WO2012077613A1 - Pressure-sensitive adhesive composition, pressure-sensitive adhesive, and pressure-sensitive adhesive sheet using same - Google Patents

Pressure-sensitive adhesive composition, pressure-sensitive adhesive, and pressure-sensitive adhesive sheet using same Download PDF

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Publication number
WO2012077613A1
WO2012077613A1 PCT/JP2011/077993 JP2011077993W WO2012077613A1 WO 2012077613 A1 WO2012077613 A1 WO 2012077613A1 JP 2011077993 W JP2011077993 W JP 2011077993W WO 2012077613 A1 WO2012077613 A1 WO 2012077613A1
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Prior art keywords
meth
acrylate
pressure
sensitive adhesive
ethylenically unsaturated
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PCT/JP2011/077993
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French (fr)
Japanese (ja)
Inventor
幸宗 神田
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日本合成化学工業株式会社
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Application filed by 日本合成化学工業株式会社 filed Critical 日本合成化学工業株式会社
Priority to KR1020137017711A priority Critical patent/KR101881618B1/en
Priority to CN201180058870.9A priority patent/CN103249791B/en
Publication of WO2012077613A1 publication Critical patent/WO2012077613A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive, and a pressure-sensitive adhesive sheet using the same. Specifically, a pressure-sensitive adhesive having a high pressure-sensitive adhesive force and a high cohesive force, particularly corrosion resistance is required.
  • the present invention relates to an adhesive suitable for an electronic member or an optical member, and an adhesive sheet using the same.
  • adhesives such as strong adhesives for the purpose of firmly bonding adherends for a long period of time, and peel-off type adhesives that are supposed to be peeled off from adherends after being attached.
  • strong adhesives for the purpose of firmly bonding adherends for a long period of time
  • peel-off type adhesives that are supposed to be peeled off from adherends after being attached.
  • types, and the most suitable adhesive is designed and used for each field.
  • optical devices such as electronic displays using metals and metal oxides such as ITO transparent electrodes used for touch panels and the like, metal meshes used for PDPs, etc.
  • optical recording disks such as digital universal disks (optical)
  • Adhesives used in optical applications require strict durability such as heat resistance in addition to corrosion resistance, and therefore require adhesives with high cohesive strength and high adhesive strength.
  • a general acid-free pressure-sensitive adhesive such as Patent Document 2 is excellent in corrosion resistance, but has insufficient adhesive force and cohesive force. Therefore, it can be used as a pressure-sensitive adhesive for optical applications. could not. Therefore, it has been desired to develop a pressure-sensitive adhesive having excellent corrosion resistance and adhesive properties (adhesive strength, cohesive strength).
  • a pressure-sensitive adhesive composition for obtaining a pressure-sensitive adhesive having high adhesive strength and high cohesive strength and having excellent corrosion resistance when it does not contain an acidic group.
  • solvent-free active energy ray curing comprising an acrylic resin, a monofunctional unsaturated monomer, a polyfunctional unsaturated monomer, and a photopolymerization initiator.
  • Type pressure-sensitive adhesive a monofunctional unsaturated monomer that is used in combination with an alicyclic structure-containing ethylenically unsaturated compound and a hydroxyl group-containing ethylenically unsaturated compound, providing a good balance between adhesive strength and cohesive strength Has been found, and the present invention has been completed.
  • the gist of the present invention is an acrylic resin (A), an ethylenically unsaturated compound (B) having one ethylenically unsaturated group, and an ethylenically unsaturated compound (C) having two or more ethylenically unsaturated groups. ), And a photopolymerization initiator (D), and an ethylenically unsaturated compound containing an alicyclic structure as an ethylenically unsaturated compound (B) having one ethylenically unsaturated group
  • the present invention relates to a pressure-sensitive adhesive composition containing (B1) and a hydroxyl group-containing ethylenically unsaturated compound (B2). Furthermore, this invention relates to an adhesive and the adhesive sheet obtained by using them.
  • the present invention includes the following aspects.
  • Acrylic resin (A) ethylenically unsaturated compound (B) having one ethylenically unsaturated group, ethylenically unsaturated compound (C) having two or more ethylenically unsaturated groups, and photopolymerization
  • a pressure-sensitive adhesive composition comprising a hydroxyl group-containing ethylenically unsaturated compound (B2).
  • the acrylic resin (A) is an acrylic resin obtained by copolymerizing a copolymer component containing an alicyclic structure-containing (meth) acrylic acid ester monomer [1] or [2] The pressure-sensitive adhesive composition according to [2].
  • a pressure-sensitive adhesive wherein the pressure-sensitive adhesive composition according to any one of [1] to [6] is cured by irradiation with active energy rays.
  • a pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive according to [7].
  • the pressure-sensitive adhesive composed of the pressure-sensitive adhesive composition of the present invention has a strong pressure-sensitive adhesive force and an excellent cohesive force, and therefore does not easily peel off from the base material even in a high-temperature environment. It is useful as an adhesive and an adhesive sheet. Furthermore, since it becomes excellent in adhesive strength and cohesive force without containing an acid in the adhesive, optical equipment such as an electronic display that requires corrosion resistance against metals and metal oxides, It is particularly effective as an optical pressure-sensitive adhesive sheet for laminating optical recording disks (optical recording media) such as digital universal disks.
  • (meth) acryl means acryl or methacryl
  • (meth) acryloyl means acryloyl or methacryloyl
  • (meth) acrylate means acrylate or methacrylate.
  • the pressure-sensitive adhesive composition of the present invention comprises an acrylic resin (A), an ethylenically unsaturated compound (B) having one ethylenically unsaturated group, and an ethylenically unsaturated compound having two or more ethylenically unsaturated groups ( C) and a photopolymerization initiator (D).
  • A acrylic resin
  • B ethylenically unsaturated compound
  • C ethylenically unsaturated compound having two or more ethylenically unsaturated groups
  • D photopolymerization initiator
  • the acrylic resin (A) has a (meth) acrylic acid ester monomer (a1) as a main component as a copolymerization component, and if necessary, a functional group-containing copolymerizable monomer (a2) and other copolymerization properties. It can be obtained by copolymerizing a copolymer component containing the monomer (a3).
  • (Meth) acrylic acid ester monomer (a1) (excluding (a2) described later) includes (meth) acrylic acid alkyl ester monomer (a1-1), alicyclic structure-containing (meth) acrylic acid And ester monomers (a1-2).
  • the alkyl group usually has 1 to 20 carbon atoms, particularly preferably 1 to 10, more preferably 1 to 8, and particularly preferably.
  • ethyl (meth) acrylate and n-butyl (meth) acrylate are preferably used in terms of copolymerizability, adhesive properties, ease of handling, and availability of raw materials. Further, n-butyl (meth) acrylate is preferably used from the viewpoint of excellent durability.
  • the alicyclic structure usually has 4 to 20 carbon atoms, particularly preferably 6 to 10 carbon atoms.
  • the content of the (meth) acrylic acid ester monomer (a1) in the copolymerization component is preferably 60 to 100% by weight, particularly preferably 70 to 95% by weight, more preferably 80 to 90% by weight, When the content of the (meth) acrylic acid ester monomer (a1) is too small, the adhesive strength when used as an adhesive tends to be insufficient.
  • Examples of the functional group-containing copolymerizable monomer (a2) include functional group-containing monomers such as a hydroxyl group-containing monomer, an oxyalkylene group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, a nitrogen-containing monomer, and a glycidyl group-containing monomer. 1 type or 2 types or more chosen from these are used. Among these, a hydroxyl group-containing monomer is preferably used from the viewpoint of obtaining high cohesive force, and 2-hydroxyethyl (meth) acrylate is particularly preferable.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meta ) Acrylate, 10-hydroxydecyl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate and other (meth) acrylic acid hydroxyalkyl esters, caprolactone-modified 2-hydroxyethyl (meth) acrylate and other caprolactone Monomers containing primary hydroxyl groups such as modified monomers, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, etc.
  • polyethylene glycol derivatives such as diethylene glycol (meth) acrylate and polyethylene glycol mono (meth) acrylate
  • polypropylene glycol derivatives such as polypropylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol-mono (meth) acrylate, poly (ethylene glycol)
  • An oxyalkylene-modified hydroxyl group-containing monomer such as -tetramethylene glycol) mono (meth) acrylate or poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate may be used.
  • Examples of the oxyalkylene group-containing monomer include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and 2-butoxydiethylene glycol.
  • amide group-containing monomers examples include acrylamide, methacrylamide, N- (n-butoxyalkyl) acrylamide, N- (n-butoxyalkyl) methacrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl.
  • amino group-containing monomer examples include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof.
  • nitrogen-containing monomer examples include acryloylmorpholine.
  • Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.
  • the content of the functional group-containing copolymerizable monomer (a2) in the copolymerization component is preferably 0.01 to 20% by weight, particularly preferably 0.1 to 15% by weight, and more preferably 0.2 to 10% by weight. If the amount of the functional group-containing copolymerizable monomer (a2) is too small, the interaction between the functional groups tends to be small and the cohesive force tends to decrease, and if too large, the adhesive force tends to decrease too much.
  • copolymerizable monomers (a3) include acrylonitrile, methacrylonitrile, styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, vinyl pyridine.
  • the content of the other copolymerizable monomer (a3) in the copolymerization component is preferably 0 to 40% by weight, particularly preferably 3 to 30% by weight, more preferably 8 to 20% by weight.
  • the content of the other copolymerizable monomer (a3) in the copolymerization component is preferably 0 to 40% by weight, particularly preferably 3 to 30% by weight, more preferably 8 to 20% by weight.
  • the acrylic resin (A) used in the present invention does not contain an acidic group from the viewpoint of excellent corrosion resistance.
  • an acrylic resin ( A) is produced.
  • Such polymerization can be carried out by methods well known to those skilled in the art, such as solution radical polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization.
  • suspension polymerization is preferably used because a polymer having a large molecular weight can be obtained and the resulting polymer can be easily isolated.
  • the acrylic resin (A) is a dry polymer obtained by suspension polymerization. A resin is preferred.
  • a dispersion stabilizer such as polyvinyl alcohol and a polymerization initiator such as azobisisobutyronitrile can be added as necessary.
