cycloolefin resin
  • a pressure-sensitive adhesive sheet according to one aspect of the present invention has a pressure-sensitive adhesive layer formed from the above-described pressure-sensitive adhesive composition according to one aspect of the present invention, and includes forms such as sheets and tapes.
  • the adhesive sheet for example, an adhesive sheet formed only from an adhesive layer, having a substrate and adhesive layers formed on both sides of the substrate, at least one adhesive layer being the adhesive of the present invention
  • the present A pressure-sensitive adhesive sheet in which substrates are arranged on both sides of a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the invention can be mentioned.
  • the base material is not particularly limited, and includes plastic base materials, nonwoven fabrics, woven fabrics, paper, metals, glass, ceramics, foams, and the like.
  • the thickness of the base material varies depending on its use, etc., and is not particularly limited, but is usually 5 to 200 ⁇ m.
  • Plastic substrates include plastic substrates selected from polyethylene terephthalate, polyvinyl chloride, polyolefin, polypropylene, polymethyl methacrylate, polycarbonate, polyimide, and ABS.
  • the substrate may be a release-treated substrate.
  • the pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet having substrates arranged on both sides of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention, at least one of the substrates is a release-treated substrate. , the release-treated substrate is removed at the time of adhesion to the adherend.
  • the thickness of the pressure-sensitive adhesive layer can be appropriately selected depending on the application, etc., and is not particularly limited, but from the viewpoint of maintaining adhesive performance, it is usually 5 to 200 ⁇ m, preferably 10 to 100 ⁇ m.
  • At least a part of the pressure-sensitive adhesive layer may be crosslinked by reacting the (meth)acrylic polymer (A) and the cross-linking agent (C) in the pressure-sensitive adhesive composition during the production process.
  • the method for producing the pressure-sensitive adhesive sheet is not particularly limited, and examples thereof are as follows.
  • the pressure-sensitive adhesive composition described above is applied onto a substrate.
  • the pressure-sensitive adhesive composition contains a solvent, it is usually dried at 50 to 150° C., preferably 60 to 100° C., usually for 1 to 10 minutes, preferably for 2 to 7 minutes to remove the solvent, and the coating film to form Subsequently, another base material is attached to the surface of the coating film on the side without the base material.
  • known methods such as spin coating, knife coating, roll coating, bar coating, blade coating, die coating, gravure coating, and doctor blade coating can be applied to a predetermined thickness. It is possible to use a method of coating and drying so as to be even.
  • a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition exhibits excellent adhesive strength even to low-polarity adherends such as polyolefins, and has excellent high-temperature properties, so it is suitable for various applications such as automobile applications. It can be used preferably.
  • ((Meth) acrylic polymer A) A method for measuring the weight average molecular weight (Mw) of the (meth)acrylic polymer (A) is as follows.
  • the weight average molecular weight (Mw) in terms of standard polystyrene was determined by gel permeation chromatography (GPC) under the following conditions.
  • ⁇ Measuring device HLC-8120GPC (manufactured by Tosoh)
  • GPC column configuration the following 5-column column (all manufactured by Tosoh) (1) TSK-GEL HXL-H (guard column) (2) TSK-GEL G7000HXL (3) TSK-GEL GMHXL (4) TSK-GEL GMHXL (5) TSK-GEL G2500HXL ⁇ Sample concentration: diluted with tetrahydrofuran to 1.0 mg/cm 3 ⁇ Mobile phase solvent: tetrahydrofuran ⁇ Flow rate: 1.0 cm 3 /min ⁇ Column temperature: 40°C [Production Example 1] (Production of acrylic polymer (A-1)) 96.8 parts by mass of 2-methoxyethyl acrylate, 3 parts by mass of acrylic acid, 0.2 parts by mass of 2-hydroxyethyl acrylate, and 37 parts by mass of toluene were added to a flask equipped with
  • Acrylic polymers (A-2) to (A-6) were prepared in the same manner as in Production Example 1, except that the types of monomers to be subjected to polymerization and the charging composition (parts by mass) were changed as shown in Table 1. , (A′-7), or (A′-8) was obtained.
  • Production Example 2 the reaction was performed by replacing the 37 parts by mass of toluene and 24 parts by mass of ethyl acetate charged at the start of polymerization in Production Example 1 with 24 parts by mass of toluene and 37 parts by mass of ethyl acetate.
  • Production Example 3 the reaction was performed by replacing 37 parts by mass of toluene and 24 parts by mass of ethyl acetate charged at the start of polymerization in Production Example 1 with 47 parts by mass of toluene and 14 parts by mass of ethyl acetate.
  • Table 1 shows the weight average molecular weight (Mw) of each obtained acrylic polymer measured by gel permeation chromatography (GPC).
  • Tackifier resin B In the following examples and comparative examples, the following tackifying resins were used.
  • each physical property of the tackifier resin was measured by the following methods.
  • the softening point was determined by the softening point test method (ring and ball method) specified in JIS K2207.
  • hydroxyl value was determined according to JIS K0070 by potentiometric titration as mg of potassium hydroxide required to neutralize acetic acid bound to hydroxyl groups when 1 g of the tackifying resin was acetylated.
  • the acid value was determined by potentiometric titration as mg of potassium hydroxide required to neutralize 1 g of the tackifying resin in accordance with JIS K0070.
  • ⁇ Measurement of liquid paraffin contact angle> 20 parts by mass of a tackifying resin and 30 parts by mass of ethyl acetate were put into a container to prepare a solution of the tackifying resin. Next, after a plastic plate was submerged in the prepared tackifying resin solution, it was dried in an environment of 80°C for 5 minutes. The droplets were allowed to stand, and the contact angle of liquid paraffin was measured in air using a KYOWA CONTACT-ANGLE METER CA-D manufactured by Kyowa Interface Science, and the average value of n 10 was used as the measured value. Measurement conditions conformed to JIS R3257.
  • Example 1 (Production of adhesive composition) To the acrylic polymer (A-1) solution obtained in Production Example 1 (100 parts by mass in terms of solid content (acrylic polymer)), 20 parts by mass of the tackifier resin (B-1) and epoxy-based cross-linking agent E-5XM ( Soken Kagaku Co., Ltd.) was added in an amount of 0.045 parts by mass in terms of solid content, and the mixture was stirred with a glass rod for 5 minutes to obtain an adhesive composition (1).
  • the obtained pressure-sensitive adhesive composition was applied to a thickness of 25 ⁇ m after drying using a doctor blade after removing the bubbles, and was heated at 80° C. for 3 minutes. The solvent was removed by drying to form a coating film to be an adhesive layer.
  • PET polyethylene terephthalate
  • a release-treated PET film was attached to the surface of the adhesive layer opposite to the surface in contact with the PET film. After that, it was allowed to stand still for 7 days under conditions of 23° C./50% RH for aging to produce a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer with a thickness of 25 ⁇ m.
  • the pressure-sensitive adhesive sheet was cut into a size of 25 mm ⁇ 100 mm to obtain a test piece.
  • the peel-treated PET film of the obtained test piece is peeled off, and the exposed adhesive layer is applied to each of the adherends PP (polypropylene) plate, PE (polyethylene) plate, and COP (cycloolefin resin) plate. After sticking and crimping with a 2-kg roller 3 reciprocations, it was allowed to stand for 20 minutes in a 23° C./50% RH environment. After that, the end portion of the test piece was pulled at a speed of 300 mm/min in the direction of 180° to various adherends, and the adhesive strength (N/25 mm) was measured.
  • a release-treated PET film was attached to the surface of the pressure-sensitive adhesive layer opposite to the surface in contact with the release-treated PET film. After that, it was aged by standing for 7 days under the conditions of 23° C./50% RH.
  • the peel-treated PET film was peeled off from one side of the obtained adhesive sheet, and the exposed adhesive layer and a glass plate (manufactured by AGC Fabritech, alkali glass FL, 1.1 mm thick, haze value: 0.1%) were separated. and pasted together.
  • the rest of the peel-treated PET film was peeled off, and the haze value of the test piece having only the adhesive layer on the glass plate was measured using a haze meter (model name HM-150, manufactured by Murakami Color Research Laboratory). did.
  • the haze (%) of the pressure-sensitive adhesive layer was obtained by subtracting 0.1, which is the haze value of only the glass plate, from the haze value of the obtained test piece.
  • Examples 2 to 11 Comparative Examples 1 to 7
  • a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet were obtained in the same manner as in Example 1, except that the types and amounts of the acrylic polymer and the tackifying resin were changed as shown in Tables 3 and 4.
  • the pressure-sensitive adhesive sheets obtained from the pressure-sensitive adhesive compositions of Examples 1 to 11 are low-polarity and difficult-to-adhere polyethylene, polypropylene, and polyolefin resin. It can be seen that it exhibits good adhesiveness to the body as well.
  • the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition described in Examples 1 to 11 has a low haze and good compatibility between the (meth)acrylic polymer (A) and the tackifier resin (B). It was shown that it can be suitably used for applications that require transparency. Furthermore, since the contact angles of liquid paraffin of the pressure-sensitive adhesive layers obtained from the pressure-sensitive adhesive compositions described in Examples 1 to 8 are all less than 40°, the tackifying resin component is sufficiently present on the pressure-sensitive adhesive layer surface. It was shown to exhibit high adhesive strength.
  • the adhesive composition of the present invention is suitable for use in forming an adhesive layer of an adhesive sheet.
  • the pressure-sensitive adhesive sheet of the present invention is suitable as a pressure-sensitive adhesive sheet for use in automotive interior and exterior materials and various structures, and is particularly used in applications where it is applied to difficult-to-adhere substrates, such as automobiles, and where heat resistance is required. It is suitable as a pressure-sensitive adhesive sheet.

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Abstract

The present invention addresses the problem of providing: an adhesive composition that exhibits high adhesiveness with respect to a low-polarity adherend and that is capable of forming an adhesive layer and the like having excellent heat resistance; and an adhesive sheet using the adhesive composition.　The adhesive composition according to the present invention contains: a (meth)acrylic polymer (A) which is a polymer of a monomer component (a) including 51-99.9 mass% of an alkoxy alkyl (meth)acrylate and 0.1-15 mass% of a cross-linkable functional group-containing monomer; a tackifying resin (B) having a hydroxyl value of 100 mgKOH/g or more; and a cross-linking agent (C). The tackifying resin (B) is contained in an amount of 10-50 parts by mass with respect to 100 parts by mass of the (meth)acrylic polymer (A).

Description

粘着剤組成物および粘着シートAdhesive composition and adhesive sheet
　本発明は、粘着剤組成物および粘着シートに関する。 The present invention relates to an adhesive composition and an adhesive sheet.
　自動車等に用いられる材料は、金属系の材料からプラスチック系の材料へと置き換えが進められている。これは自動車の軽量化の求められていること、並びにプラスチック材料の高強度化が進んできたことが背景にある。 Materials used in automobiles, etc. are being replaced from metal-based materials to plastic-based materials. This is due to the fact that automobiles are required to be lighter and the strength of plastic materials has been increased.
　一般に、プラスチック系材料は低極性であり、汎用性のあるポリプロピレン、ポリエチレン、およびシクロオレフィン系樹脂等の材料は難接着性の被着体として知られている。このため、自動車用途等に使用される粘着シートには、難接着性の低極性被着体に対して良好な接着性を有することが求められる。 In general, plastic materials have low polarity, and versatile materials such as polypropylene, polyethylene, and cycloolefin resins are known to be difficult-to-adhere adherends. Therefore, pressure-sensitive adhesive sheets used for automotive applications and the like are required to have good adhesion to low-polarity adherends that are difficult to adhere to.
