WO2022219969A1 - 粘着剤組成物および粘着シート - Google Patents

粘着剤組成物および粘着シート 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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Prior art keywords
meth
sensitive adhesive
pressure
mass
adhesive composition
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PCT/JP2022/009805
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English (en)
French (fr)
Japanese (ja)
Inventor
雄也 米川
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綜研化学株式会社
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Priority to CN202280026040.6A priority Critical patent/CN117120571A/zh
Priority to JP2023514515A priority patent/JPWO2022219969A1/ja
Publication of WO2022219969A1 publication Critical patent/WO2022219969A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024095957A1 (ja) * 2022-10-31 2024-05-10 三菱ケミカル株式会社 エステル化合物含有組成物及びその製造方法、重合性組成物、（メタ）アクリル系重合体及びその製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07102230A (ja) * 1993-09-30 1995-04-18 Nippon Synthetic Chem Ind Co Ltd:The 感圧性接着剤組成物
JP2012172045A (ja) * 2011-02-21 2012-09-10 Nitto Denko Corp 粘接着剤組成物、粘接着剤層、および粘接着シート
JP2015021083A (ja) * 2013-07-19 2015-02-02 日東電工株式会社 再剥離粘着剤組成物、粘着シート及びテープ
JP2018159018A (ja) * 2017-03-23 2018-10-11 綜研化学株式会社 粘着剤組成物および粘着シート

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07102230A (ja) * 1993-09-30 1995-04-18 Nippon Synthetic Chem Ind Co Ltd:The 感圧性接着剤組成物
JP2012172045A (ja) * 2011-02-21 2012-09-10 Nitto Denko Corp 粘接着剤組成物、粘接着剤層、および粘接着シート
JP2015021083A (ja) * 2013-07-19 2015-02-02 日東電工株式会社 再剥離粘着剤組成物、粘着シート及びテープ
JP2018159018A (ja) * 2017-03-23 2018-10-11 綜研化学株式会社 粘着剤組成物および粘着シート

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024095957A1 (ja) * 2022-10-31 2024-05-10 三菱ケミカル株式会社 エステル化合物含有組成物及びその製造方法、重合性組成物、（メタ）アクリル系重合体及びその製造方法

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