  • the acrylic resin used in the pressure-sensitive adhesive composition is often produced by solvent-based polymerization using an organic solvent at the time of production.
  • a solvent-based polymerized acrylic resin is used in the pressure-sensitive adhesive composition, it is necessary to dry the pressure-sensitive adhesive composition solution at a high temperature, which requires a lot of energy and the organic solvent ignites. Not only is it easy to cause air pollution, but a large-scale solvent recovery device and safety device are required.
  • the acrylic resin (A) of dry resin obtained by the suspension polymerization is used, the pressure-sensitive adhesive composition can be produced without containing such an organic solvent.
  • the weight average molecular weight (Mw) of the acrylic resin (A) is preferably 500,000 to 3,000,000, particularly preferably 850,000 to 2,500,000, and more preferably 1,000,000 to 2,000,000. If the weight-average molecular weight of the acrylic resin (A) is too small, the cohesive force of the pressure-sensitive adhesive obtained by irradiation with active energy rays tends to decrease, and if it is too large, a uniformly compatible pressure-sensitive adhesive composition is difficult to obtain. Tend to be.
  • the degree of dispersion (Mw / Mn) of the acrylic resin (A) is preferably 7 or less, particularly 5 or less, and further preferably 4 or less.
  • the lower limit of the degree of dispersion (Mw / Mn) is usually 2.
  • said Mn means a number average molecular weight.
  • the glass transition temperature (Tg) of the acrylic resin (A) is preferably ⁇ 70 to 20 ° C., particularly preferably ⁇ 60 to 0 ° C., and further preferably ⁇ 55 to ⁇ 10 ° C.
  • Tg glass transition temperature
  • the weight average molecular weight means a weight average molecular weight in terms of standard polystyrene molecular weight. Specifically, high-performance liquid chromatography (manufactured by Waters, Japan, “Waters 2695 (main body)” and “Waters 2414 (detection)). Column): Shodex GPC KF-806L (exclusion limit molecular weight: 2 ⁇ 10 7 , separation range: 100 to 2 ⁇ 10 7 , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinyl It is measured by using three series of benzene copolymer and filler particle size: 10 ⁇ m. Similarly, the number average molecular weight is measured using the above measuring apparatus.
  • the glass transition temperature is calculated from the following Fox equation.
  • the content of the acrylic resin (A) is 5 to 50 weights with respect to a total of 100 parts by weight of the acrylic resin (A) and an ethylenically unsaturated compound (B) having one ethylenically unsaturated group described later. Parts, preferably 7 to 45 parts by weight, more preferably 10 to 40 parts by weight.
  • Examples of the ethylenically unsaturated compound (B) having one ethylenically unsaturated group include an alicyclic structure-containing ethylenically unsaturated compound. It is necessary to contain a compound (B1) and a hydroxyl-containing ethylenically unsaturated compound (B2).
  • (B1) and (B2) are used in combination as essential components, high adhesive strength due to the effect of suppressing the release of the adhesive derived from the alicyclic structure-containing ethylenically unsaturated compound (B1), in particular.
  • high cohesive force due to hydrogen bonding derived from the hydroxyl group-containing ethylenically unsaturated compound (B2) is exhibited in a well-balanced manner.
  • the alicyclic structure-containing ethylenically unsaturated compound (B1) is preferably an alicyclic structure-containing (meth) acrylate compound, and the alicyclic structure usually has 4 to 20 carbon atoms. And particularly preferably 6 to 10.
  • Examples include 1,4-cyclohexanedimethanol mono (meth) acrylate, and among these, cyclohexyl (meth) acrylate is preferable, and cyclohexyl is particularly preferable in terms of excellent compatibility with the acrylic resin (A). Acrylate.
  • the hydroxyl group-containing ethylenically unsaturated compound (B2) is preferably a hydroxyl group-containing (meth) acrylate compound, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, (4-hydroxymethylcyclohexyl) ) Hydroxyalkyl esters of (meth) acrylic acid such as methyl (meth) acrylate, caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth) acrylate, 2-acryloyloxyethyl-2-hydro Primary hydroxyl group-containing ethylenically unsaturated compounds such as ethyl phthalate
  • primary hydroxyl group-containing ethylenically unsaturated compounds are preferable, and 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like because they are excellent in viscosity and compatibility with acrylic resins and easily available.
  • Hydroxypropyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate are preferable, and 4-hydroxybutyl (meth) acrylate is more preferable.
  • the monofunctional unsaturated compound (B) is an ethylene other than the alicyclic structure-containing ethylenically unsaturated compound (B1) and the hydroxyl group-containing ethylenically unsaturated compound (B2) as long as the effects of the present invention are not impaired. It is preferable to use an unsaturated compound (B3) having one ionic unsaturated group (hereinafter sometimes referred to as “monofunctional unsaturated compound (B3)”), but in terms of excellent corrosion resistance, It is preferable not to use a compound having an acidic group.
  • Examples of the monofunctional unsaturated compound (B3) include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 30 carbon atoms, and specifically include ethyl (meth) acrylate, n-propyl ( (Meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, 2-ethylhexyl (meth) Examples include acrylate, nonyl (meth) acrylate, n-decyl (meth) acrylate, iso-decyl (meth) acrylate, methyl (meth) acrylate, and the like.
  • the monofunctional unsaturated compound (B3) includes glycidyl group-containing unsaturated monomers such as glycidyl (meth) acrylate and allyl glycidyl (meth) acrylate; t-butylaminoethyl (meth) acrylate, diethylamino Amino group-containing monomers such as ethyl (meth) acrylate and dimethylaminoethyl (meth) acrylate; acetoacetyl group-containing monomers such as 2- (acetoacetoxy) ethyl (meth) acrylate and allyl acetoacetate; 2-methoxyethyl (meth) Alkoxy (poly) alkylene glycol mono (meth) acrylates such as acrylate, 3-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate; N-acrylamidomethyltrimethylammoni
  • the content of the alicyclic structure-containing ethylenically unsaturated compound (B1) with respect to the whole monofunctional unsaturated compound (B) is preferably 0.5 to 70% by weight, particularly preferably 1 to 60% by weight, More preferably, it is 3 to 50% by weight, particularly preferably 5 to 40% by weight. If the content of the alicyclic structure-containing ethylenically unsaturated compound (B1) is too high or too low, the adhesive strength tends to decrease.
  • the content ratio of the hydroxyl group-containing ethylenically unsaturated compound (B2) to the monofunctional unsaturated compound (B) is preferably 1 to 70% by weight, particularly preferably 3 to 60% by weight, and more preferably 5 to 5%. 50% by weight, particularly preferably 7 to 40% by weight. If the content ratio of the hydroxyl group-containing ethylenically unsaturated compound (B2) is too high, the cohesive force tends to be too high, and if it is too low, the durability tends to decrease.
  • the total content of the alicyclic structure-containing ethylenically unsaturated compound (B1) and the hydroxyl group-containing ethylenically unsaturated compound (B2) with respect to the entire monofunctional unsaturated compound (B) is preferably 10 to 75. % By weight, particularly preferably 20 to 70% by weight, more preferably 25 to 65% by weight, particularly preferably 30 to 60% by weight.
  • the content ratio of the total amount of the alicyclic structure-containing ethylenically unsaturated compound (B1) and the hydroxyl group-containing ethylenically unsaturated compound (B2) is too high, the cohesive force tends to be too high. There is a tendency that sufficient effects cannot be obtained.
  • the content of the monofunctional unsaturated compound (B) is preferably 50 to 95 parts by weight with respect to 100 parts by weight in total of the acrylic resin (A) and the monofunctional unsaturated compound (B).
  • the amount is particularly preferably 55 to 93 parts by weight, more preferably 60 to 90 parts by weight.
  • Examples of the ethylenically unsaturated compound (C) containing two or more ethylenically unsaturated groups include bifunctional (meta ) Acrylate monomers, tri- or higher functional (meth) acrylate monomers, urethane (meth) acrylate compounds, epoxy (meth) acrylate compounds, and polyester (meth) acrylate compounds can be used. Moreover, these can be used individually or in combination of 2 or more types.
  • the bifunctional (meth) acrylate monomer may be any monomer containing two (meth) acryloyl groups.
  • the trifunctional or higher functional (meth) acrylate monomer may be any monomer containing at least three (meth) acryloyl groups, such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxy Trimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, ethylene oxide modified Dipentaerythritol penta (
  • the urethane (meth) acrylate compound is a (meth) acrylate compound having a urethane bond in the molecule, a (meth) acrylic compound containing a hydroxyl group and a polyvalent isocyanate compound (if necessary, a polyol compound) What is necessary is just to use what is obtained by making a compound) react by a well-known general method, and what is usually used is 300-4000 as the weight average molecular weight.
  • the content of the polyfunctional unsaturated compound (C) is 0.005 to 15 parts by weight with respect to 100 parts by weight in total of the acrylic resin (A) and the monofunctional unsaturated compound (B). It is preferably 0.01 to 13 parts by weight, more preferably 0.1 to 10 parts by weight.
  • the photopolymerization initiator (D) is not particularly limited as long as it generates radicals by the action of active energy rays such as light. Intramolecular self-cleavage type photopolymerization initiator and hydrogen abstraction type photopolymerization start An agent is used.
  • Examples of the intramolecular self-cleaving photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- (4-Isopropylenephenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2 -Hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzoin, Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Ter, benzoin isobutyl ether, benzyldimethyl
  • hydrogen abstraction type photopolymerization initiator examples include benzophenone, 4-phenylbenzophenone, hydroxybenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone.
  • These photopolymerization initiators (D) are used alone or in combination of two or more.
  • triazine photopolymerization initiator examples include 2,4,6-trisubstituted-s-triazine represented by the following general formula (a).
  • R 1 , R 2 and R 3 are each an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group or an alkoxy group, and they may be the same or different from each other. However, at least one is a monohalogen-substituted methyl group, a dihalogen-substituted methyl group, or a trihalogen-substituted methyl group.
  • alkyl group examples include an alkyl group having 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-hexyl group, and the like. It is done.
  • substituted alkyl group examples include an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, specifically, a trichloromethyl group, a tribromomethyl group, an ⁇ , ⁇ , ⁇ -trichloroethyl group, and the like. It is done.