　低極性被着体へ対して高い接着性を示す粘着剤を得る手法として、例えば、特許文献１には、核水添テルペンフェノール樹脂を含むアクリル系粘着剤組成物を使用することが記載されている。また、特許文献２には、ガラス転移温度が－４０℃以下である（メタ）アクリル系ポリマーと、前記（メタ）アクリル系ポリマー１００重量部に対して５重量部以上４０重量部以下の粘着付与樹脂とを含有する樹脂組成物を使用することが記載されている。 As a technique for obtaining a pressure-sensitive adhesive exhibiting high adhesion to low-polarity adherends, for example, Patent Document 1 describes the use of an acrylic pressure-sensitive adhesive composition containing a nuclear hydrogenated terpene phenolic resin. there is Further, in Patent Document 2, a (meth)acrylic polymer having a glass transition temperature of −40° C. or lower, and 5 parts by weight or more and 40 parts by weight or less of tackifier with respect to 100 parts by weight of the (meth)acrylic polymer The use of a resin composition containing a resin is described.
　しかしながら、近年の自動車用途等においては、被着体種を問わず高い接着性を示すことなど、より高度な要求がある。 However, in recent years, in automotive applications, etc., there are more advanced demands, such as showing high adhesiveness regardless of the type of adherend.
特開２００７－２２４２５８号公報JP 2007-224258 A 特開２０１９－１１９８４５号公報JP 2019-119845 A
　本発明は、ポリプロピレン、ポリエチレン、シクロオレフィン系樹脂等の低極性被着体に対して、高い接着性を示すとともに、耐熱性にも優れる粘着剤層を形成することが可能な粘着剤組成物およびそれを用いた粘着シートを提供することを課題とする。 The present invention provides a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer exhibiting high adhesion to low-polar adherends such as polypropylene, polyethylene, and cycloolefin-based resins and having excellent heat resistance, and An object of the present invention is to provide a pressure-sensitive adhesive sheet using the same.
　本発明者は、上記事情に鑑みて鋭意検討した結果、アルコキシアルキル（メタ）アクリレートを主とするアクリル系重合体に、高水酸基価の粘着付与樹脂を配合した粘着剤組成物が、低極性被着体に対して、高い接着性を発現することを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the above circumstances, the present inventors have found that a pressure-sensitive adhesive composition obtained by blending an acrylic polymer mainly composed of alkoxyalkyl (meth)acrylate with a tackifying resin having a high hydroxyl value has a low polarity. The inventors have found that high adhesiveness is exhibited to an adherent, and have completed the present invention.
　すなわち本発明は、以下の〔１〕～〔７〕に関する。
〔１〕アルコキシアルキル（メタ）アクリレートを５１～９９．９質量％と、架橋性官能基含有モノマーを０．１～１５質量％とを含むモノマー成分（ａ）の重合体である、（メタ）アクリル重合体（Ａ）と、
　水酸基価が１００ｍｇＫＯＨ／ｇ以上である粘着付与樹脂（Ｂ）と、
　架橋剤（Ｃ）とを含み、
　前記（メタ）アクリル重合体（Ａ）１００質量部に対して、前記粘着付与樹脂（Ｂ）を１０～５０質量部含む粘着剤組成物。
〔２〕前記（メタ）アクリル重合体（Ａ）が、アルコキシアルキル（メタ）アクリレートを５１～９９．９質量％と、カルボキシ基含有モノマーを０．１～１５質量％と、水酸基含有モノマーを０～５質量％とを含むモノマー成分（ａ）の重合体である、〔１〕に記載の粘着剤組成物。
〔３〕前記粘着剤組成物より得られた厚さ２５μｍの粘着剤層のヘイズが５％未満である、〔１〕または〔２〕に記載の粘着剤組成物。
〔４〕前記粘着剤組成物より得られる粘着剤層表面と、流動パラフィンとの接触角が４０°未満である、〔１〕～〔３〕のいずれかに記載の粘着剤組成物。
〔５〕前記粘着付与樹脂（Ｂ）の酸価が５ｍｇＫＯＨ／ｇ未満である、〔１〕～〔４〕のいずれかに記載の粘着剤組成物。
〔６〕前記粘着付与樹脂（Ｂ）が、フェノール骨格を有する樹脂である、〔１〕～〔５〕のいずれかに記載の粘着剤組成物。
〔７〕〔１〕～〔６〕のいずれかに記載の粘着剤組成物より形成された粘着剤層を有する粘着シート。 That is, the present invention relates to the following [1] to [7].
[1] A polymer of a monomer component (a) containing 51 to 99.9% by mass of an alkoxyalkyl (meth)acrylate and 0.1 to 15% by mass of a crosslinkable functional group-containing monomer, (meth) an acrylic polymer (A);
a tackifying resin (B) having a hydroxyl value of 100 mgKOH/g or more;
and a cross-linking agent (C),
A pressure-sensitive adhesive composition containing 10 to 50 parts by mass of the tackifying resin (B) with respect to 100 parts by mass of the (meth)acrylic polymer (A).
[2] The (meth)acrylic polymer (A) contains 51 to 99.9% by mass of an alkoxyalkyl (meth)acrylate, 0.1 to 15% by mass of a carboxy group-containing monomer, and 0% of a hydroxyl group-containing monomer. The pressure-sensitive adhesive composition according to [1], which is a polymer of the monomer component (a) containing up to 5% by mass.
[3] The pressure-sensitive adhesive composition according to [1] or [2], wherein the pressure-sensitive adhesive layer with a thickness of 25 µm obtained from the pressure-sensitive adhesive composition has a haze of less than 5%.
[4] The pressure-sensitive adhesive composition according to any one of [1] to [3], wherein the contact angle between the surface of the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition and liquid paraffin is less than 40°.
[5] The pressure-sensitive adhesive composition according to any one of [1] to [4], wherein the tackifying resin (B) has an acid value of less than 5 mgKOH/g.
[6] The pressure-sensitive adhesive composition according to any one of [1] to [5], wherein the tackifying resin (B) is a resin having a phenol skeleton.
[7] A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of [1] to [6].
　本発明によれば、ポリオレフィン等の低極性被着体に対して、接着性に優れる粘着剤層等を形成することが可能な粘着剤組成物、ならびに低極性被着体に対して接着性に優れる粘着剤層を有する粘着シートを提供することができる。 According to the present invention, a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer having excellent adhesion to a low-polar adherend such as a polyolefin, and a low-polarity adherend. A pressure-sensitive adhesive sheet having an excellent pressure-sensitive adhesive layer can be provided.
　以下、本発明を詳細に説明する。本明細書においては、アクリルおよびメタクリルを総称して「（メタ）アクリル」、アクリレートおよびメタクリレートを総称して「（メタ）アクリレート」とも記載する。また、重合および共重合を総称して「重合」、重合体および共重合体を総称して「重合体」とも記載する。 The present invention will be described in detail below. In this specification, acryl and methacryl are also collectively referred to as "(meth)acryl", and acrylate and methacrylate are also collectively referred to as "(meth)acrylate". In addition, polymerization and copolymerization are collectively referred to as "polymerization", and polymers and copolymers are collectively referred to as "polymer".
　［粘着剤組成物］
　本発明の一態様に係る粘着剤組成物は、特定の（メタ）アクリル重合体（Ａ）と、水酸基価が１００ｍｇＫＯＨ／ｇ以上である粘着付与樹脂（Ｂ）と、架橋剤（Ｃ）とを含む。 [Adhesive composition]
The pressure-sensitive adhesive composition according to one aspect of the present invention comprises a specific (meth)acrylic polymer (A), a tackifying resin (B) having a hydroxyl value of 100 mgKOH/g or more, and a cross-linking agent (C). include.
　（メタ）アクリル重合体（Ａ）
　本発明の粘着剤組成物に含まれる（メタ）アクリル重合体（Ａ）は、アルコキシアルキル（メタ）アクリレートを５１～９９．９質量％と、架橋性官能基含有モノマーを０．１～１５質量％とを含むモノマー成分（ａ）の重合体である。このモノマー成分（ａ）は、アルコキシアルキル（メタ）アクリレートと、架橋性官能基含有モノマーのみから構成されていてもよく、その他のモノマーを含んでいてもよい。
・アルコキシアルキル（メタ）アクリレート
　アルコキシアルキル（メタ）アクリレートにおけるアルコキシアルキル基の炭素数は、通常は２～１８、好ましくは２～１２、より好ましくは２～１０である。アルコキシアルキル（メタ）アクリレートとしては、例えば、メトキシメチル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、３－メトキシプロピル（メタ）アクリレート、３－エトキシプロピル（メタ）アクリレート、４－メトキシブチル（メタ）アクリレート、４－エトキシブチル（メタ）アクリレートが挙げられる。 (Meth) acrylic polymer (A)
The (meth)acrylic polymer (A) contained in the adhesive composition of the present invention contains 51 to 99.9% by mass of alkoxyalkyl (meth)acrylate and 0.1 to 15% by mass of a crosslinkable functional group-containing monomer. % of monomer component (a). This monomer component (a) may be composed only of an alkoxyalkyl (meth)acrylate and a crosslinkable functional group-containing monomer, or may contain other monomers.
Alkoxyalkyl (meth)acrylate The number of carbon atoms in the alkoxyalkyl group in the alkoxyalkyl (meth)acrylate is usually 2-18, preferably 2-12, more preferably 2-10. Alkoxyalkyl (meth)acrylates include, for example, methoxymethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl ( meth)acrylate, 4-methoxybutyl (meth)acrylate, 4-ethoxybutyl (meth)acrylate.
　アルコキシアルキル（メタ）アクリレートは１種単独で用いてもよく、２種以上を用いてもよいが、２－メトキシエチル（メタ）アクリレートが好ましい。
　全モノマー成分（ａ）中の前記アルコキシアルキル（メタ）アクリレートの使用量は、５１～９９．９質量％であり、好ましくは７１～９９．９質量％であり、より好ましくは８１～９８質量％である。 One type of alkoxyalkyl (meth)acrylate may be used alone, or two or more types may be used, but 2-methoxyethyl (meth)acrylate is preferred.
The amount of the alkoxyalkyl (meth)acrylate used in the total monomer component (a) is 51 to 99.9% by mass, preferably 71 to 99.9% by mass, more preferably 81 to 98% by mass. is.
　アルコキシアルキル（メタ）アクリレートの使用量が前記範囲であると、低極性被着体に対し、十分な接着性が発現する。
・架橋性官能基含有モノマー
　前記架橋性官能基含有モノマーとしては、架橋性官能基として、カルボキシ基および水酸基の少なくとも一方を有するモノマーが好ましく、カルボキシ基含有モノマーおよび水酸基含有モノマーから選択される少なくとも１種のモノマーであることがより好ましい。 When the amount of the alkoxyalkyl (meth)acrylate used is within the above range, sufficient adhesion to low-polar adherends is exhibited.
Crosslinkable functional group-containing monomer The crosslinkable functional group-containing monomer is preferably a monomer having at least one of a carboxy group and a hydroxyl group as a crosslinkable functional group, and at least one selected from a carboxy group-containing monomer and a hydroxyl group-containing monomer More preferably, it is a seed monomer.
　前記カルボキシ基含有モノマーとしては、例えば、（メタ）アクリル酸、２－カルボキシエチル（メタ）アクリレート、３－カルボキシプロピル（メタ）アクリレート、４－カルボキシブチル（メタ）アクリレート、イタコン酸、クロトン酸、マレイン酸、フマル酸および無水マレイン酸が挙げられ、（メタ）アクリル酸が好ましい。前記カルボキシ基含有モノマーとしては、１種単独で用いても、２種以上を用いてもよい。 Examples of the carboxy group-containing monomer include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, 4-carboxybutyl (meth) acrylate, itaconic acid, crotonic acid, and malein. Acids include fumaric acid and maleic anhydride, with (meth)acrylic acid being preferred. As the carboxy group-containing monomer, one type may be used alone, or two or more types may be used.