  • aryl group and substituted aryl group examples include those having 6 to 20 carbon atoms, such as a phenyl group, a p-methoxyphenyl group, a p-methylthiophenyl group, a p-chlorophenyl group, and 4-biphenylyl. Group, naphthyl group, 4-methoxy-1-naphthyl group and the like.
  • alkenyl group examples include those having 2 to 12 carbon atoms such as a vinyl group, an allyl group, and a 2-phenylethenyl group.
  • alkoxy group examples include those having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group.
  • the monohalogen-substituted methyl group, dihalogen-substituted methyl group or trihalogen-substituted methyl group includes chloromethyl group, bromomethyl group, iodomethyl group, dichloromethyl group, dibromomethyl group, diiodomethyl group, trichloromethyl group, tribromomethyl. Group and triiodomethyl group. Of these, a trichloromethyl group substituted with a chlorine atom is preferred.
  • Such 2,4,6-trisubstituted-s-triazines represented by general formula (a) are, for example, JournalJof American Chemical Society Vol. 72, 3257-3528 (1950) It can be synthesized according to the methods described in Society 74 74, 5633-5636 (1952), Juatus Lieblgs Annalen der Chemie 577, 77-95 (1952).
  • 2,4,6-trisubstituted-s-triazine represented by the general formula (a) include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6 6-tris (tribromomethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-methyl-s-triazine, 2,4-bis (tribromomethyl) -6-methyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-tolyl) -s-triazine, 2,4-bis (trichloromethyl) -6-n-propyl-s-triazine, 2- ( ⁇ , ⁇ , ⁇ -Trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl)
  • auxiliary of the photopolymerization initiator (D) for example, triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2- Dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethyl It is also possible to use thioxanthone, 2,4-diisopropylthioxanthone, etc. in combination.
  • the content of the photopolymerization initiator (D) is 0.1 to 20 parts by weight with respect to 100 parts by weight in total of the monofunctional unsaturated compound (B) and the polyfunctional unsaturated compound (C). It is preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight. If the content of the photopolymerization initiator (D) is too small, there is a tendency that the polymerization due to irradiation with active energy rays such as ultraviolet rays tends to be uneven. Tend to be.
  • the triazine photopolymerization initiator When the triazine photopolymerization initiator is used alone as the photopolymerization initiator (D), the total amount of the monofunctional unsaturated compound (B) and the polyfunctional unsaturated compound (C) is 100 parts by weight.
  • the triazine photopolymerization initiator is preferably contained in an amount of 0.01 to 0.5 parts by weight, particularly preferably 0.05 to 0.45 parts by weight, more preferably 0.1 to 0.4 parts by weight. Particularly preferred is 0.15 to 0.35 parts by weight.
  • the pressure-sensitive adhesive composition of the present invention comprising the acrylic resin (A), the monofunctional unsaturated compound (B), the polyfunctional unsaturated compound (C), and the photopolymerization initiator (D).
  • crosslinking agents other adhesives, urethane resins, rosins, rosin esters, hydrogenated rosin esters, phenol resins, aromatic modified terpene resins, aliphatic petroleum resins, alicyclic petroleum resins, Mixing tackifiers such as styrene resins and xylene resins, known additives and compounds that cause coloration or discoloration upon irradiation with ultraviolet rays or radiation It can be. Further, in addition to the above-mentioned compounding agent, a small amount of impurities and the like contained in the raw materials for producing the constituent components of the pressure-sensitive adhesive composition may be contained. What is necessary is just to set suitably the compounding quantity of these compounding agents so that the desired physical property may be obtained.
  • the pressure-sensitive adhesive composition is preferably substantially free of acid from the viewpoint of excellent corrosion resistance, and substantially free of acid means that the acid value of the pressure-sensitive adhesive composition is usually 1 mgKOH / g or less, It means preferably 0.5 mgKOH / g or less, particularly preferably 0.
  • the pressure-sensitive adhesive composition obtained in the present invention preferably contains substantially no solvent such as water, an aqueous solvent or an organic solvent, and is an acrylic resin (A), a polyfunctional unsaturated compound (C), photopolymerization.
  • the initiator (D) and other components added as necessary are dissolved or uniformly dispersed in the monofunctional unsaturated compound (B).
  • Such a pressure-sensitive adhesive composition is blended as necessary with acrylic resin (A), monofunctional unsaturated compound (B), polyfunctional unsaturated compound (C), photopolymerization initiator (D).
  • Other components can be prepared by heating to room temperature or about 60 ° C. and then mixing.
  • the pressure-sensitive adhesive composition of the present invention is obtained, the pressure-sensitive adhesive composition is cured by irradiation with active energy rays to obtain the pressure-sensitive adhesive of the present invention.
  • rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and ⁇ rays, electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet irradiation is advantageous because of its availability and price.
  • a high-pressure mercury lamp, ultrahigh-pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp, or the like that emits light in the wavelength range of 150 to 450 nm can be used.
  • the irradiation amount of the active energy ray is preferably 500 mJ / cm 2 or more, further 1000 mJ / cm 2 or more, and particularly preferably at 1500 mJ / cm 2 or more. If the amount of irradiation is too small, there is a tendency that the polymerization by irradiation with active energy rays tends to vary.
  • the upper limit of the irradiation amount is usually 10,000 mJ / cm 2 , and if the irradiation amount is too large, the relationship between the apparatus and the cost tends to be uneconomical.
  • the pressure-sensitive adhesive of the present invention is preferably used as a pressure-sensitive adhesive sheet.
  • a method for producing the pressure-sensitive adhesive sheet [I] a method in which a pressure-sensitive adhesive composition is applied on a substrate, irradiated with active energy rays to form a pressure-sensitive adhesive layer, and then a release sheet is bonded; [II] pressure-sensitive adhesive A method of applying an adhesive composition on a substrate and pasting a release sheet, and then irradiating active energy rays to form an adhesive layer, [III] applying an adhesive composition on the release sheet, A method of pasting a base material or a release sheet after irradiating an active energy ray to form an adhesive layer, [IV] Applying an adhesive composition on the release sheet, and pasting the base material or the release sheet After combining, there is a method of forming an adhesive layer by irradiating with active energy rays.
  • the base material examples include metal foils such as aluminum, copper, and iron; polyester resins such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer; polyethylene, polypropylene, polymethylpentene, etc.
  • Polyolefin resins such as polyvinyl fluoride, polyvinylidene fluoride, and polyfluorinated ethylene; polyamides such as nylon 6 and nylon 6, 6; polyvinyl chloride, polyvinyl chloride / vinyl acetate copolymer, ethylene Vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, vinyl polymers such as polyvinyl alcohol and vinylon; cellulose resins such as cellulose triacetate and cellophane; polymethyl methacrylate, polymethacryl Acrylic resins such as ethyl, polyethyl acrylate, and polybutyl acrylate; synthetic resin films or sheets such as polystyrene, polycarbonate, polyarylate, polyimide, paper such as fine paper, glassine paper, glass fibers, natural fibers, synthetic fibers A monolayer or a multi-layer selected from the above. Moreover, it can also be used for uses, such as a double-sided tape, using a nonwoven fabric,
  • the thickness of the substrate is not particularly limited, but is usually 500 ⁇ m or less, preferably 5 to 300 ⁇ m, more preferably 10 to 200 ⁇ m.
  • release sheet it is possible to use, for example, various synthetic resin sheets exemplified in the support base material, paper, cloth, non-woven fabric, and the like subjected to release treatment.
  • the coating method of the pressure-sensitive adhesive composition is not particularly limited as long as it is a general coating method, and examples thereof include roll coating, die coating, gravure coating, comma coating, and screen printing.
  • the thickness of the pressure-sensitive adhesive layer formed on the substrate after irradiation with active energy rays is appropriately set depending on the application, but is usually 5 to 300 ⁇ m, preferably 10 to 250 ⁇ m. If the thickness of the pressure-sensitive adhesive layer is too thin, the adhesive physical properties tend to be difficult to stabilize, and if it is too thick, adhesive residue tends to occur.
  • polyester resins such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer
  • Polyolefin resins such as polyethylene, polypropylene, and polymethylpentene
  • Polyfluorinated ethylene resins such as polyvinyl fluoride, polyvinylidene fluoride, and polyfluorinated ethylene
  • Polyamides such as nylon 6, nylon 6, and 6
  • Polyvinyl chloride Polyvinyl chloride / Vinyl acetate copolymers, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, vinyl polymers such as polyvinyl alcohol and vinylon
  • cellulose resins such as cellulose triacetate and cellophane
  • the article having the metal surface includes a metal surface, and the pressure-sensitive adhesive sheet is directly or at least partially bonded to the metal surface.
  • the adherend to which the pressure-sensitive adhesive sheet is bonded (sometimes referred to as a “metal face-containing adherend”) has at least a partial metal face.
  • the part where the metal surface is formed is not particularly limited as long as it is a part where the adhesive sheet can be directly attached, and may be an outer surface, Further, it may be an inner surface or the like.
  • these plurality of metal surfaces may be surfaces formed of the same metal material or formed of different metal materials. It may be a surface.
  • the metal surface in the metal surface-containing adherend may be the surface of a metal surface-containing adherend formed of a metal material, or formed on the surface of a substrate (or structure) formed of various materials. It may be the surface of the metal layer (particularly, the surface of the metal thin film layer). In any case, the metal surface may be a surface made of a metal material.
  • the metal layer such as the metal thin film layer can be formed at a predetermined site on the surface of the base material (or structure) made of various materials.
  • the thickness of the metal thin film layer can be appropriately selected according to the type of the metal surface-containing adherend, and may be, for example, 0.1 ⁇ m or more.
  • the upper limit of the thickness of the metal thin film layer is not particularly limited as long as it is generally regarded as a thin film layer.
  • Examples of the metal material for forming the metal surface include metal materials made of simple metals such as aluminum, silver, gold, copper, iron, titanium, platinum and nickel; gold alloys (for example, gold-copper alloys), Copper alloys (eg, copper-zinc alloy (brass), copper-aluminum alloy, etc.), aluminum alloys (eg, aluminum-molybdenum alloy, aluminum-tantalum alloy, aluminum-cobalt alloy, aluminum-chromium alloy, aluminum-titanium alloy, Aluminum-platinum alloy, etc.), nickel alloys (eg, nickel-chromium alloy, copper-nickel alloy, zinc-nickel alloy, etc.), tin alloys, metal materials made of various alloys such as stainless steel, and the like. These metal materials can be used alone or in combination of two or more.
  • the metal material may be a metal material containing only a metal element, or a metal material containing a non-metal element together with a metal element [eg, metal oxide, hydroxide, halide (chloride, etc.) And metal compounds such as oxo acid salts (nitrates, sulfates, phosphates, carbonates, etc.).
  • a metal element eg, metal oxide, hydroxide, halide (chloride, etc.
  • metal compounds such as oxo acid salts (nitrates, sulfates, phosphates, carbonates, etc.).
  • a window material having a metal surface such as a metal thin film layer surface
  • a member for constituting the window material or a metal thin film
  • examples thereof include an optical product having an electromagnetic wave shielding layer formed of layers, or a member for constituting the optical product.
  • the optical product having the electromagnetic wave shielding layer include optical devices such as an electronic display (plasma display and the like), optically recordable discs (optical recording discs) such as a digital universal disc, and the like.
  • the suspension was heated to 68 ° C. while stirring and kept constant for 4 hours. Then, it cooled to room temperature (about 25 degreeC). Next, the reaction product was separated into solid and liquid, thoroughly washed with water, and then dried at 70 ° C. for 12 hours using a dryer to obtain a bulk acrylic resin (A-1).
  • the resulting acrylic resin (A-1) had a weight average molecular weight (Mw) of 1.3 million, a dispersity (Mw / Mn) of 4.6, and a glass transition temperature of ⁇ 47 ° C.
  • the suspension was heated to 68 ° C. while stirring and kept constant for 4 hours. Then, it cooled to room temperature (about 25 degreeC). Next, the reaction product was separated into solid and liquid, thoroughly washed with water, and then dried at 70 ° C. for 12 hours using a dryer to obtain a bulk acrylic resin (A-2).
  • the resulting acrylic resin (A-2) had a weight average molecular weight (Mw) of 950,000, a dispersity (Mw / Mn) of 3.5, and a glass transition temperature of ⁇ 5 ° C.
  • acrylic resin (A) 12 parts of acrylic resin (A-1), as monofunctional unsaturated compound (B), 18 parts of 4-hydroxybutyl acrylate (HBA: (B2)), cyclohexyl acrylate (CHA: (B1)) 20 parts, 2-ethylhexyl acrylate (2EHA: (B3)) 50 parts, and polyfunctional unsaturated compound (C) 0.3 parts of trimethylolpropane triacrylate (TMPTA) were equipped with a stirrer. The mixture was placed in a container and stirred for 24 hours to dissolve.
  • HBA 4-hydroxybutyl acrylate
  • CHA cyclohexyl acrylate
  • 2EHA: (B3) 2-ethylhexyl acrylate
  • TMPTA trimethylolpropane triacrylate
  • the pressure-sensitive adhesive composition obtained above was coated on a polyethylene terephthalate (PET) substrate having a thickness of 100 ⁇ m so as to have a thickness of 130 ⁇ m. Furthermore, the coated surface was coated so that the release-treated surface was in contact with the coated surface, using a PET substrate that had been subjected to a release treatment. Then, using the ultraviolet irradiation apparatus shown below, the pressure-sensitive adhesive composition is irradiated with ultraviolet rays so that the integrated light amount becomes 2400 mJ / cm 2 from a high-pressure mercury lamp adjusted so that the irradiation intensity becomes 200 mW / cm 2. A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer obtained by curing the product was obtained.
  • PET polyethylene terephthalate
  • Example 2 adhesion was performed in the same manner as in Example 1 except that the blending ratio of 4-hydroxybutyl acrylate (HBA), cyclohexyl acrylate (CHA) and 2-ethylhexyl acrylate (2EHA) was changed as shown in Table 1 below. An agent composition and an adhesive sheet were obtained.
  • HBA 4-hydroxybutyl acrylate
  • CHA cyclohexyl acrylate
  • 2EHA 2-ethylhexyl acrylate
  • Example 9 Example 1 is the same as Example 1 except that acrylic resin (A-2) is used instead of acrylic resin (A-1) and the blending ratio of other components is changed as shown in Table 2 below. Thus, a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet were obtained.
  • Example 1 adhesion was performed in the same manner as in Example 1 except that the blending ratio of 4-hydroxybutyl acrylate (HBA), cyclohexyl acrylate (CHA) and 2-ethylhexyl acrylate (2EHA) was changed as shown in Table 1 below. An agent composition and an adhesive sheet were obtained.
  • HBA 4-hydroxybutyl acrylate
  • CHA cyclohexyl acrylate
  • 2EHA 2-ethylhexyl acrylate
  • Example 4 the pressure-sensitive adhesive composition was composed of 14.6 parts acrylic resin (A-1), 39.4 parts 2-ethylhexyl acrylate (2EHA), 39.4 parts butyl acrylate (BA), acrylic acid ( AAc) 6.6 parts, trimethylolpropane triacrylate (TMPTA) 0.3 part, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: “Darocur 1173”; Ciba Specialty)
  • a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet were obtained in the same manner as in Example 1, except that 1 part of Chemicals Co., Ltd. (HMPP) was used.
  • the gel fraction, pressure-sensitive adhesive force, holding power (cohesive force), and corrosion resistance of the pressure-sensitive adhesive layer were measured and evaluated by the following methods. The results are also shown in Table 2 below.
  • ⁇ Corrosion resistance> The obtained pressure-sensitive adhesive sheet was bonded to a copper foil (thickness: 130 ⁇ m) and then stored in an atmosphere of 60 ° C. ⁇ 90% RH for 250 hours. Thereafter, the surface of the copper foil was visually observed from the polyethylene terephthalate film side to confirm the presence or absence of corrosion on the surface of the copper foil to which the adhesive sheet was bonded. (Evaluation criteria) ⁇ ⁇ ⁇ ⁇ No corrosion ⁇ ⁇ ⁇ ⁇ Corrosion
  • the adhesives of Examples 1 to 9 consisting of an adhesive composition containing both an alicyclic structure-containing ethylenically unsaturated compound and a hydroxyl group-containing ethylenically unsaturated compound balance the adhesive force and cohesive strength (holding power). It can be seen that it is excellent and also has excellent corrosion resistance because it does not contain acid.
  • the pressure-sensitive adhesive of Comparative Example 1 that does not contain both the alicyclic structure-containing ethylenically unsaturated compound and the hydroxyl group-containing ethylenically unsaturated compound is inferior in both adhesive strength and cohesive strength (holding power).
  • the adhesive of Comparative Example 2 that does not contain a cyclic structure-containing ethylenically unsaturated compound is inferior in adhesive strength
  • the adhesive of Comparative Example 3 that does not contain a hydroxyl group-containing ethylenically unsaturated compound is inferior in cohesive strength (holding power).
  • the adhesive of the comparative example 4 which consists of an adhesive composition with which the acrylic acid which has an acidic group was mix
  • ⁇ Haze> Manufacture of sample for haze measurement Cut out the obtained adhesive sheet to 3 cm x 4 cm, peel off the release release sheet, and press the adhesive layer side against an alkali-free glass plate (Corning Corp., Eagle XG), The sample was subjected to autoclave (50 ° C., 0.5 MPa ⁇ 20 min) to obtain a sample for haze measurement. -Measurement of haze value The haze of the sample for haze measurement was measured under the following conditions. -Initial haze: Measured after creating a sample for haze measurement. -Humid heat haze 1: Measured after preparation of a sample for haze measurement and standing at 60 ° C.
  • Humid heat haze 2 Measured after preparing a sample for haze measurement, after standing at 60 ° C. ⁇ 90% RH for 100 hours, and then standing at room temperature for 3 hours.
  • the diffuse transmittance and total light transmittance were measured using HAZE MATER NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.). This machine conforms to JIS K7361-1. The values of the obtained diffuse transmittance and total light transmittance were substituted into the following formula to calculate haze.
  • Haze value (%) (diffuse transmittance / total light transmittance) ⁇ 100
  • the pressure-sensitive adhesive composition of Example 9 comprising a pressure-sensitive adhesive composition using an acrylic resin (A-2) obtained by copolymerizing an alicyclic structure-containing (meth) acrylic acid ester-based monomer has a haze even under wet heat conditions. It can be seen that there is little change in the resistance to heat and heat resistance.
  • the pressure-sensitive adhesive composed of the pressure-sensitive adhesive composition of the present invention has strong adhesive force and excellent cohesive force, and therefore hardly peels off from the substrate even in a high-temperature environment.
  • Optical equipment such as an electronic display that is useful as a sheet, and that is capable of satisfying adhesive properties without causing acid in the adhesive, and that requires corrosion resistance against metals and metal oxides. It is also useful as an optical pressure-sensitive adhesive sheet for laminating an optical recording disk (optical recording medium) such as a digital universal disk.

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Abstract

Provided is a pressure-sensitive adhesive having a high adhesive strength and a high cohesive strength, which is cured by active energy ray irradiation. The present invention relates to a pressure-sensitive adhesive composition comprising: an acrylic resin (A); an ethylenically unsaturated compound containing one ethylenically unsaturated group (B); an ethylenically unsaturated compound containing two or more ethylenically unsaturated groups (C); and a photoinitiator (D). The pressure-sensitive adhesive composition is characterized by comprising an ethylenically unsaturated compound containing an alicyclic structure (B1) and a hydroxyl group-containing ethylenically unsaturated compound (B2) as the ethylenically unsaturated compound containing one ethylenically unsaturated group (B).

Description

粘着剤組成物、粘着剤、およびそれを用いてなる粘着シートPSA composition, PSA, and PSA sheet using the same
　本発明は、粘着剤組成物、粘着剤、およびそれを用いてなる粘着シートに関するものであり、詳しくは、高い粘着力と、高い凝集力を有する粘着剤、中でも特に耐腐食性が必要とされる電子部材や光学部材用に適した粘着剤、およびそれを用いた粘着シートに関するものである。 The present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive, and a pressure-sensitive adhesive sheet using the same. Specifically, a pressure-sensitive adhesive having a high pressure-sensitive adhesive force and a high cohesive force, particularly corrosion resistance is required. The present invention relates to an adhesive suitable for an electronic member or an optical member, and an adhesive sheet using the same.