　前記水酸基含有モノマーとしては、例えば、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、２－ヒドロキシプロピル（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、６－ヒドロキシヘキシル（メタ）アクリレート、１，４－シクロヘキサンジメタノールモノ（メタ）アクリレート、クロロ－２－ヒドロキシプロピルアクリレート、ジエチレングリコールモノ（メタ）アクリレート、アリルアルコールが挙げられ、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）アクリレートが好ましい。前記水酸基含有モノマーとしては、１種単独で用いても、２種以上を用いてもよい。 Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl ( meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, chloro-2-hydroxypropyl acrylate, diethylene glycol mono (meth) acrylate, allyl alcohol, 2-hydroxyethyl (meth) acrylate, 4-hydroxy Butyl (meth)acrylate is preferred. As the hydroxyl group-containing monomer, one type may be used alone, or two or more types may be used.
　架橋性官能基含有モノマー由来のカルボキシ基および水酸基の少なくとも一部は、（メタ）アクリル系共重合体（Ａ）中で架橋点となり、後述する架橋剤（Ｃ）と反応することで、架橋構造を形成することができる。 At least part of the carboxyl groups and hydroxyl groups derived from the crosslinkable functional group-containing monomer becomes a crosslink point in the (meth)acrylic copolymer (A), and reacts with a crosslinker (C) described later to form a crosslinked structure. can be formed.
　前記架橋性官能基含有モノマーとしては、１種単独で用いても、２種以上を用いてもよい。全モノマー成分（ａ）中の前記架橋性官能基含有モノマーの使用量は、０．１～１５質量％であり、好ましくは０．５～１０質量％であり、より好ましくは１～５質量％である。このような態様であると、（メタ）アクリル重合体（Ａ）の架橋構造が適度に形成され、適度な柔軟性を有する粘着剤層が得られる。
・その他のモノマー
　モノマー成分（ａ）に含まれてもよいその他のモノマーとしては、前記アルコキシアルキル（メタ）アクリレートおよび前記架橋性官能基含有モノマーと共重合しうるモノマーを、特に制限なく用いることができるが、例えば、（メタ）アクリル酸アルキルエステル、脂環式炭化水素基含有（メタ）アクリレート、窒素原子含有モノマー、エポキシ基含有（メタ）アクリレート、アセトアセチル基含有（メタ）アクリレート、芳香環含有モノマー、メタクリロキシプロピルメトキシシラン、酢酸ビニル、塩化ビニル、（メタ）アクリロニトリルが挙げられる。 As the crosslinkable functional group-containing monomer, one type may be used alone, or two or more types may be used. The amount of the crosslinkable functional group-containing monomer used in the total monomer component (a) is 0.1 to 15% by mass, preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass. is. In such a mode, a crosslinked structure of the (meth)acrylic polymer (A) is appropriately formed, and a pressure-sensitive adhesive layer having appropriate flexibility can be obtained.
Other monomers As other monomers that may be contained in the monomer component (a), monomers that can be copolymerized with the alkoxyalkyl (meth)acrylate and the crosslinkable functional group-containing monomer can be used without particular limitation. For example, (meth)acrylic acid alkyl esters, alicyclic hydrocarbon group-containing (meth)acrylates, nitrogen atom-containing monomers, epoxy group-containing (meth)acrylates, acetoacetyl group-containing (meth)acrylates, aromatic ring-containing Monomers, methacryloxypropylmethoxysilane, vinyl acetate, vinyl chloride, (meth)acrylonitrile.
　前記（メタ）アクリル酸アルキルエステルとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｉｓｏ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｉｓｏ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ｎ－ヘプチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、ｉｓｏ－オクチル（メタ）アクリレート、ｎ－ノニル（メタ）アクリレート、ｉｓｏ－ノニル（メタ）アクリレート、ｎ－デシル（メタ）アクリレート、ｉｓｏ－デシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、ｉｓｏ－ステアリル（メタ）アクリレートを挙げることができる。 Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, iso -butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, n-heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate , iso-octyl (meth) acrylate, n-nonyl (meth) acrylate, iso-nonyl (meth) acrylate, n-decyl (meth) acrylate, iso-decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) ) acrylate, iso-stearyl (meth)acrylate.
　前記脂環式炭化水素基含有（メタ）アクリレートとしては、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレートを挙げることができる。 Examples of the alicyclic hydrocarbon group-containing (meth)acrylate include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate.
　前記窒素原子含有モノマーとしては、アミド基およびアミノ基の少なくとも一方の官能基を有するモノマーが挙げられ、具体的には（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、アクリロイルモルホリン、Ｎ－ビニルアセトアミド、ダイアセトン（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、ビニルピロリドン、メチロール（メタ）アクリルアミド、メトキシエチル（メタ）アクリルアミド等のアミド基含有モノマー；Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、アミノエチル（メタ）アクリレート等のアミノ基含有モノマーが挙げられる。 Examples of the nitrogen atom-containing monomer include monomers having at least one functional group of an amide group and an amino group, specifically (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-isopropyl (meth) ) acrylamide, N,N-diethyl (meth)acrylamide, acryloylmorpholine, N-vinylacetamide, diacetone (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, vinylpyrrolidone, methylol (meth)acrylamide, methoxy Amide group-containing monomers such as ethyl (meth)acrylamide; N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, aminoethyl ( Amino group-containing monomers such as meth)acrylates can be mentioned.
　前記エポキシ基含有（メタ）アクリレートとしては、グリシジル（メタ）アクリレートを挙げることができる。
　前記アセトアセチル基含有（メタ）アクリレートとしては、アセトアセトキシエチル（メタ）アクリレートを挙げることができる。 Examples of the epoxy group-containing (meth)acrylate include glycidyl (meth)acrylate.
Examples of the acetoacetyl group-containing (meth)acrylate include acetoacetoxyethyl (meth)acrylate.
　前記芳香環含有モノマーとしては、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、スチレン、メチルスチレン、ビニルトルエンを挙げることができる。 Examples of the aromatic ring-containing monomer include benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, styrene, methylstyrene, and vinyltoluene.
　前記モノマー成分（ａ）が前記その他のモノマーを含む場合には、前記その他のモノマーは、前記モノマー成分（ａ）１００質量％中に、通常３０質量％以下、好ましくは０．１～３０質量％、より好ましくは０．２～２５質量％含まれる。前記その他のモノマーとしては、１種単独で用いても、２種以上を用いてもよい。 When the monomer component (a) contains the other monomer, the other monomer is usually 30% by mass or less, preferably 0.1 to 30% by mass, in 100% by mass of the monomer component (a). , more preferably 0.2 to 25% by mass. As said other monomer, it may be used individually by 1 type, or 2 or more types may be used.
　（メタ）アクリル重合体（Ａ）のゲルパーミエーションクロマトグラフィー（ＧＰＣ）による重量平均分子量（Ｍｗ）は、通常は３０万～１５０万である。このような態様であると、高温耐久性に優れた粘着剤を得ることができる。また、粘着剤組成物の塗工性にも優れる。 The weight average molecular weight (Mw) of the (meth)acrylic polymer (A) by gel permeation chromatography (GPC) is usually 300,000 to 1,500,000. With such an aspect, it is possible to obtain a pressure-sensitive adhesive excellent in high-temperature durability. Moreover, the coating property of the pressure-sensitive adhesive composition is also excellent.
　（（メタ）アクリル重合体（Ａ）の製造条件）
　前記（メタ）アクリル重合体（Ａ）は、前記モノマー成分（ａ）を、溶液重合法、塊状重合法、乳化重合法および懸濁重合法等の従来公知の重合法により重合することで得ることができるが、溶液重合法により製造したものが好ましい。（メタ）アクリル重合体（Ａ）は、該重合体と、有機溶媒とからなるポリマー溶液として得てもよい。重合に使用できる有機溶媒としては、溶液重合に用いる重合溶媒として後述する有機溶媒が挙げられる。 (Conditions for producing (meth)acrylic polymer (A))
The (meth)acrylic polymer (A) is obtained by polymerizing the monomer component (a) by a conventionally known polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method and a suspension polymerization method. However, those produced by a solution polymerization method are preferred. The (meth)acrylic polymer (A) may be obtained as a polymer solution containing the polymer and an organic solvent. Examples of the organic solvent that can be used for polymerization include organic solvents that will be described later as polymerization solvents used for solution polymerization.
　例えば、反応容器内に重合溶媒と、モノマー成分（ａ）とを仕込み、窒素ガス等の不活性ガス雰囲気下で重合開始剤を添加し、反応開始温度を通常４０～１００℃、好ましくは５０～９０℃に設定し、通常５０～９０℃、好ましくは６０～９０℃の温度に反応系を維持して、３～２０時間反応させることにより（メタ）アクリル重合体（Ａ）を得ることができる。 For example, a polymerization solvent and a monomer component (a) are charged into a reaction vessel, a polymerization initiator is added under an inert gas atmosphere such as nitrogen gas, and the reaction initiation temperature is usually 40 to 100° C., preferably 50 to The temperature is set to 90° C., and the reaction system is usually maintained at a temperature of 50 to 90° C., preferably 60 to 90° C., and reacted for 3 to 20 hours to obtain a (meth)acrylic polymer (A). .
　重合開始剤としては、例えば、過酸化物系重合開始剤、アゾ系開始剤が挙げられる。
　過酸化物系重合開始剤としては、例えば、ｔ－ブチルハイドロパーオキサイド、クメンハイドロオキサイド、ジクミルパーオキサイド、ベンゾイルパーオキシド、ラウロイルパーオキシド、カプロイルパーオキシド、ジ－ｉ－プロピルパーオキシジカーボネート、ジ－２－エチルヘキシルパーオキシジカーボネート、ｔ－ブチルパーオキシピバレート、２，２－ビス（４，４－ジ－ｔ－ブチルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジ－ｔ－アミルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジ－ｔ－オクチルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジ－α－クミルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジ－ｔ－ブチルパーオキシシクロヘキシル）ブタン、２，２－ビス（４，４－ジ－ｔ－オクチルパーオキシシクロヘキシル）ブタンが挙げられる。 Examples of polymerization initiators include peroxide polymerization initiators and azo initiators.
Peroxide-based polymerization initiators include, for example, t-butyl hydroperoxide, cumene hydroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-i-propylperoxydicarbonate. , di-2-ethylhexyl peroxydicarbonate, t-butyl peroxypivalate, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 2,2-bis(4,4- Di-t-amylperoxycyclohexyl)propane, 2,2-bis(4,4-di-t-octylperoxycyclohexyl)propane, 2,2-bis(4,4-di-α-cumylperoxycyclohexyl) ) propane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)butane, and 2,2-bis(4,4-di-t-octylperoxycyclohexyl)butane.
　アゾ系開始剤としては、例えば、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２－シクロプロピルプロピオニトリル）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２－メチルブチロニトリル）、１，１’－アゾビス（シクロヘキサン－１－カルボニトリル）、２－（カルバモイルアゾ）イソブチロニトリル、２－フェニルアゾ－４－メトキシ－２，４－ジメチルバレロニトリル、２，２’－アゾビス（２－アミジノプロパン）ジヒドロクロリド、２，２’－アゾビス（Ｎ，Ｎ’－ジメチレンイソブチルアミジン）、２，２’－アゾビス〔２－メチル－Ｎ－（２－ヒドロキシエチル）－プロピオンアミド〕、２，２’－アゾビス（イソブチルアミド）ジヒドレート、４，４’－アゾビス（４－シアノペンタン酸）、２，２’－アゾビス（２－シアノプロパノール）、ジメチル－２，２’－アゾビス（２－メチルプロピオネート）、２，２’－アゾビス（２－メチル－Ｎ－（２－ヒドロキシエチル）プロピオンアミド）等のアゾ化合物が挙げられる。 Examples of azo initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2- cyclopropylpropionitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane-1-carbo nitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis(2-amidinopropane) dihydrochloride, 2,2′- azobis(N,N'-dimethyleneisobutylamidine), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(isobutylamide) dihydrate, 4 , 4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (2-cyanopropanol), dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis ( 2-methyl-N-(2-hydroxyethyl)propionamide) and other azo compounds.