　粘着剤には、被着体を強固に長期間貼り合わせることを目的とする強粘着性の粘着剤や、貼り付け後に被着体から剥離することを前提とする剥離タイプの粘着剤など様々なタイプが存在しており、各種分野ごとに最適の粘着剤が設計され使用されている。 There are various types of adhesives, such as strong adhesives for the purpose of firmly bonding adherends for a long period of time, and peel-off type adhesives that are supposed to be peeled off from adherends after being attached. There are types, and the most suitable adhesive is designed and used for each field.
　例えば、強粘着性を示すタイプの粘着剤については、通常、粘着剤中に酸性の官能基を多く導入したり、粘着付与樹脂を大量に使用したりすることによって高い粘着力が付与されており、種々の強粘着性が必要とされる分野で使用されている（例えば、特許文献１参照。）。 For example, for a type of adhesive that exhibits strong tackiness, high adhesive strength is usually imparted by introducing many acidic functional groups into the adhesive or using a large amount of tackifying resin. And used in fields where various strong adhesive properties are required (for example, see Patent Document 1).
　ところが、これら強粘着性の粘着剤は、導入されている酸性の官能基のために被着体を腐食してしまったり、酸性の官能基に由来するアウトガスが発生してしまうために、電子部材、特に精密電子部材に貼り合わせて用いる情報ラベル用途や、電子部材固定用途には適さないものであった。
　従って、これら光学用途で使用する粘着剤には、酸を用いないタイプ（酸フリー）の粘着剤（例えば、特許文献２参照。）を使用することが必要となっていた。 However, these strongly adhesive pressure-sensitive adhesives corrode the adherend due to the introduced acidic functional group, or outgas derived from the acidic functional group is generated. In particular, it is not suitable for information label applications that are used by being bonded to precision electronic members or for electronic member fixing applications.
Therefore, it is necessary to use an acid-free type (acid-free) pressure-sensitive adhesive (for example, refer to Patent Document 2) as the pressure-sensitive adhesive used in these optical applications.
日本国特開２００７－２１７６７４号公報Japanese Laid-Open Patent Publication No. 2007-217674 日本国特開２００３－２６８３３５号公報Japanese Unexamined Patent Publication No. 2003-268335
　しかしながら、特にタッチパネル等に用いられるＩＴＯ透明電極やＰＤＰ等に用いられる金属メッシュ等の金属及び金属酸化物等が使用される電子ディスプレイ等の光学機器や、デジタル万能ディスク等の光学的記録ディスク（光学的記録媒体）などの光学用途で使用する粘着剤には、耐腐食性に加えて、耐熱性等の厳しい耐久性が必要となるため、高い凝集力と高い粘着力を有する粘着剤が必要とさていたが、特許文献２のような一般的な酸フリーの粘着剤では、耐腐食性には優れるものの、粘着力、凝集力が充分ではないため、光学用途の粘着剤としては使用することができなかった。
　そこで、優れた耐腐食性と粘着物性(粘着力、凝集力）を兼ね備えた粘着剤の開発が望まれていた。 However, optical devices such as electronic displays using metals and metal oxides such as ITO transparent electrodes used for touch panels and the like, metal meshes used for PDPs, etc., and optical recording disks such as digital universal disks (optical) Adhesives used in optical applications such as optical recording media) require strict durability such as heat resistance in addition to corrosion resistance, and therefore require adhesives with high cohesive strength and high adhesive strength. However, a general acid-free pressure-sensitive adhesive such as Patent Document 2 is excellent in corrosion resistance, but has insufficient adhesive force and cohesive force. Therefore, it can be used as a pressure-sensitive adhesive for optical applications. could not.
Therefore, it has been desired to develop a pressure-sensitive adhesive having excellent corrosion resistance and adhesive properties (adhesive strength, cohesive strength).
　そこで、本発明ではこのような背景下において、高い粘着力と高い凝集力を有し、かつ酸性基を含有しない場合には耐腐食性に優れる粘着剤を得るための粘着剤組成物の提供を目的とする。 Therefore, in the present invention, in such a background, the provision of a pressure-sensitive adhesive composition for obtaining a pressure-sensitive adhesive having high adhesive strength and high cohesive strength and having excellent corrosion resistance when it does not contain an acidic group. Objective.
　しかるに本発明者は、かかる事情に鑑み鋭意研究を重ねた結果、アクリル系樹脂、単官能性不飽和モノマー、多官能性不飽和モノマー、および光重合開始剤からなる無溶剤タイプの活性エネルギー線硬化型粘着剤において、単官能性不飽和モノマーとして、脂環式構造含有エチレン性不飽和化合物と水酸基含有エチレン性不飽和化合物とを併用することにより、粘着力と凝集力にバランスよく優れた粘着剤が得られることを見出し、本発明を完成させるに至った。 However, the present inventor has conducted extensive research in view of such circumstances, and as a result, solvent-free active energy ray curing comprising an acrylic resin, a monofunctional unsaturated monomer, a polyfunctional unsaturated monomer, and a photopolymerization initiator. Type pressure-sensitive adhesive, a monofunctional unsaturated monomer that is used in combination with an alicyclic structure-containing ethylenically unsaturated compound and a hydroxyl group-containing ethylenically unsaturated compound, providing a good balance between adhesive strength and cohesive strength Has been found, and the present invention has been completed.
　即ち、本発明の要旨は、アクリル系樹脂（Ａ）、エチレン性不飽和基を１個有するエチレン性不飽和化合物（Ｂ）、エチレン性不飽和基を２個以上有するエチレン性不飽和化合物（Ｃ）、および光重合開始剤（Ｄ）を含有する粘着剤組成物であって、エチレン性不飽和基を１個有するエチレン性不飽和化合物（Ｂ）として、脂環式構造含有エチレン性不飽和化合物（Ｂ１）、及び水酸基含有エチレン性不飽和化合物（Ｂ２）を含有することを特徴とする粘着剤組成物に関するものである。
　更には、本発明は、粘着剤、それらを用いて得られる粘着シートに関するものである。 That is, the gist of the present invention is an acrylic resin (A), an ethylenically unsaturated compound (B) having one ethylenically unsaturated group, and an ethylenically unsaturated compound (C) having two or more ethylenically unsaturated groups. ), And a photopolymerization initiator (D), and an ethylenically unsaturated compound containing an alicyclic structure as an ethylenically unsaturated compound (B) having one ethylenically unsaturated group The present invention relates to a pressure-sensitive adhesive composition containing (B1) and a hydroxyl group-containing ethylenically unsaturated compound (B2).
Furthermore, this invention relates to an adhesive and the adhesive sheet obtained by using them.
　本発明は以下の態様を含む。
[１]　アクリル系樹脂（Ａ）、エチレン性不飽和基を１個有するエチレン性不飽和化合物（Ｂ）、エチレン性不飽和基を２個以上有するエチレン性不飽和化合物（Ｃ）、および光重合開始剤（Ｄ）を含有する粘着剤組成物であって、エチレン性不飽和基を１個有するエチレン性不飽和化合物（Ｂ）として、脂環式構造含有エチレン性不飽和化合物（Ｂ１）、及び水酸基含有エチレン性不飽和化合物（Ｂ２）を含有することを特徴とする粘着剤組成物。
[２]　アクリル系樹脂（Ａ）が、懸濁重合により得られたドライレジンであることを特徴とする[１]記載の粘着剤組成物。
[３]　アクリル系樹脂（Ａ）が、脂環式構造含有（メタ）アクリル酸エステル系モノマーを含有する共重合成分を共重合させてなるアクリル系樹脂であることを特徴とする[１]または [２]記載の粘着剤組成物。
[４]　エチレン性不飽和基を１個有するエチレン性不飽和化合物（Ｂ）中における脂環式構造含有エチレン性不飽和化合物（Ｂ１）及び水酸基含有エチレン性不飽和化合物（Ｂ２）の合計量の含有割合が、１０～７０重量％であることを特徴とする[１]から[３]のいずれかに記載の粘着剤組成物。
[５]　実質的に酸を含まないことを特徴とする[１]から[４]のいずれかに記載の粘着剤組成物。
[６]　溶剤を含有しないことを特徴とする[１] から[５]のいずれかに記載の粘着剤組成物。
[７]　 [１] から[６]のいずれかに記載の粘着剤組成物が、活性エネルギー線照射により硬化されてなることを特徴とする粘着剤。
[８]　基材と、[７]記載の粘着剤からなる粘着剤層を含有することを特徴とする粘着シート。 The present invention includes the following aspects.
[1] Acrylic resin (A), ethylenically unsaturated compound (B) having one ethylenically unsaturated group, ethylenically unsaturated compound (C) having two or more ethylenically unsaturated groups, and photopolymerization An adhesive composition containing an initiator (D), wherein the ethylenically unsaturated compound (B) having one ethylenically unsaturated group is an alicyclic structure-containing ethylenically unsaturated compound (B1), and A pressure-sensitive adhesive composition comprising a hydroxyl group-containing ethylenically unsaturated compound (B2).
[2] The pressure-sensitive adhesive composition according to [1], wherein the acrylic resin (A) is a dry resin obtained by suspension polymerization.
[3] The acrylic resin (A) is an acrylic resin obtained by copolymerizing a copolymer component containing an alicyclic structure-containing (meth) acrylic acid ester monomer [1] or [2] The pressure-sensitive adhesive composition according to [2].
[4] The total amount of the alicyclic structure-containing ethylenically unsaturated compound (B1) and the hydroxyl group-containing ethylenically unsaturated compound (B2) in the ethylenically unsaturated compound (B) having one ethylenically unsaturated group The pressure-sensitive adhesive composition according to any one of [1] to [3], wherein the content is 10 to 70% by weight.
[5] The pressure-sensitive adhesive composition according to any one of [1] to [4], which is substantially free of an acid.
[6] The pressure-sensitive adhesive composition according to any one of [1] to [5], which does not contain a solvent.
[7] A pressure-sensitive adhesive, wherein the pressure-sensitive adhesive composition according to any one of [1] to [6] is cured by irradiation with active energy rays.
[8] A pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive according to [7].
　本発明の粘着剤組成物からなる粘着剤は、強固な粘着力と優れた凝集力を有するものであり、そのために高温環境下でも基材からの剥がれが生じにくく、特に光学部材貼合わせ用の粘着剤、粘着シートとして有用である。更に、粘着剤中に酸を含有させなくても粘着力と凝集力に優れたものとなるため、金属や金属酸化物等に対して耐腐食性が要求される電子ディスプレイ等の光学機器や、デジタル万能ディスク等の光学的記録ディスク（光学的記録媒体）を貼合わせるための光学用粘着シートとして特に有効である。 The pressure-sensitive adhesive composed of the pressure-sensitive adhesive composition of the present invention has a strong pressure-sensitive adhesive force and an excellent cohesive force, and therefore does not easily peel off from the base material even in a high-temperature environment. It is useful as an adhesive and an adhesive sheet. Furthermore, since it becomes excellent in adhesive strength and cohesive force without containing an acid in the adhesive, optical equipment such as an electronic display that requires corrosion resistance against metals and metal oxides, It is particularly effective as an optical pressure-sensitive adhesive sheet for laminating optical recording disks (optical recording media) such as digital universal disks.
　以下、本発明を詳細に説明するが、これらは望ましい実施態様の一例を示すものである。
　なお、本発明において、（メタ）アクリルとはアクリルあるいはメタクリルを、（メタ）アクリロイルとはアクリロイルあるいはメタクリロイルを、（メタ）アクリレートとはアクリレートあるいはメタクリレートをそれぞれ意味するものである。 The present invention will be described in detail below, but these show examples of desirable embodiments.
In the present invention, (meth) acryl means acryl or methacryl, (meth) acryloyl means acryloyl or methacryloyl, and (meth) acrylate means acrylate or methacrylate.
　まず、本発明の粘着剤組成物について説明する。
　本発明の粘着剤組成物は、アクリル系樹脂（Ａ）、エチレン性不飽和基を１個有するエチレン性不飽和化合物（Ｂ）、エチレン性不飽和基を２個以上有するエチレン性不飽和化合物（Ｃ）、および光重合開始剤（Ｄ）を含有するものである。 First, the pressure-sensitive adhesive composition of the present invention will be described.
The pressure-sensitive adhesive composition of the present invention comprises an acrylic resin (A), an ethylenically unsaturated compound (B) having one ethylenically unsaturated group, and an ethylenically unsaturated compound having two or more ethylenically unsaturated groups ( C) and a photopolymerization initiator (D).
　アクリル系樹脂（Ａ）は、共重合成分として、（メタ）アクリル酸エステル系モノマー（ａ１）を主成分とし、必要に応じて、官能基含有共重合性モノマー（ａ２）、その他の共重合性モノマー（ａ３）を含有してなる共重合成分を共重合して得ることができる。 The acrylic resin (A) has a (meth) acrylic acid ester monomer (a1) as a main component as a copolymerization component, and if necessary, a functional group-containing copolymerizable monomer (a2) and other copolymerization properties. It can be obtained by copolymerizing a copolymer component containing the monomer (a3).
　（メタ）アクリル酸エステル系モノマー（ａ１）（ただし、後述の（ａ２）を除く）としては、（メタ）アクリル酸アルキルエステル系モノマー（ａ１－１）、脂環式構造含有（メタ）アクリル酸エステル系モノマー（ａ１－２）等が挙げられる。 (Meth) acrylic acid ester monomer (a1) (excluding (a2) described later) includes (meth) acrylic acid alkyl ester monomer (a1-1), alicyclic structure-containing (meth) acrylic acid And ester monomers (a1-2).
　かかる（メタ）アクリル酸アルキルエステル系モノマー（ａ１－１）としては、アルキル基の炭素数が、通常１～２０であり、特に好ましくは１～１０、更に好ましくは１～８、殊に好ましくは１～４であり、具体的には、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、ｎ－ブチル（メタ）アクリレート、ｉｓｏ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｎ－ヘキシル（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－オクチルアクリレート、ノニル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、ｉｓｏ―ステアリルアクリレート等が挙げられる。これらは１種を単独で又は２種以上を併せて用いることができる。
　これら（メタ）アクリル酸アルキルエステル系モノマーの中でも、共重合性、粘着物性、取り扱いやすさ及び原料入手しやすさの点で、エチル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレートが好ましく用いられ、更に好ましく耐久性に優れる点でｎ－ブチル（メタ）アクリレートが用いられる。 In such a (meth) acrylic acid alkyl ester monomer (a1-1), the alkyl group usually has 1 to 20 carbon atoms, particularly preferably 1 to 10, more preferably 1 to 8, and particularly preferably. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert -Butyl (meth) acrylate, n-propyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl acrylate, nonyl (meth) acrylate, Isodecyl (meth) acrylate, lauryl (meth) acrylate, Chill (meth) acrylate, stearyl (meth) acrylate, iso- stearyl acrylate. These can be used alone or in combination of two or more.
Among these (meth) acrylic acid alkyl ester monomers, ethyl (meth) acrylate and n-butyl (meth) acrylate are preferably used in terms of copolymerizability, adhesive properties, ease of handling, and availability of raw materials. Further, n-butyl (meth) acrylate is preferably used from the viewpoint of excellent durability.
　上記脂環式構造含有（メタ）アクリル酸エステル系モノマー（ａ１－２）としては、脂環式構造の炭素数が、通常、炭素数４～２０であり、特に好ましくは６～１０であり、具体的には、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、２－メチルシクロヘキシル（メタ）アクリレート、トリシクロ［５．２．１．０２，６］デカン－８－イル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、２－ジシクロペンタニルオキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、４－ｔ－ブチルシクロヘキシル（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）アクリレート等が挙げられるが、これらの中でも粘着物性、モノマーとの相溶性からイソボルニル（メタ）アクリレートが好ましく用いられる。 In the alicyclic structure-containing (meth) acrylic acid ester monomer (a1-2), the alicyclic structure usually has 4 to 20 carbon atoms, particularly preferably 6 to 10 carbon atoms. Specifically, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.02,6] decane-8 -Yl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 4-t-butylcyclohexyl ( (Meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) Acrylate and the like, but the adhesive properties Among these, compatibility from isobornyl (meth) acrylate with monomers is preferably used.
　（メタ）アクリル酸エステル系モノマー（ａ１）の共重合成分中における含有量としては、好ましくは６０～１００重量％、特に好ましくは７０～９５重量％、更に好ましくは８０～９０重量％であり、（メタ）アクリル酸エステル系モノマー（ａ１）の含有量が少なすぎると、粘着剤として使用した場合の粘着力が不足する傾向にある。 The content of the (meth) acrylic acid ester monomer (a1) in the copolymerization component is preferably 60 to 100% by weight, particularly preferably 70 to 95% by weight, more preferably 80 to 90% by weight, When the content of the (meth) acrylic acid ester monomer (a1) is too small, the adhesive strength when used as an adhesive tends to be insufficient.
　本発明の粘着剤組成物を硬化して得られる粘着剤に透明性が求められる場合には、ヘイズ変化を抑制することができる点で、（メタ）アクリル酸エステル系モノマー（ａ１）として、脂環式構造含有（メタ）アクリル酸エステル系モノマーを用いることが好ましい。 When transparency is required for the pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition of the present invention, as the (meth) acrylic acid ester monomer (a1), fat can be suppressed. It is preferable to use a cyclic structure-containing (meth) acrylic acid ester monomer.
　また、かかる環式構造含有（メタ）アクリル酸エステル系モノマー（ａ１－２）と、（メタ）アクリル酸アルキルエステル系モノマー（ａ１－１）との含有割合（重量比）としては、（ａ１－２）：（ａ１－１）＝５：９５～９５：５が好ましく、特に好ましくは（ａ１－２）：（ａ１－１）＝１０：９０～９０：１０、更に好ましくは（ａ１－２）：（ａ１－１）＝２０：８０～８０：２０である。 Further, the content ratio (weight ratio) between the cyclic structure-containing (meth) acrylic acid ester monomer (a1-2) and the (meth) acrylic acid alkyl ester monomer (a1-1) is (a1- 2): (a1-1) = 5: 95 to 95: 5 is preferable, (a1-2) :( a1-1) = 10: 90 to 90:10 is more preferable, and (a1-2) is more preferable. : (A1-1) = 20: 80 to 80:20.
　官能基含有共重合性モノマー（ａ２）としては、水酸基含有モノマー、オキシアルキレン基含有モノマー、アミド基含有モノマー、アミノ基含有モノマー、窒素含有モノマー、グリシジル基含有モノマー等の官能基含有モノマーがあげられ、これらから選ばれる１種もしくは２種以上が用いられる。
　これらの中でも、高い凝集力得られる点で、水酸基含有モノマーが好ましく用いられ、特には好ましくは、２－ヒドロキシエチル（メタ）アクリレートである。 Examples of the functional group-containing copolymerizable monomer (a2) include functional group-containing monomers such as a hydroxyl group-containing monomer, an oxyalkylene group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, a nitrogen-containing monomer, and a glycidyl group-containing monomer. 1 type or 2 types or more chosen from these are used.
Among these, a hydroxyl group-containing monomer is preferably used from the viewpoint of obtaining high cohesive force, and 2-hydroxyethyl (meth) acrylate is particularly preferable.
　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、５－ヒドロキシペンチル（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、８－ヒドロキシオクチル（メタ）アクリレート、１０－ヒドロキシデシル（メタ）アクリレート、（４－ヒドロキシメチルシクロへキシル）メチル（メタ）アクリレート等の（メタ）アクリル酸ヒドロキシアルキルエステル、カプロラクトン変性２－ヒドロキシエチル（メタ）アクリレート等のカプロラクトン変性モノマー、２－アクリロイルオキシエチル－２－ヒドロキシエチルフタル酸、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－ヒドロキシエチル（メタ）アクリルアミド等の１級水酸基含有モノマー；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、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート等の２級水酸基含有モノマー；２，２－ジメチル－２－ヒドロキシエチル（メタ）アクリレート等の３級水酸基含有モノマーがあげられる。 Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meta ) Acrylate, 10-hydroxydecyl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate and other (meth) acrylic acid hydroxyalkyl esters, caprolactone-modified 2-hydroxyethyl (meth) acrylate and other caprolactone Monomers containing primary hydroxyl groups such as modified monomers, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, etc. 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3 -Secondary hydroxyl group-containing monomers such as phenoxypropyl (meth) acrylate; tertiary hydroxyl group-containing monomers such as 2,2-dimethyl-2-hydroxyethyl (meth) acrylate.