　重合開始剤は１種単独で用いてもよく、２種以上を用いてもよい。また、重合中に、重合開始剤を複数回添加することも制限されない。
　重合開始剤は、（メタ）アクリル重合体（Ａ）を形成するモノマー成分（ａ）１００質量部に対して、通常０．００１～５質量部、好ましくは０．００５～３質量部の範囲内の量で使用される。また、上記重合反応中に、重合開始剤、連鎖移動剤、重合性単量体、重合溶媒を適宜追加添加してもよい。 One type of polymerization initiator may be used alone, or two or more types may be used. Moreover, it is not limited to adding the polymerization initiator multiple times during the polymerization.
The polymerization initiator is usually in the range of 0.001 to 5 parts by mass, preferably 0.005 to 3 parts by mass with respect to 100 parts by mass of the monomer component (a) forming the (meth)acrylic polymer (A). used in the amount of Moreover, a polymerization initiator, a chain transfer agent, a polymerizable monomer, and a polymerization solvent may be added as appropriate during the polymerization reaction.
　溶液重合に用いる重合溶媒としては、例えば、ベンゼン、トルエン、キシレン等の芳香族炭化水素類；ｎ－ペンタン、ｎ－ヘキサン、ｎ－ヘプタン、ｎ－オクタン等の脂肪族炭化水素類；シクロペンタン、シクロヘキサン、シクロヘプタン、シクロオクタン等の脂環式炭化水素類；ジエチルエーテル、ジイソプロピルエーテル、１，２－ジメトキシエタン、ジブチルエーテル、テトラヒドロフラン、ジオキサン、アニソール、フェニルエチルエーテル、ジフェニルエーテル等のエーテル類；クロロホルム、四塩化炭素、１，２－ジクロロエタン、クロロベンゼン等のハロゲン化炭化水素類；酢酸エチル、酢酸プロピル、酢酸ブチル、プロピオン酸メチル等のエステル類；アセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセタミド、Ｎ－メチルピロリドン等のアミド類；アセトニトリル、ベンゾニトリル等のニトリル類；ジメチルスルホキシド、スルホラン等のスルホキシド類等が挙げられる。 Examples of the polymerization solvent used for solution polymerization include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; cyclopentane, cyclohexane, cycloheptane, alicyclic hydrocarbons such as cyclooctane; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, Halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane, chlorobenzene; Esters such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; Acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. ketones; amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; sulfoxides such as dimethylsulfoxide and sulfolane;
　重合溶媒は１種単独で用いてもよく、２種以上を用いてもよい。
　粘着付与樹脂（Ｂ）
　本発明の粘着剤組成物に含まれる粘着付与樹脂（Ｂ）は、水酸基価が１００ｍｇＫＯＨ／ｇ以上である。 One type of polymerization solvent may be used alone, or two or more types may be used.
Tackifying resin (B)
The tackifier resin (B) contained in the pressure-sensitive adhesive composition of the present invention has a hydroxyl value of 100 mgKOH/g or more.
　前記粘着付与樹脂（Ｂ）の水酸基価は、１００ｍｇＫＯＨ／ｇ以上が好ましく、１１０ｍｇＫＯＨ／ｇ以上がより好ましい。また、水酸基価は、３００ｍｇＫＯＨ／ｇ以下が好ましく、２５０ｍｇＫＯＨ／ｇ以下がより好ましい。粘着付与樹脂（Ｂ）の水酸基価は、電位差滴定法によって測定することができる。水酸基価が上記の範囲であると、前記（メタ）アクリル重合体（Ａ）との相溶性が良く、かつ、得られる粘着シートの低極性被着体に対する接着力を高いものとすることができる。また、（メタ）アクリル重合体（Ａ）と粘着付与樹脂（Ｂ）との相溶性が優れることから、粘着シートを製造した後に、粘着剤層表面に粘着付与樹脂（Ｂ）がブリードアウトすることが抑制される。 The hydroxyl value of the tackifier resin (B) is preferably 100 mgKOH/g or more, more preferably 110 mgKOH/g or more. Moreover, the hydroxyl value is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less. The hydroxyl value of the tackifier resin (B) can be measured by potentiometric titration. When the hydroxyl value is within the above range, the compatibility with the (meth)acrylic polymer (A) is good, and the resulting pressure-sensitive adhesive sheet can have high adhesion to low-polar adherends. . In addition, since the (meth)acrylic polymer (A) and the tackifying resin (B) have excellent compatibility, the tackifying resin (B) does not bleed out on the surface of the pressure-sensitive adhesive layer after the pressure-sensitive adhesive sheet is produced. is suppressed.
　前記粘着付与樹脂（Ｂ）の酸価は、特に限定されるものではないが、通常１０ｍｇＫＯＨ／ｇ以下であり、５ｍｇＫＯＨ／ｇ以下が好ましく、３ｍｇＫＯＨ／ｇ以下がより好ましく、特に好ましくは０～１ｍｇＫＯＨ／ｇである。粘着付与樹脂（Ｂ）の酸価は、電位差滴定法によって測定することができる。酸価が前記範囲であると、前記（メタ）アクリル重合体（Ａ）との相溶性が良く、かつ、得られる粘着シートのタック性に優れる。 The acid value of the tackifying resin (B) is not particularly limited, but is usually 10 mgKOH/g or less, preferably 5 mgKOH/g or less, more preferably 3 mgKOH/g or less, and particularly preferably 0 to 1 mgKOH. /g. The acid value of the tackifier resin (B) can be measured by potentiometric titration. When the acid value is within the above range, the compatibility with the (meth)acrylic polymer (A) is good, and the pressure-sensitive adhesive sheet obtained has excellent tackiness.
　前記粘着付与樹脂（Ｂ）の軟化点は、所望の粘着特性により適宜選択でき、特に限定されるものではないが、通常９０～１８０℃、好ましくは９５～１７０℃、より好ましくは１００～１６０℃である。軟化点が前記範囲であると、得られる粘着剤組成物を、耐熱性を求められる自動車用途等に好適に使用することができる。 The softening point of the tackifying resin (B) can be appropriately selected depending on the desired adhesive property, and is not particularly limited, but is usually 90 to 180°C, preferably 95 to 170°C, more preferably 100 to 160°C. is. When the softening point is within the above range, the pressure-sensitive adhesive composition obtained can be suitably used for automobile applications where heat resistance is required.
　前記粘着付与樹脂（Ｂ）は、水酸基価が１００ｍｇＫＯＨ／ｇ以上のものであればよく、その構造を特に限定するものではないが、たとえば、粘着性を有する樹脂であって、フェノール骨格を有する樹脂、水酸基変性した樹脂、高水酸基の（メタ）アクリル系低分子量体から得られる樹脂等が挙げられる。これらのうちでは、入手が容易であり、安価で経済的であることから、フェノール骨格を有する樹脂が好ましい。前記粘着付与樹脂（Ｂ）として用いられるフェノール骨格を有する樹脂としては、水酸基価が１００ｍｇＫＯＨ／ｇ以上であって、主鎖あるいは側鎖にフェノール骨格を有する樹脂が挙げられ、たとえば、フェノール樹脂、テルペンフェノール樹脂、フェノール骨格をグラフト変性で導入した樹脂などが挙げられる。 The tackifying resin (B) may have a hydroxyl value of 100 mgKOH/g or more, and its structure is not particularly limited. , hydroxyl-modified resins, and resins obtained from (meth)acrylic low-molecular-weight substances having high hydroxyl groups. Among these, resins having a phenol skeleton are preferred because they are readily available, inexpensive, and economical. Examples of the resin having a phenol skeleton used as the tackifying resin (B) include resins having a hydroxyl value of 100 mgKOH/g or more and having a phenol skeleton in the main chain or side chain. Examples include phenol resins and resins in which a phenol skeleton is introduced by graft modification.
　前記粘着付与樹脂（Ｂ）としては、例えば、ヤスハラケミカル製のＹＳポリスターＧ１２５（水酸基価１１５ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇ、軟化点１２５℃）、ＹＳポリスターＧ１５０（水酸基価１１５ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇ、軟化点１５０℃）、ＹＳポリスターＮ１２５（水酸基価１４５ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇ、軟化点１２５℃）、ＹＳポリスターＫ１２５（水酸基価２０５ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇ、軟化点１２５℃）、ＹＳポリスターＫ１４０（水酸基価２００ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇ、軟化点１４０℃）が挙げられる。また、フドー製のＨＰ－２１０（水酸基価２４０ｍｇＫＯＨ／ｇ、酸価０ｍｇＫＯＨ／ｇ、軟化点１００℃）等が挙げられる。 Examples of the tackifying resin (B) include YS Polystar G125 (hydroxyl value 115 mgKOH/g, acid value 0 mgKOH/g, softening point 125° C.) manufactured by Yasuhara Chemical, YS Polystar G150 (hydroxyl value 115 mgKOH/g, acid value 0 mgKOH). / g, softening point 150 ° C.), YS Polystar N125 (hydroxyl value 145 mg KOH / g, acid value 0 mg KOH / g, softening point 125 ° C.), YS Poly Star K125 (hydroxyl value 205 mg KOH / g, acid value 0 mg KOH / g, softening point 125 ° C.), YS Polystar K140 (hydroxyl value: 200 mgKOH/g, acid value: 0 mgKOH/g, softening point: 140° C.). In addition, HP-210 manufactured by Fudo Co., Ltd. (hydroxyl value: 240 mgKOH/g, acid value: 0 mgKOH/g, softening point: 100° C.) and the like can be mentioned.
　本発明に係る粘着剤組成物中の粘着付与樹脂（Ｂ）の配合量は、（メタ）アクリル重合体（Ａ）１００質量部に対して、通常１０～５０質量部であり、好ましくは１０～４０質量部であり、より好ましくは１５～３０質量部である。粘着付与樹脂（Ｂ）の配合量が前記範囲であると、高温特性に優れた粘着シートが得られる。 The amount of the tackifying resin (B) in the pressure-sensitive adhesive composition according to the present invention is usually 10 to 50 parts by mass, preferably 10 to 50 parts by mass, based on 100 parts by mass of the (meth)acrylic polymer (A). 40 parts by mass, more preferably 15 to 30 parts by mass. When the amount of the tackifying resin (B) is within the above range, a pressure-sensitive adhesive sheet having excellent high-temperature properties can be obtained.
　架橋剤（Ｃ）
　本発明に係る粘着剤組成物に含まれる架橋剤（Ｃ）としては、（メタ）アクリル重合体（Ａ）を架橋することができればよく、特に制限はない。架橋剤（Ｃ）としては、例えばイソシアネート化合物（Ｃ１）、エポキシ化合物（Ｃ２）、金属キレート化合物（Ｃ３）等の、前記（メタ）アクリル重合体（Ａ）と反応し得る架橋剤を用いることができる。 Crosslinking agent (C)
The cross-linking agent (C) contained in the pressure-sensitive adhesive composition according to the present invention is not particularly limited as long as it can cross-link the (meth)acrylic polymer (A). As the cross-linking agent (C), a cross-linking agent capable of reacting with the (meth)acrylic polymer (A), such as an isocyanate compound (C1), an epoxy compound (C2), a metal chelate compound (C3), etc., can be used. can.