　また、ジエチレングリコール（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート等のポリエチレングリコール誘導体、ポリプロピレングリコールモノ（メタ）アクリレート等のポリプロピレングリコール誘導体、ポリエチレングリコール－ポリプロピレングリコール－モノ（メタ）アクリレート、ポリ（エチレングリコール－テトラメチレングリコール）モノ（メタ）アクリレート、ポリ（プロピレングリコール－テトラメチレングリコール）モノ（メタ）アクリレート等のオキシアルキレン変性の水酸基含有モノマーを用いてもよい。 In addition, polyethylene glycol derivatives such as diethylene glycol (meth) acrylate and polyethylene glycol mono (meth) acrylate, polypropylene glycol derivatives such as polypropylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol-mono (meth) acrylate, poly (ethylene glycol) An oxyalkylene-modified hydroxyl group-containing monomer such as -tetramethylene glycol) mono (meth) acrylate or poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate may be used.
　オキシアルキレン基含有モノマーとしては、例えば、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－メトキシブチル（メタ）アクリレート、２－ブトキシエチル（メタ）アクリレート、２－ブトキシジエチレングリコール（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート、メトキシトリエチレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、メトキシジプロピレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、オクトキシポリエチレングリコール-ポリプロピレングリコールモノ（メタ）アクリレート、ラウロキシポリエチレングリコールモノ（メタ）アクリレート、ステアロキシポリエチレングリコールモノ（メタ）アクリレート等の脂肪族系の（メタ）アクリル酸エステルや、２－フェノキシエチル（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール-ポリプロピレングリコール（メタ）アクリレート、ノニルフェノールエチレンオキサイド付加物（メタ）アクリレート等の芳香族系の（メタ）アクリル酸エステル等があげられる。 Examples of the oxyalkylene group-containing monomer include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and 2-butoxydiethylene glycol. (Meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, octoxypolyethylene glycol- Polypropylene glycol mono (meth) acrylate, Lauroxy polyethylene glycol mono (meth) acrylate, steer Aliphatic (meth) acrylic esters such as loxypolyethyleneglycol mono (meth) acrylate, 2-phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxypolyethyleneglycol-polypropyleneglycol (meth) acrylate, Examples thereof include aromatic (meth) acrylic acid esters such as nonylphenol ethylene oxide adduct (meth) acrylate.
　アミド基含有モノマーとしては、例えば、アクリルアミド、メタクリルアミド、Ｎ－（ｎ－ブトキシアルキル）アクリルアミド、Ｎ－（ｎ－ブトキシアルキル）メタクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、アクリルアミド－３－メチルブチルメチルアミン、ジメチルアミノアルキルアクリルアミド、ジメチルアミノアルキルメタクリルアミド等があげられる。 Examples of amide group-containing monomers include acrylamide, methacrylamide, N- (n-butoxyalkyl) acrylamide, N- (n-butoxyalkyl) methacrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl. (Meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, acrylamide-3-methylbutylmethylamine, dimethylaminoalkylacrylamide, dimethylaminoalkylmethacrylamide and the like.
　アミノ基含有モノマーとしては、例えば、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレートやその４級化物等があげられる。 Examples of the amino group-containing monomer include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof.
　窒素含有モノマーとしては、例えば、アクリロイルモルフォリン等があげられる。 Examples of the nitrogen-containing monomer include acryloylmorpholine.
　グリシジル基含有モノマーとしては、例えば、グリシジル（メタ）アクリレート、アリルグリシジルエーテル等があげられる。 Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.
　官能基含有共重合性モノマー（ａ２）の共重合成分中における含有割合は、好ましくは０．０１～２０重量％、特に好ましくは０．１～１５重量％、更に好ましくは０．２～１０重量％であり、官能基含有共重合性モノマー（ａ２）が少なすぎると官能基間の相互作用が小さくなり凝集力が低下する傾向があり、多すぎると粘着力が下がりすぎる傾向がある。 The content of the functional group-containing copolymerizable monomer (a2) in the copolymerization component is preferably 0.01 to 20% by weight, particularly preferably 0.1 to 15% by weight, and more preferably 0.2 to 10% by weight. If the amount of the functional group-containing copolymerizable monomer (a2) is too small, the interaction between the functional groups tends to be small and the cohesive force tends to decrease, and if too large, the adhesive force tends to decrease too much.
　その他の共重合性モノマー（ａ３）としては、アクリロニトリル、メタクリロニトリル、スチレン、α－メチルスチレン、酢酸ビニル、プロピオン酸ビニル、ステアリン酸ビニル、塩化ビニル、塩化ビニリデン、アルキルビニルエーテル、ビニルトルエン、ビニルピリジン、ビニルピロリドン、イタコン酸ジアルキルエステル、フマル酸ジアルキルエステル、アリルアルコール、アクリルクロライド、メチルビニルケトン、Ｎ－アクリルアミドメチルトリメチルアンモニウムクロライド、アリルトリメチルアンモニウムクロライド、ジメチルアリルビニルケトン等が挙げられる。 Other copolymerizable monomers (a3) include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, vinyl pyridine. Vinyl pyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, acrylic chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallyl vinylketone, and the like.
　その他の共重合性モノマー（ａ３）の共重合成分中における含有割合は、好ましくは０～４０重量％、特には好ましくは３～３０重量％、更に好ましくは８～２０重量％であり、その他の共重合性モノマー（ａ３）の含有量が多すぎると粘着性能が低下しやすい傾向がある。 The content of the other copolymerizable monomer (a3) in the copolymerization component is preferably 0 to 40% by weight, particularly preferably 3 to 30% by weight, more preferably 8 to 20% by weight. When there is too much content of a copolymerizable monomer (a3), there exists a tendency for adhesive performance to fall easily.
　本発明で用いられるアクリル系樹脂（Ａ）は、耐腐食性に優れる点で、酸性基を含有しないものであることが好ましい。 It is preferable that the acrylic resin (A) used in the present invention does not contain an acidic group from the viewpoint of excellent corrosion resistance.
　上記（メタ）アクリル酸エステル系モノマー（ａ１）、必要に応じて官能基含有共重合性モノマー（ａ２）、その他の共重合性モノマー（ａ３）を共重合成分として重合することによりアクリル系樹脂（Ａ）を製造するのであるが、かかる重合にあたっては、溶液ラジカル重合、懸濁重合、塊状重合、乳化重合など当業者周知の方法によって製造することができる。 By polymerizing the (meth) acrylic acid ester monomer (a1), if necessary, a functional group-containing copolymerizable monomer (a2), and other copolymerizable monomers (a3) as a copolymerization component, an acrylic resin ( A) is produced. Such polymerization can be carried out by methods well known to those skilled in the art, such as solution radical polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization.
　これらの中でも、懸濁重合が、分子量の大きいポリマーを得ることができ、また生成ポリマーの単離も容易であるため好ましく用いられ、アクリル系樹脂（Ａ）は、懸濁重合により得られたドライレジンであることが好ましい。 Among these, suspension polymerization is preferably used because a polymer having a large molecular weight can be obtained and the resulting polymer can be easily isolated. The acrylic resin (A) is a dry polymer obtained by suspension polymerization. A resin is preferred.
　上記重合に際し、必要に応じて、ポリビニルアルコール等の分散安定剤や、アゾビスイソブチロニトリル等の重合開始剤を添加することができる。 In the above polymerization, a dispersion stabilizer such as polyvinyl alcohol and a polymerization initiator such as azobisisobutyronitrile can be added as necessary.
　なお、一般に、粘着剤組成物に用いられるアクリル系樹脂は、その製造時に有機溶剤を使用する溶剤系重合により製造されることが多い。このような溶剤系重合のアクリル系樹脂を粘着剤組成物に用いる場合、粘着剤組成物溶液を高温で乾燥することを要するため、多くのエネルギーが必要となったり、また、有機溶剤は引火しやすいだけでなく大気汚染も引き起こすため、溶剤の大規模な回収装置や安全装置が必要となる。しかしながら、上記懸濁重合により得られたドライレジンのアクリル系樹脂（Ａ）を用いると、このような有機溶剤を含有せずに粘着剤組成物を製造することができる。 In general, the acrylic resin used in the pressure-sensitive adhesive composition is often produced by solvent-based polymerization using an organic solvent at the time of production. When such a solvent-based polymerized acrylic resin is used in the pressure-sensitive adhesive composition, it is necessary to dry the pressure-sensitive adhesive composition solution at a high temperature, which requires a lot of energy and the organic solvent ignites. Not only is it easy to cause air pollution, but a large-scale solvent recovery device and safety device are required. However, when the acrylic resin (A) of dry resin obtained by the suspension polymerization is used, the pressure-sensitive adhesive composition can be produced without containing such an organic solvent.
　アクリル系樹脂（Ａ）の重量平均分子量（Ｍｗ）は、５０万～３００万であることが好ましく、特に好ましくは８５万～２５０万、更に好ましくは１００万～２００万である。アクリル系樹脂（Ａ）の重量平均分子量が小さすぎると、活性エネルギー線照射によって得られる粘着剤の凝集力が低下する傾向があり、大きすぎると、均一に相溶した粘着剤組成物が得難くなる傾向がある。 The weight average molecular weight (Mw) of the acrylic resin (A) is preferably 500,000 to 3,000,000, particularly preferably 850,000 to 2,500,000, and more preferably 1,000,000 to 2,000,000. If the weight-average molecular weight of the acrylic resin (A) is too small, the cohesive force of the pressure-sensitive adhesive obtained by irradiation with active energy rays tends to decrease, and if it is too large, a uniformly compatible pressure-sensitive adhesive composition is difficult to obtain. Tend to be.