　前記架橋剤（Ｃ）は、１種単独で用いても、２種以上を用いてもよい。
　（イソシアネート化合物（Ｃ１））
　イソシアネート化合物（Ｃ１）としては、例えば、１分子中のイソシアネート基数が２以上のイソシアネート化合物が通常用いられ、好ましくは２～８であり、より好ましくは３～６である。イソシアネート基数が前記範囲にあると、（メタ）アクリル重合体（Ａ）とイソシアネート化合物との架橋反応効率の点、および粘着剤層の柔軟性を保つ点で好ましい。 The said crosslinking agent (C) may be used individually by 1 type, or may use 2 or more types.
(Isocyanate compound (C1))
As the isocyanate compound (C1), for example, an isocyanate compound having 2 or more isocyanate groups in one molecule is usually used, preferably 2 to 8, more preferably 3 to 6. When the number of isocyanate groups is within the above range, it is preferable from the viewpoint of efficiency of the cross-linking reaction between the (meth)acrylic polymer (A) and the isocyanate compound and the flexibility of the pressure-sensitive adhesive layer.
　１分子中のイソシアネート基数が２のジイソシアネート化合物としては、例えば、脂肪族ジイソシアネート、脂環族ジイソシアネート、芳香族ジイソシアネートが挙げられる。脂肪族ジイソシアネートとしては、エ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、ペンタメ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、２－メチル－１，５－ペンタンジイソシアネート、３－メチル－１，５－ペンタンジイソシアネート、２，２，４－トリメチル－１，６－ヘキサメチレンジイソシアネート等の炭素数４～３０の脂肪族ジイソシアネートが挙げられる。脂環族ジイソシアネートとしては、イソホロンジイソシアネート、シクロペンチルジイソシアネート、シクロヘキシルジイソシアネート、水素添加キシリレンジイソシアネート、水素添加トリレンジイソシアネート、水素添加ジフェニルメタンジイソシアネート、水素添加テトラメチルキシレンジイソシアネート等の炭素数７～３０の脂環族ジイソシアネートが挙げられる。芳香族ジイソシアネートとしては、例えば、フェニレンジイソシアネート、トリレンジイソシアネート、キシリレンジイソシアネート、ナフチレンジイソシアネート、ジフェニルエーテルジイソシアネート、ジフェニルメタンジイソシアネート、ジフェニルプロパンジイソシアネート等の炭素数８～３０の芳香族ジイソシアネートが挙げられる。 Examples of diisocyanate compounds having two isocyanate groups in one molecule include aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates. Aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, 2,2,4-trimethyl Aliphatic diisocyanates having 4 to 30 carbon atoms such as -1,6-hexamethylene diisocyanate can be mentioned. The alicyclic diisocyanate includes alicyclic compounds having 7 to 30 carbon atoms such as isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylene diisocyanate. Diisocyanates can be mentioned. Examples of aromatic diisocyanates include aromatic diisocyanates having 8 to 30 carbon atoms such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenylether diisocyanate, diphenylmethane diisocyanate and diphenylpropane diisocyanate.
　１分子中のイソシアネート基数が３以上のイソシアネート化合物としては、例えば、芳香族ポリイソシアネート、脂肪族ポリイソシアネート、脂環族ポリイソシアネートが挙げられる。具体的には、２，４，６－トリイソシアネートトルエン、１，３，５－トリイソシアネートベンゼン、４，４’，４”－トリフェニルメタントリイソシアネートが挙げられる。 Examples of isocyanate compounds having 3 or more isocyanate groups in one molecule include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Specific examples include 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, and 4,4',4''-triphenylmethane triisocyanate.
　また、イソシアネート化合物としては、例えば、イソシアネート基数が２または３以上の上記イソシアネート化合物の、多量体（例えば２量体または３量体、ビウレット体、イソシアヌレート体）、誘導体（例えば、多価アルコールと２分子以上のジイソシアネート化合物との付加反応生成物）、重合物が挙げられる。前記誘導体における多価アルコールとしては、低分子量多価アルコールとして、例えば、トリメチロールプロパン、グリセリン、ペンタエリトリトール等の３価以上のアルコールが挙げられ、高分子量多価アルコールとして、例えば、ポリエーテルポリオール、ポリエステルポリオール、アクリルポリオール、ポリブタジエンポリオール、ポリイソプレンポリオールが挙げられる。 Examples of isocyanate compounds include polymers (e.g. dimers or trimers, biuret forms, isocyanurate forms) and derivatives (e.g., polyhydric alcohols and addition reaction products with diisocyanate compounds having two or more molecules) and polymers. Examples of the polyhydric alcohol in the derivative include low-molecular-weight polyhydric alcohols such as trimethylolpropane, glycerin, and pentaerythritol, and trihydric or higher alcohols. High-molecular-weight polyhydric alcohols include, for example, polyether polyol, polyester polyols, acrylic polyols, polybutadiene polyols, and polyisoprene polyols.
　このようなイソシアネート化合物としては、例えば、ジフェニルメタンジイソシアネートの３量体、ポリメチレンポリフェニルポリイソシアネート、ヘキサメチレンジイソシアネートまたはトリレンジイソシアネートのビウレット体またはイソシアヌレート体、トリメチロールプロパンとトリレンジイソシアネートまたはキシリレンジイソシアネートとの反応生成物（例えばトリレンジイソシアネートまたはキシリレンジイソシアネートの３分子付加物）、トリメチロールプロパンとヘキサメチレンジイソシアネートとの反応生成物（例えばヘキサメチレンジイソシアネートの３分子付加物）、ポリエーテルポリイソシアネート、ポリエステルポリイソシアネートが挙げられる。 Examples of such isocyanate compounds include trimers of diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, biuret or isocyanurate of hexamethylene diisocyanate or tolylene diisocyanate, trimethylolpropane and tolylene diisocyanate or xylylene diisocyanate. (e.g. trimolecular adducts of tolylene diisocyanate or xylylene diisocyanate), reaction products of trimethylolpropane with hexamethylene diisocyanate (e.g. trimolecular adducts of hexamethylene diisocyanate), polyether polyisocyanates, Polyester polyisocyanates are mentioned.
　イソシアネート化合物の中でも、難黄変性の点で、キシリレンジイソシアネート系およびヘキサメチレンジイソシアネート系の架橋剤が好ましく、応力緩和性の観点からトリレンジイソシアネート系の架橋剤が好ましい。キシリレンジイソシアネート系架橋剤としては、例えば、キシリレンジイソシアネートおよびその多量体や誘導体、重合物が挙げられ、ヘキサメチレンジイソシアネート系架橋剤としては、例えば、ヘキサメチレンジイソシアネートおよびその多量体や誘導体、重合物が挙げられ、トリレンジイソシアネート系架橋剤としては、例えば、トリレンジイソシアネートおよびその多量体や誘導体、重合物が挙げられる。 Among isocyanate compounds, xylylene diisocyanate-based and hexamethylene diisocyanate-based cross-linking agents are preferred from the viewpoint of resistance to yellowing, and tolylene diisocyanate-based cross-linking agents are preferred from the viewpoint of stress relaxation. Examples of xylylene diisocyanate-based cross-linking agents include xylylene diisocyanate, polymers and derivatives thereof, and polymers. Examples of hexamethylene diisocyanate-based cross-linking agents include hexamethylene diisocyanate, polymers and derivatives thereof, and polymers. Examples of tolylene diisocyanate-based cross-linking agents include tolylene diisocyanate, its multimers, derivatives, and polymers.
　（エポキシ化合物（Ｃ２））
　エポキシ化合物（Ｃ２）としては、例えば、分子中に２個以上のエポキシ基を有する化合物が挙げられ、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、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、ジアミングリシジルアミン、Ｎ，Ｎ，Ｎ'，Ｎ'－テトラグリシジル－ｍ－キシリレンジアミン、１，３－ビス（Ｎ，Ｎ'－ジアミングリシジルアミノメチル）が挙げられる。 (Epoxy compound (C2))
Examples of the epoxy compound (C2) include compounds having two or more epoxy groups in the molecule, such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidylaniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis( N,N'-diamineglycidylaminomethyl).
　（金属キレート化合物（Ｃ３））
　金属キレート化合物（Ｃ３）としては、例えば、アルミニウム、鉄、銅、亜鉛、スズ、チタン、ニッケル、アンチモン、マグネシウム、バナジウム、クロム、ジルコニウム等の多価金属に、アルコキシド、アセチルアセトン、アセト酢酸エチル等が配位した化合物が挙げられる。具体的には、アルミニウムイソプロピレート、アルミニウムセカンダリーブチレート、アルミニウムエチルアセトアセテート・ジイソプロピレート、アルミニウムトリスエチルアセトアセテート、アルミニウムトリスアセチルアセトネートが挙げられる。 (Metal chelate compound (C3))
Examples of metal chelate compounds (C3) include polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium, and alkoxides, acetylacetone, ethyl acetoacetate, and the like. Coordinated compounds are included. Specific examples include aluminum isopropylate, aluminum secondary butyrate, aluminum ethylacetoacetate/diisopropylate, aluminum trisethylacetoacetate, and aluminum trisacetylacetonate.
　前記粘着剤組成物中の架橋剤（Ｃ）の配合量としては、（メタ）アクリル重合体（Ａ）１００質量部に対して、通常は０．０１～１０質量部であり、好ましくは０．０２～５質量部であり、より好ましくは０．０３～２．５質量部である。このような態様であると、架橋構造が充分かつ適度に形成され、凝集力が高く、また粘着物性のバランスに優れ、耐久性に優れた粘着剤を得ることができる。 The amount of the cross-linking agent (C) in the pressure-sensitive adhesive composition is usually 0.01 to 10 parts by mass, preferably 0.01 to 10 parts by mass, per 100 parts by mass of the (meth)acrylic polymer (A). 02 to 5 parts by mass, more preferably 0.03 to 2.5 parts by mass. In such a mode, a sufficiently and moderately crosslinked structure is formed, a cohesive force is high, and a pressure-sensitive adhesive having excellent balance of adhesive physical properties and excellent durability can be obtained.
　有機溶媒（Ｄ）
　本発明の粘着剤組成物は、塗工性を調整するために有機溶媒（Ｄ）を含有していてもよい。有機溶媒（Ｄ）としては、前述の（メタ）アクリル重合体（Ａ）の製造条件で挙げた有機溶媒が挙げられる。なお、（メタ）アクリル重合体（Ａ）の製造時に使用した有機溶媒と、粘着剤組成物に含まれる有機溶媒（Ｄ）は同種の有機溶媒であっても、別種の有機溶媒であってもよい。有機溶媒としては１種単独で用いても、２種以上を用いてもよい。 Organic solvent (D)
The pressure-sensitive adhesive composition of the present invention may contain an organic solvent (D) in order to adjust coatability. Examples of the organic solvent (D) include the organic solvents listed in the production conditions for the (meth)acrylic polymer (A) described above. The organic solvent used in the production of the (meth)acrylic polymer (A) and the organic solvent (D) contained in the pressure-sensitive adhesive composition may be the same organic solvent or different organic solvents. good. As the organic solvent, one type may be used alone, or two or more types may be used.
　粘着剤組成物が有機溶媒（Ｄ）を含む場合には、粘着剤組成物１００質量％中に、通常は３０～９０質量％、好ましくは４０～９０質量％である。
　添加剤（Ｅ）
　本発明の粘着剤組成物は、上記（Ａ）～（Ｄ）成分のほか、本発明の効果を損なわない範囲で、添加剤（Ｅ）を含んでいてもよい。 When the adhesive composition contains the organic solvent (D), it is usually 30 to 90% by mass, preferably 40 to 90% by mass, based on 100% by mass of the adhesive composition.
Additive (E)
The pressure-sensitive adhesive composition of the present invention may contain an additive (E) in addition to the components (A) to (D) as long as the effects of the present invention are not impaired.
　添加剤（Ｅ）としては、例えば、前記粘着付与樹脂（Ｂ）以外の粘着付与樹脂、シランカップリング剤、帯電防止剤、酸化防止剤、光安定剤、金属腐食防止剤、可塑剤、架橋促進剤、およびリワーク剤が挙げられる。添加剤（Ｅ）としては、１種単独で用いても、２種以上を用いてもよい。前記粘着剤組成物が、添加剤（Ｅ）を含有する場合の量としては、添加剤（Ｅ）の種類によっても異なり、特に制限はないが、粘着剤組成物１００質量％中に、通常は０．０１～１０質量％、好ましくは０．１～５質量％である。 The additive (E) includes, for example, a tackifying resin other than the tackifying resin (B), a silane coupling agent, an antistatic agent, an antioxidant, a light stabilizer, a metal corrosion inhibitor, a plasticizer, and a cross-linking accelerator. and rework agents. As the additive (E), one type may be used alone, or two or more types may be used. When the pressure-sensitive adhesive composition contains the additive (E), the amount varies depending on the type of the additive (E) and is not particularly limited. 0.01 to 10 mass %, preferably 0.1 to 5 mass %.
　（粘着剤組成物）
　本発明の粘着剤組成物は、例えば、上記各成分を従来公知の方法により混合することで調製することができる。例えば、（メタ）アクリル重合体（Ａ）を含む溶液と、粘着付与樹脂（Ｂ）と、架橋剤（Ｃ）と、必要に応じて用いられる添加剤等の他の成分とを混合することにより、粘着剤組成物を調製することができる。 (Adhesive composition)
The pressure-sensitive adhesive composition of the present invention can be prepared, for example, by mixing the components described above by a conventionally known method. For example, by mixing a solution containing a (meth)acrylic polymer (A), a tackifying resin (B), a cross-linking agent (C), and optionally other components such as additives, , an adhesive composition can be prepared.
　（粘着剤層）
　前記（メタ）アクリル重合体（Ａ）と、前記粘着付与樹脂（Ｂ）と、前記架橋剤（Ｃ）からなる粘着剤組成物より形成される粘着剤層は、厚さ２５μｍ におけるヘイズが５．０％以下であることが好ましく、０．５～４．５％であることがより好ましく、１．０～２．５％であることがさらに好ましい。ヘイズが前記範囲であることは、前記（メタ）アクリル重合体（Ａ）と前記粘着付与樹脂（Ｂ）とが、適度に相溶していることを示し、得られる粘着シートの低極性被着体に対する高接着性を発現する。なお、透明性を要さない用途に用いる場合においては、前記粘着剤組成物は、充填剤、顔料等の透明性を阻害する添加剤等を含有してもよいが、前記（メタ）アクリル重合体（Ａ）と前記粘着付与樹脂（Ｂ）、前記架橋剤（Ｃ）からなる厚さ２５μｍ における粘着剤層のヘイズが前記範囲となるようにすることが好ましい。 (Adhesive layer)
The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition comprising the (meth)acrylic polymer (A), the tackifying resin (B), and the cross-linking agent (C) has a haze of 5.0 at a thickness of 25 μm. It is preferably 0% or less, more preferably 0.5 to 4.5%, even more preferably 1.0 to 2.5%. The fact that the haze is in the above range indicates that the (meth)acrylic polymer (A) and the tackifying resin (B) are appropriately compatible, and the obtained pressure-sensitive adhesive sheet has low polarity adhesion. It exhibits high adhesiveness to the body. When used for applications that do not require transparency, the pressure-sensitive adhesive composition may contain additives that inhibit transparency such as fillers and pigments. It is preferable that the haze of the pressure-sensitive adhesive layer with a thickness of 25 μm consisting of the combination (A), the tackifying resin (B) and the cross-linking agent (C) is within the above range.
　また、本発明の粘着剤組成物より形成される粘着剤層表面と、流動パラフィンとの接触角が４０°未満であることが好ましく、１０～３５°であることがより好ましい。接触角が前記範囲であることは、被着体と接触する粘着剤層の表面に粘着付与樹脂（Ｂ）が適度に存在することを示す。 Further, the contact angle between the surface of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention and liquid paraffin is preferably less than 40°, more preferably 10 to 35°. A contact angle within the above range indicates that the tackifying resin (B) is appropriately present on the surface of the pressure-sensitive adhesive layer that contacts the adherend.
　前記粘着剤組成物より形成される粘着剤層は、上記の性質を示すため例えば、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、シクロオレフィン系樹脂（ＣＯＰ）などの各種ポリオレフィンなどの低極性の被着体に対しても高い接着性を発現する。 The pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition exhibits the above properties, for example, polyethylene (PE), polypropylene (PP), various polyolefins such as cycloolefin resin (COP), etc. It also exhibits high adhesiveness to the body.
　［粘着シート］
　本発明の一態様に係る粘着シートは、上述した本発明の一態様に係る粘着剤組成物より形成された粘着剤層を有するものであって、シート状、テープ状等の形態を包含する。 [Adhesive sheet]
A pressure-sensitive adhesive sheet according to one aspect of the present invention has a pressure-sensitive adhesive layer formed from the above-described pressure-sensitive adhesive composition according to one aspect of the present invention, and includes forms such as sheets and tapes.
　粘着シートとしては、例えば、粘着剤層のみから形成される粘着シート、基材と、基材の両面に形成された粘着剤層とを有し、少なくとも一方の粘着剤層が本発明の粘着剤組成物より形成された粘着剤層である両面粘着シート、基材と、基材の一方の面に形成された本発明の粘着剤組成物より形成された粘着剤層を有する片面粘着シート、本発明の粘着剤組成物より形成された粘着剤層の両面に基材が配置された粘着シートが挙げられる。 As the adhesive sheet, for example, an adhesive sheet formed only from an adhesive layer, having a substrate and adhesive layers formed on both sides of the substrate, at least one adhesive layer being the adhesive of the present invention The present A pressure-sensitive adhesive sheet in which substrates are arranged on both sides of a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the invention can be mentioned.
　前記基材としては、特に制限はなく、プラスチック基材、不織布、織布、紙、金属、ガラス、セラミックス、フォーム等が挙げられる。基材の厚さはその用途等によってもことなり、特に制限はないが、通常は５～２００μｍである。 The base material is not particularly limited, and includes plastic base materials, nonwoven fabrics, woven fabrics, paper, metals, glass, ceramics, foams, and the like. The thickness of the base material varies depending on its use, etc., and is not particularly limited, but is usually 5 to 200 μm.
　プラスチック基材としては、ポリエチレンテレフタレート、ポリ塩化ビニル、ポリオレフィン、ポリプロピレン、ポリメチルメタクリレート、ポリカーボネート、ポリイミド、およびＡＢＳから選択されるプラスチックの基材が挙げられる。 Plastic substrates include plastic substrates selected from polyethylene terephthalate, polyvinyl chloride, polyolefin, polypropylene, polymethyl methacrylate, polycarbonate, polyimide, and ABS.
　基材は、剥離処理された基材であってもよい。粘着シートが、本発明の粘着剤組成物より形成された粘着剤層の両面に基材が配置された粘着シートである場合には、少なくとも一方の基材は、剥離処理された基材であり、被着体との接着時に、剥離処理された基材は除去される。 The substrate may be a release-treated substrate. When the pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet having substrates arranged on both sides of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention, at least one of the substrates is a release-treated substrate. , the release-treated substrate is removed at the time of adhesion to the adherend.
　粘着剤層の厚さは、用途等により適宜選択することができ、特に限定されるものではないが、粘着性能維持の観点から、通常は５～２００μｍ、好ましくは１０～１００μｍである。 The thickness of the pressure-sensitive adhesive layer can be appropriately selected depending on the application, etc., and is not particularly limited, but from the viewpoint of maintaining adhesive performance, it is usually 5 to 200 μm, preferably 10 to 100 μm.
　粘着剤層は、その製造過程で粘着剤組成物中の、（メタ）アクリル重合体（Ａ）と架橋剤（Ｃ）とが反応することにより、少なくとも一部が架橋されていてもよい。
　粘着シートの製造方法としては特に制限はないが、例えば以下のとおりである。前述の粘着剤組成物を基材上に塗布する。前記粘着剤組成物が溶媒を含有する場合、通常は５０～１５０℃、好ましくは６０～１００℃で、通常は１～１０分間、好ましくは２～７分間乾燥して溶媒を除去し、塗膜を形成する。続いて、塗膜の基材がない側の表面へ、別の基材を貼り合わせる。続いて、通常は１日以上、好ましくは３～１０日間、通常は５～６０℃、好ましくは１５～４０℃、通常は３０～７０％ＲＨ、好ましくは４０～７０％ＲＨの環境下で養生し、粘着シートを製造する。前記養生を熟成ともいう。前記条件で熟成を行うと、熟成中に架橋が進行し、効率よく架橋体の形成が可能である。 At least a part of the pressure-sensitive adhesive layer may be crosslinked by reacting the (meth)acrylic polymer (A) and the cross-linking agent (C) in the pressure-sensitive adhesive composition during the production process.
The method for producing the pressure-sensitive adhesive sheet is not particularly limited, and examples thereof are as follows. The pressure-sensitive adhesive composition described above is applied onto a substrate. When the pressure-sensitive adhesive composition contains a solvent, it is usually dried at 50 to 150° C., preferably 60 to 100° C., usually for 1 to 10 minutes, preferably for 2 to 7 minutes to remove the solvent, and the coating film to form Subsequently, another base material is attached to the surface of the coating film on the side without the base material. Subsequently, usually 1 day or more, preferably 3 to 10 days, usually 5 to 60 ° C., preferably 15 to 40 ° C., usually 30 to 70% RH, preferably 40 to 70% RH environment. and produce an adhesive sheet. The curing is also called aging. When aging is performed under the above conditions, cross-linking proceeds during aging and efficient formation of a cross-linked product is possible.
　粘着剤組成物の塗布方法としては、公知の方法、例えばスピンコート法、ナイフコート法、ロールコート法、バーコート法、ブレードコート法、ダイコート法、グラビアコート法、ドクターブレード法により、所定の厚さになるように塗布・乾燥する方法を用いることができる。 As a method for applying the pressure-sensitive adhesive composition, known methods such as spin coating, knife coating, roll coating, bar coating, blade coating, die coating, gravure coating, and doctor blade coating can be applied to a predetermined thickness. It is possible to use a method of coating and drying so as to be even.
　前記粘着剤組成物から得られる粘着剤層を有する粘着シートは、ポリオレフィン等の低極性被着体に対しても優れた粘着力を示すとともに、高温特性に優れるため、自動車用途等の各種用途に好適に用いることができる。 A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition exhibits excellent adhesive strength even to low-polarity adherends such as polyolefins, and has excellent high-temperature properties, so it is suitable for various applications such as automobile applications. It can be used preferably.
　以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。以下の実施例等の記載において、特に言及しない限り、「部」は「質量部」を示す。 The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. In the following descriptions of Examples and the like, "parts" means "parts by mass" unless otherwise specified.
　（（メタ）アクリル重合体Ａ）
　（メタ）アクリル重合体（Ａ）の重量平均分子量（Ｍｗ）の測定方法は、以下のとおりである。 ((Meth) acrylic polymer A)
A method for measuring the weight average molecular weight (Mw) of the (meth)acrylic polymer (A) is as follows.
　（メタ）アクリル系共重合体（Ａ）について、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により、下記条件で標準ポリスチレン換算による重量平均分子量（Ｍｗ）を求めた。 For the (meth)acrylic copolymer (A), the weight average molecular weight (Mw) in terms of standard polystyrene was determined by gel permeation chromatography (GPC) under the following conditions.
　・測定装置：ＨＬＣ－８１２０ＧＰＣ（東ソー製）
　・ＧＰＣカラム構成：以下の５連カラム（すべて東ソー製）
　　（１）ＴＳＫ－ＧＥＬ ＨＸＬ－Ｈ （ガードカラム）
　　（２）ＴＳＫ－ＧＥＬ Ｇ７０００ＨＸＬ
　　（３）ＴＳＫ－ＧＥＬ ＧＭＨＸＬ
　　（４）ＴＳＫ－ＧＥＬ ＧＭＨＸＬ
　　（５）ＴＳＫ－ＧＥＬ Ｇ２５００ＨＸＬ
　・サンプル濃度：１．０ｍｇ／ｃｍ3となるように、テトラヒドロフランで希釈
　・移動相溶媒：テトラヒドロフラン
　・流量：１．０ｃｍ3／ｍｉｎ
　・カラム温度：４０℃
　［製造例１］
（アクリル重合体（Ａ－１）の製造）
　攪拌装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、２－メトキシエチルアクリレート９６．８質量部、アクリル酸３質量部、２－ヒドロキシエチルアクリレート０．２質量部、トルエン３７質量部、酢酸エチル２４質量部を仕込み、フラスコ内に窒素ガスを導入しながらフラスコの内容物を８５℃に加熱した。次いで、十分に窒素ガス置換したアゾビスイソブチロニトリル０．１質量部を攪拌下にフラスコ内に添加した。フラスコ内の内容物の温度を８５～８６℃に維持し、加熱及び冷却を４時間行った。温度を９５℃に昇温させた後、２間還流を行い、最後にトルエン１９質量部、酢酸エチル７８質量部を添加し、アクリル重合体（Ａ－１）を含む溶液を得た。得られたアクリル重合体（Ａ－１）のゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した重量平均分子量（Ｍｗ）は６５万であった。 ・ Measuring device: HLC-8120GPC (manufactured by Tosoh)
・ GPC column configuration: the following 5-column column (all manufactured by Tosoh)
(1) TSK-GEL HXL-H (guard column)
(2) TSK-GEL G7000HXL
(3) TSK-GEL GMHXL
(4) TSK-GEL GMHXL
(5) TSK-GEL G2500HXL
・Sample concentration: diluted with tetrahydrofuran to 1.0 mg/cm 3・Mobile phase solvent: tetrahydrofuran ・Flow rate: 1.0 cm 3 /min
・Column temperature: 40°C
[Production Example 1]
(Production of acrylic polymer (A-1))
96.8 parts by mass of 2-methoxyethyl acrylate, 3 parts by mass of acrylic acid, 0.2 parts by mass of 2-hydroxyethyl acrylate, and 37 parts by mass of toluene were added to a flask equipped with a stirrer, nitrogen gas inlet tube, thermometer and reflux condenser. Parts by mass and 24 parts by mass of ethyl acetate were charged, and the content of the flask was heated to 85° C. while introducing nitrogen gas into the flask. Then, 0.1 part by mass of azobisisobutyronitrile which was sufficiently replaced with nitrogen gas was added into the flask while stirring. The temperature of the contents in the flask was maintained at 85-86°C and heating and cooling were performed for 4 hours. After raising the temperature to 95° C., the mixture was refluxed for 2 minutes, and finally 19 parts by mass of toluene and 78 parts by mass of ethyl acetate were added to obtain a solution containing acrylic polymer (A-1). The weight average molecular weight (Mw) of the obtained acrylic polymer (A-1) measured by gel permeation chromatography (GPC) was 650,000.
　［製造例２～８］
　重合に供するモノマーの種類および仕込み組成（質量部）を、表１に記載したとおりに変更したこと以外は、製造例１と同様にして、アクリル重合体（Ａ－２）～（Ａ－６）、（Ａ’－７）、または（Ａ’－８）を含む溶液を得た。 [Production Examples 2 to 8]
Acrylic polymers (A-2) to (A-6) were prepared in the same manner as in Production Example 1, except that the types of monomers to be subjected to polymerization and the charging composition (parts by mass) were changed as shown in Table 1. , (A′-7), or (A′-8) was obtained.
　なお、製造例２においては、製造例１における重合開始時に仕込むトルエン３７質量部、酢酸エチル２４質量部を、トルエン２４質量部、酢酸エチル３７質量部に代えて反応を行った。また、製造例３においては、製造例１における重合開始時に仕込むトルエン３７質量部、酢酸エチル２４質量部を、トルエン４７質量部、酢酸エチル１４質量部に代えて反応を行った。 In Production Example 2, the reaction was performed by replacing the 37 parts by mass of toluene and 24 parts by mass of ethyl acetate charged at the start of polymerization in Production Example 1 with 24 parts by mass of toluene and 37 parts by mass of ethyl acetate. In Production Example 3, the reaction was performed by replacing 37 parts by mass of toluene and 24 parts by mass of ethyl acetate charged at the start of polymerization in Production Example 1 with 47 parts by mass of toluene and 14 parts by mass of ethyl acetate.
　得られた各アクリル重合体の、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した重量平均分子量（Ｍｗ）を表１に示す。 Table 1 shows the weight average molecular weight (Mw) of each obtained acrylic polymer measured by gel permeation chromatography (GPC).
Figure JPOXMLDOC01-appb-T000001
 　（粘着付与樹脂Ｂ）
　以下の実施例及び比較例では、粘着付与樹脂として以下のものを用いた。
Figure JPOXMLDOC01-appb-T000001
 (Tackifier resin B)
In the following examples and comparative examples, the following tackifying resins were used.
Figure JPOXMLDOC01-appb-T000002
 　なお、粘着付与樹脂の各物性は、以下の方法で測定した。
Figure JPOXMLDOC01-appb-T000002
 In addition, each physical property of the tackifier resin was measured by the following methods.
　＜軟化点＞
　軟化点は、ＪＩＳ Ｋ２２０７に規定される、軟化点試験方法（環球法）により求めた。 <Softening point>
The softening point was determined by the softening point test method (ring and ball method) specified in JIS K2207.
　＜水酸基価＞
　水酸基価は、ＪＩＳ　Ｋ００７０に準拠し、粘着付与樹脂１ｇをアセチル化させた時、水酸基と結合した酢酸を中和するのに必要な水酸化カリウムのｍｇ数として、電位差滴定法により求めた。 <Hydroxyl value>
The hydroxyl value was determined according to JIS K0070 by potentiometric titration as mg of potassium hydroxide required to neutralize acetic acid bound to hydroxyl groups when 1 g of the tackifying resin was acetylated.
　＜酸価＞
　酸価は、ＪＩＳ　Ｋ００７０に準拠し、粘着付与樹脂１ｇを中和するのに必要な水酸化カリウムのｍｇ数として、電位差滴定法により求めた。 <Acid value>
The acid value was determined by potentiometric titration as mg of potassium hydroxide required to neutralize 1 g of the tackifying resin in accordance with JIS K0070.
　＜流動パラフィン接触角測定＞
　容器内に、粘着付与樹脂２０質量部と、酢酸エチル３０質量部とを投入し、粘着付与樹脂の溶解液を作製した。次いで、作製した粘着付与樹脂溶液にプラスチック板を潜らせた後、８０℃環境下で５分乾燥させ、形成された粘着付与樹脂膜の表面に流動パラフィン（純正化学製）の約１μｌの微少液滴を静置し、協和界面科学製　ＫＹＯＷＡ　ＣＯＮＴＡＣＴ－ＡＮＧＬＥ　ＭＥＴＥＲ　ＣＡ－Ｄ型を用いて、大気中にて流動パラフィン接触角を測定し、ｎ＝１０の平均値を測定値とした。測定条件は、ＪＩＳ Ｒ３２５７に準拠した。 <Measurement of liquid paraffin contact angle>
20 parts by mass of a tackifying resin and 30 parts by mass of ethyl acetate were put into a container to prepare a solution of the tackifying resin. Next, after a plastic plate was submerged in the prepared tackifying resin solution, it was dried in an environment of 80°C for 5 minutes. The droplets were allowed to stand, and the contact angle of liquid paraffin was measured in air using a KYOWA CONTACT-ANGLE METER CA-D manufactured by Kyowa Interface Science, and the average value of n=10 was used as the measured value. Measurement conditions conformed to JIS R3257.
　［実施例１］
　（粘着剤組成物の製造）
　製造例１で得たアクリル重合体（Ａ－１）溶液（固形分（アクリル重合体）換算１００質量部）に、粘着付与樹脂（Ｂ－１）２０質量部およびエポキシ系架橋剤Ｅ－５ＸＭ（綜研化学製）を固形分換算で０．０４５質量部を添加し、ガラス棒で、５分撹拌して粘着剤組成物（１）を得た。 [Example 1]
(Production of adhesive composition)
To the acrylic polymer (A-1) solution obtained in Production Example 1 (100 parts by mass in terms of solid content (acrylic polymer)), 20 parts by mass of the tackifier resin (B-1) and epoxy-based cross-linking agent E-5XM ( Soken Kagaku Co., Ltd.) was added in an amount of 0.045 parts by mass in terms of solid content, and the mixture was stirred with a glass rod for 5 minutes to obtain an adhesive composition (1).
　（粘着シートの製造）
　厚さ２５μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム上に、得られた粘着剤組成物を、泡抜け後、ドクターブレードを用いて乾燥後の厚さが２５μｍとなるように塗布し、８０℃で３分間乾燥させ溶媒を除去して、粘着剤層となる塗膜を形成した。 (Manufacturing of adhesive sheet)
On a polyethylene terephthalate (PET) film having a thickness of 25 μm, the obtained pressure-sensitive adhesive composition was applied to a thickness of 25 μm after drying using a doctor blade after removing the bubbles, and was heated at 80° C. for 3 minutes. The solvent was removed by drying to form a coating film to be an adhesive layer.
　粘着剤層のＰＥＴフィルムと接している面とは反対側表面に、剥離処理されたＰＥＴフィルムを貼り合わせた。その後、２３℃／５０％ＲＨの条件で７日間静置して熟成させて、厚さ２５μｍの粘着剤層を有する粘着シートを製造した。 A release-treated PET film was attached to the surface of the adhesive layer opposite to the surface in contact with the PET film. After that, it was allowed to stand still for 7 days under conditions of 23° C./50% RH for aging to produce a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer with a thickness of 25 μm.
　（物性評価）
　得られた粘着シートを用い、以下のようにして物性の測定及び評価を行った。結果を表３に示す。 (Evaluation of the physical properties)
Using the obtained pressure-sensitive adhesive sheet, physical properties were measured and evaluated as follows. Table 3 shows the results.
　＜粘着力評価＞
　粘着シートを２５ｍｍ×１００ｍｍのサイズに裁断し試験片を得た。得られた試験片の剥離処理されたＰＥＴフィルムを剥がし、露出した粘着剤層を、被着体であるＰＰ（ポリプロピレン）板、ＰＥ（ポリエチレン）板、ＣＯＰ（シクロオレフィン系樹脂）板のそれぞれに貼付して、２ｋｇローラー３往復にて圧着した後、２３℃／５０％ＲＨ環境下に２０分放置した。その後、各種被着体に対して１８０°方向に３００ｍｍ／ｍｉｎの速度で試験片端部を引っぱり、粘着力（Ｎ／２５ｍｍ）を測定した。 <Adhesive strength evaluation>
The pressure-sensitive adhesive sheet was cut into a size of 25 mm×100 mm to obtain a test piece. The peel-treated PET film of the obtained test piece is peeled off, and the exposed adhesive layer is applied to each of the adherends PP (polypropylene) plate, PE (polyethylene) plate, and COP (cycloolefin resin) plate. After sticking and crimping with a 2-kg roller 3 reciprocations, it was allowed to stand for 20 minutes in a 23° C./50% RH environment. After that, the end portion of the test piece was pulled at a speed of 300 mm/min in the direction of 180° to various adherends, and the adhesive strength (N/25 mm) was measured.
　＜流動パラフィン接触角測定＞
　得られた粘着シートの片面から剥離処理されたＰＥＴフィルムを剥がし、露出した粘着剤層の表面に、流動パラフィン（純正化学製）の約１μｌの微少液滴を静置し、協和界面科学製　ＫＹＯＷＡ　ＣＯＮＴＡＣＴ－ＡＮＧＬＥ　ＭＥＴＥＲ　ＣＡ－Ｄ型を用いて、大気中にて流動パラフィン接触角を測定し、ｎ＝１０の平均値を測定値とした。測定条件は、ＪＩＳ Ｒ３２５７に準拠した。 <Measurement of liquid paraffin contact angle>
The release-treated PET film was peeled off from one side of the resulting adhesive sheet, and about 1 μl of microdroplets of liquid paraffin (manufactured by Junsei Chemical) were placed on the surface of the exposed adhesive layer. Using a CONTACT-ANGLE METER CA-D model, the liquid paraffin contact angle was measured in air, and the average value of n=10 was used as the measured value. Measurement conditions conformed to JIS R3257.
　＜ヘイズ測定＞
　剥離処理されたＰＥＴフィルム上に、実施例・比較例で得られた粘着剤組成物を、泡抜け後、ドクターブレードを用いて乾燥後の厚さが２５μｍとなるように塗布し、８０℃で３分間乾燥させ溶媒を除去して、粘着剤層となる塗膜を形成した。 <Haze measurement>
After removing the bubbles, the pressure-sensitive adhesive compositions obtained in Examples and Comparative Examples were applied to the release-treated PET film using a doctor blade so that the thickness after drying was 25 μm. The coating was dried for 3 minutes to remove the solvent to form a coating film to be an adhesive layer.
　粘着剤層の剥離処理されたＰＥＴフィルムと接している面とは反対側表面に、剥離処理されたＰＥＴフィルムを貼り合わせた。その後、２３℃／５０％ＲＨの条件で７日間静置して熟成させた。 A release-treated PET film was attached to the surface of the pressure-sensitive adhesive layer opposite to the surface in contact with the release-treated PET film. After that, it was aged by standing for 7 days under the conditions of 23° C./50% RH.
　得られた粘着シートの片面から剥離処理されたＰＥＴフィルムを剥がし、露出した粘着剤層と、ガラス板（ＡＧＣファブリテック社製、アルカリガラスＦＬ、１．１ｍｍ厚、ヘイズ値：０．１％）とを張り合わせた。 The peel-treated PET film was peeled off from one side of the obtained adhesive sheet, and the exposed adhesive layer and a glass plate (manufactured by AGC Fabritech, alkali glass FL, 1.1 mm thick, haze value: 0.1%) were separated. and pasted together.
　その後、残りの剥離処理されたＰＥＴフィルムを剥がし、前記ガラス板上に粘着剤層のみを有する試験片のヘイズ値をヘイズメーター（型名ＨＭ－１５０、村上色彩技術研究所製）を用いて測定した。得られた試験片のヘイズ値から、ガラス板のみのヘイズ値である０．１を差し引いた値を、粘着剤層のヘイズ（％）として求めた。 After that, the rest of the peel-treated PET film was peeled off, and the haze value of the test piece having only the adhesive layer on the glass plate was measured using a haze meter (model name HM-150, manufactured by Murakami Color Research Laboratory). did. The haze (%) of the pressure-sensitive adhesive layer was obtained by subtracting 0.1, which is the haze value of only the glass plate, from the haze value of the obtained test piece.
　［実施例２～１１、比較例１～７］
　アクリル重合体及び粘着付与樹脂の種類および量を、表３、表４に記載したように変更した以外は、実施例１と同様に行い、粘着剤組成物および粘着シートを得た。 [Examples 2 to 11, Comparative Examples 1 to 7]
A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet were obtained in the same manner as in Example 1, except that the types and amounts of the acrylic polymer and the tackifying resin were changed as shown in Tables 3 and 4.
　得られた粘着シートを用いて、実施例１と同様の方法で物性評価を行った。結果を表３、表４に示す。 Using the obtained adhesive sheet, physical properties were evaluated in the same manner as in Example 1. Tables 3 and 4 show the results.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
 　表３、表４より、実施例１～１１に記載の粘着剤組成物より得られる粘着シートは、低極性で難接着性であるポリエチレン製、ポリプロピレン製、およびポリオレフィン系樹脂製のいずれの被着体に対しても、良好な粘着性を示すことがわかる。
Figure JPOXMLDOC01-appb-T000004
 From Tables 3 and 4, the pressure-sensitive adhesive sheets obtained from the pressure-sensitive adhesive compositions of Examples 1 to 11 are low-polarity and difficult-to-adhere polyethylene, polypropylene, and polyolefin resin. It can be seen that it exhibits good adhesiveness to the body as well.
　また、実施例１～１１に記載の粘着剤組成物より得られる粘着剤層は、ヘイズが低く、（メタ）アクリル重合体（Ａ）と、粘着付与樹脂（Ｂ）との相溶性が良く、透明性を求められる用途に好適に使用できることが示された。さらに実施例１～８に記載の粘着剤組成物より得られる粘着剤層の流動パラフィンに対する接触角は、いずれも４０°未満であることから、粘着付与樹脂成分が粘着剤層表面に十分に存在し、高い粘着力を発揮することが示された。 In addition, the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition described in Examples 1 to 11 has a low haze and good compatibility between the (meth)acrylic polymer (A) and the tackifier resin (B). It was shown that it can be suitably used for applications that require transparency. Furthermore, since the contact angles of liquid paraffin of the pressure-sensitive adhesive layers obtained from the pressure-sensitive adhesive compositions described in Examples 1 to 8 are all less than 40°, the tackifying resin component is sufficiently present on the pressure-sensitive adhesive layer surface. It was shown to exhibit high adhesive strength.
　本発明の粘着剤組成物は、粘着シートの粘着剤層を形成する用途に好適である。本発明の粘着シートは、自動車内外装材や各種構造物に用いる粘着シートとして好適であり、特に自動車用等の、難接着性基材へ適用される用途、ならびに耐熱性が求められる用途に用いられる粘着シートとして好適である。 The adhesive composition of the present invention is suitable for use in forming an adhesive layer of an adhesive sheet. The pressure-sensitive adhesive sheet of the present invention is suitable as a pressure-sensitive adhesive sheet for use in automotive interior and exterior materials and various structures, and is particularly used in applications where it is applied to difficult-to-adhere substrates, such as automobiles, and where heat resistance is required. It is suitable as a pressure-sensitive adhesive sheet.

Claims (7)

  1. 　アルコキシアルキル（メタ）アクリレートを５１～９９．９質量％と、架橋性官能基含有モノマーを０．１～１５質量％とを含むモノマー成分（ａ）の重合体である、（メタ）アクリル重合体（Ａ）と、
    　水酸基価が１００ｍｇＫＯＨ／ｇ以上である粘着付与樹脂（Ｂ）と、
    　架橋剤（Ｃ）とを含み、
    　前記（メタ）アクリル重合体（Ａ）１００質量部に対して、前記粘着付与樹脂（Ｂ）を１０～５０質量部含む粘着剤組成物。     A (meth)acrylic polymer that is a polymer of the monomer component (a) containing 51 to 99.9% by mass of an alkoxyalkyl (meth)acrylate and 0.1 to 15% by mass of a crosslinkable functional group-containing monomer. (A) and
    a tackifying resin (B) having a hydroxyl value of 100 mgKOH/g or more;
    and a cross-linking agent (C),
    A pressure-sensitive adhesive composition containing 10 to 50 parts by mass of the tackifying resin (B) with respect to 100 parts by mass of the (meth)acrylic polymer (A).
  2. 　前記（メタ）アクリル重合体（Ａ）が、アルコキシアルキル（メタ）アクリレートを５１～９９．９質量％と、カルボキシ基含有モノマーを０．１～１５質量％と、水酸基含有モノマーを０～５質量％とを含むモノマー成分（ａ）の重合体である、請求項１に記載の粘着剤組成物。 The (meth)acrylic polymer (A) contains 51 to 99.9% by mass of an alkoxyalkyl (meth)acrylate, 0.1 to 15% by mass of a carboxy group-containing monomer, and 0 to 5% by mass of a hydroxyl group-containing monomer. %.
  3. 　前記粘着剤組成物より得られた厚さ２５μｍの粘着剤層のヘイズが５％未満である、請求項１または請求項２に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the pressure-sensitive adhesive layer with a thickness of 25 µm obtained from the pressure-sensitive adhesive composition has a haze of less than 5%.
  4. 　前記粘着剤組成物より得られる粘着剤層表面と、流動パラフィンとの接触角が４０°未満である、請求項１～３のいずれか１項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the contact angle between the surface of the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition and liquid paraffin is less than 40°.
  5. 　前記粘着付与樹脂（Ｂ）の酸価が５ｍｇＫＯＨ／ｇ未満である、請求項１～４のいずれか１項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 4, wherein the tackifying resin (B) has an acid value of less than 5 mgKOH/g.
  6. 　前記粘着付与樹脂（Ｂ）が、フェノール骨格を有する樹脂である、請求項１～５のいずれか１項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 5, wherein the tackifying resin (B) is a resin having a phenol skeleton.
  7. 　請求項１～６のいずれか１項に記載の粘着剤組成物より形成された粘着剤層を有する粘着シート。 A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of claims 1 to 6.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024095957A1 (en) * 2022-10-31 2024-05-10 三菱ケミカル株式会社 Ester compound-containing composition, method for producing same, polymerizable composition, (meth)acrylic polymer, and method for producing same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07102230A (en) * 1993-09-30 1995-04-18 Nippon Synthetic Chem Ind Co Ltd:The Pressure-sensitive adhesive composition
JP2012172045A (en) * 2011-02-21 2012-09-10 Nitto Denko Corp Adhesive agent composition, adhesive agent layer, and adhesive sheet
JP2015021083A (en) * 2013-07-19 2015-02-02 日東電工株式会社 Re-peeling adhesive composition, adhesive sheet and tape
JP2018159018A (en) * 2017-03-23 2018-10-11 綜研化学株式会社 Adhesive composition and adhesive sheet

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07102230A (en) * 1993-09-30 1995-04-18 Nippon Synthetic Chem Ind Co Ltd:The Pressure-sensitive adhesive composition
JP2012172045A (en) * 2011-02-21 2012-09-10 Nitto Denko Corp Adhesive agent composition, adhesive agent layer, and adhesive sheet
JP2015021083A (en) * 2013-07-19 2015-02-02 日東電工株式会社 Re-peeling adhesive composition, adhesive sheet and tape
JP2018159018A (en) * 2017-03-23 2018-10-11 綜研化学株式会社 Adhesive composition and adhesive sheet

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024095957A1 (en) * 2022-10-31 2024-05-10 三菱ケミカル株式会社 Ester compound-containing composition, method for producing same, polymerizable composition, (meth)acrylic polymer, and method for producing same

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