　アクリル系樹脂（Ａ）の分散度（Ｍｗ／Ｍｎ）は、７以下であることが好ましく、特には５以下、更には４以下であることが好ましい。アクリル系樹脂（Ａ）の分散度（Ｍｗ／Ｍｎ）が大きすぎると、凝集力や粘着物性において活性エネルギー線照射条件による振れが大きくなる傾向がみられる。また、分散度（Ｍｗ／Ｍｎ）の下限値としては通常２である。なお、上記Ｍｎとは、数平均分子量のことをいう。 The degree of dispersion (Mw / Mn) of the acrylic resin (A) is preferably 7 or less, particularly 5 or less, and further preferably 4 or less. When the degree of dispersion (Mw / Mn) of the acrylic resin (A) is too large, there is a tendency that the shake due to the active energy ray irradiation condition increases in the cohesive force and the adhesive physical properties. The lower limit of the degree of dispersion (Mw / Mn) is usually 2. In addition, said Mn means a number average molecular weight.
　アクリル系樹脂（Ａ）のガラス転移温度（Ｔｇ）は、－７０～２０℃であることが好ましく、特に好ましくは－６０～０℃、更に好ましくは－５５～－１０℃である。アクリル系樹脂（Ａ）のガラス転移温度（Ｔｇ）が低すぎると、凝集力が低下する傾向がみられ、高すぎると、粘着剤の脆質化を招く傾向がみられる。 The glass transition temperature (Tg) of the acrylic resin (A) is preferably −70 to 20 ° C., particularly preferably −60 to 0 ° C., and further preferably −55 to −10 ° C. When the glass transition temperature (Tg) of the acrylic resin (A) is too low, the cohesive force tends to decrease, and when it is too high, the pressure-sensitive adhesive tends to become brittle.
　なお、本発明において重量平均分子量とは、標準ポリスチレン分子量換算による重量平均分子量をいい、具体的には、高速液体クロマトグラフィー（日本Ｗａｔｅｒｓ社製、「Ｗａｔｅｒｓ　２６９５（本体）」と「Ｗａｔｅｒｓ　２４１４（検出器）」）に、カラム：Ｓｈｏｄｅｘ　ＧＰＣ　ＫＦ－８０６Ｌ（排除限界分子量：２×１０７、分離範囲：１００～２×１０７、理論段数：１０、０００段／本、充填剤材質：スチレン－ジビニルベンゼン共重合体、充填剤粒径：１０μｍ）の３本直列を用いることにより測定されるものである。数平均分子量においても同様に、上記測定装置を用いて測定されるものである。 In the present invention, the weight average molecular weight means a weight average molecular weight in terms of standard polystyrene molecular weight. Specifically, high-performance liquid chromatography (manufactured by Waters, Japan, “Waters 2695 (main body)” and “Waters 2414 (detection)). Column): Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 7 , separation range: 100 to 2 × 10 7 , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinyl It is measured by using three series of benzene copolymer and filler particle size: 10 μm. Similarly, the number average molecular weight is measured using the above measuring apparatus.
　また、本発明においてガラス転移温度とは、下記Ｆｏｘの式より算出されるものである。 In the present invention, the glass transition temperature is calculated from the following Fox equation.
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000001
　アクリル系樹脂（Ａ）の含有量は、アクリル系樹脂（Ａ）と後述のエチレン性不飽和基を１個有するエチレン性不飽和化合物（Ｂ）の合計１００重量部に対して、５～５０重量部であることが好ましく、特に好ましくは７～４５重量部、更に好ましくは１０～４０重量部である。
　アクリル系樹脂（Ａ）の含有量が少なすぎると、粘度が低すぎて塗工しにくくなる傾向があり、多すぎると粘度が高く塗工しにくくなる傾向がある。 The content of the acrylic resin (A) is 5 to 50 weights with respect to a total of 100 parts by weight of the acrylic resin (A) and an ethylenically unsaturated compound (B) having one ethylenically unsaturated group described later. Parts, preferably 7 to 45 parts by weight, more preferably 10 to 40 parts by weight.
When there is too little content of acrylic resin (A), there exists a tendency for a viscosity to be too low and to become difficult to apply, and when too much, there exists a tendency for a viscosity to become high and to become difficult to apply.
　エチレン性不飽和基を１個有するエチレン性不飽和化合物（Ｂ）（以下、「単官能性不飽和化合物（Ｂ）」と記すことがある。）としては、脂環式構造含有エチレン性不飽和化合物（Ｂ１）および水酸基含有エチレン性不飽和化合物（Ｂ２）を含有することが必要である。
　本発明においては、かかる（Ｂ１）および（Ｂ２）を必須成分として併用することにより、とりわけ脂環式構造含有エチレン性不飽和化合物（Ｂ１）に由来する粘着剤の離型抑制効果による高い粘着力と、とりわけ水酸基含有エチレン性不飽和化合物（Ｂ２）に由来する水素結合による高い凝集力がバランスよく発揮されるものである。 Examples of the ethylenically unsaturated compound (B) having one ethylenically unsaturated group (hereinafter sometimes referred to as “monofunctional unsaturated compound (B)”) include an alicyclic structure-containing ethylenically unsaturated compound. It is necessary to contain a compound (B1) and a hydroxyl-containing ethylenically unsaturated compound (B2).
In the present invention, when (B1) and (B2) are used in combination as essential components, high adhesive strength due to the effect of suppressing the release of the adhesive derived from the alicyclic structure-containing ethylenically unsaturated compound (B1), in particular. In particular, high cohesive force due to hydrogen bonding derived from the hydroxyl group-containing ethylenically unsaturated compound (B2) is exhibited in a well-balanced manner.
　脂環式構造含有エチレン性不飽和化合物（Ｂ１）としては、脂環式構造含有（メタ）アクリレート系化合物であることが好ましく、脂環式構造の炭素数としては、通常、炭素数４～２０であり、特に好ましくは６～１０であり、具体的には、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、２－メチルシクロヘキシル（メタ）アクリレート、トリシクロ［５．２．１．０２，６］デカン－８－イル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、２－ジシクロペンタニルオキシエチル（メタ）アクリレート、イソボロニル（メタ）アクリレート、４－ｔ－ブチルシクロヘキシル（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）アクリレート等が挙げられるが、これらの中でも、アクリル系樹脂（Ａ）との相溶性が優れる点で、シクロヘキシル（メタ）アクリレートが好ましく、特に好ましくは、シクロヘキシルアクリレートである。 The alicyclic structure-containing ethylenically unsaturated compound (B1) is preferably an alicyclic structure-containing (meth) acrylate compound, and the alicyclic structure usually has 4 to 20 carbon atoms. And particularly preferably 6 to 10. Specifically, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5 .2.1.02,6] decan-8-yl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, isobornyl (Meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate Examples include 1,4-cyclohexanedimethanol mono (meth) acrylate, and among these, cyclohexyl (meth) acrylate is preferable, and cyclohexyl is particularly preferable in terms of excellent compatibility with the acrylic resin (A). Acrylate.
　水酸基含有エチレン性不飽和化合物（Ｂ２）としては、水酸基含有（メタ）アクリレート系化合物であることが好ましく、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、５－ヒドロキシペンチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート、１０－ヒドロキシデシル（メタ）アクリレート、（４－ヒドロキシメチルシクロへキシル）メチル（メタ）アクリレート等の（メタ）アクリル酸ヒドロキシアルキルエステル、カプロラクトン変性２－ヒドロキシエチル（メタ）アクリレート等のカプロラクトン変性モノマー、２－アクリロイルオキシエチル－２－ヒドロキシエチルフタル酸、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－ヒドロキシエチル（メタ）アクリルアミド等の１級水酸基含有エチレン性不飽和化合物；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、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート等の２級水酸基含有エチレン性不飽和化合物；２，２－ジメチル－２－ヒドロキシエチル（メタ）アクリレート等の３級水酸基含有エチレン性不飽和化合物が挙げられる。
　これらの中でも、１級水酸基含有エチレン性不飽和化合物が好ましく、粘度およびアクリル系樹脂との相溶性に優れ、入手が容易である点で、特に好ましくは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－ヒドロキシエチル（メタ）アクリレートであり、更に好ましくは、４－ヒドロキシブチル（メタ）アクリレートである。 The hydroxyl group-containing ethylenically unsaturated compound (B2) is preferably a hydroxyl group-containing (meth) acrylate compound, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, (4-hydroxymethylcyclohexyl) ) Hydroxyalkyl esters of (meth) acrylic acid such as methyl (meth) acrylate, caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth) acrylate, 2-acryloyloxyethyl-2-hydro Primary hydroxyl group-containing ethylenically unsaturated compounds such as ethyl phthalate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide; 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2 Secondary hydroxyl group-containing ethylenically unsaturated compounds such as 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate; 2 And tertiary hydroxyl group-containing ethylenically unsaturated compounds such as 2-dimethyl-2-hydroxyethyl (meth) acrylate.
Among these, primary hydroxyl group-containing ethylenically unsaturated compounds are preferable, and 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like because they are excellent in viscosity and compatibility with acrylic resins and easily available. Hydroxypropyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate are preferable, and 4-hydroxybutyl (meth) acrylate is more preferable.
　単官能性不飽和化合物（Ｂ）としては、本発明の効果を損なわない範囲で、上記脂環式構造含有エチレン性不飽和化合物（Ｂ１）、水酸基含有エチレン性不飽和化合物（Ｂ２）以外のエチレン性不飽和基を１個有する不飽和化合物（Ｂ３）（以下、「単官能性不飽和化合物（Ｂ３）」と記すことがある。）を用いることが好ましいが、耐腐食性に優れる点で、酸性基を有する化合物は用いないことが好ましい。 The monofunctional unsaturated compound (B) is an ethylene other than the alicyclic structure-containing ethylenically unsaturated compound (B1) and the hydroxyl group-containing ethylenically unsaturated compound (B2) as long as the effects of the present invention are not impaired. It is preferable to use an unsaturated compound (B3) having one ionic unsaturated group (hereinafter sometimes referred to as “monofunctional unsaturated compound (B3)”), but in terms of excellent corrosion resistance, It is preferable not to use a compound having an acidic group.
　単官能性不飽和化合物（Ｂ３）としては、例えば、アルキル基の炭素数が１～３０の（メタ）アクリル酸アルキルエステルがあげられ、具体的には、エチル（メタ）アクリレート、ｎ－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、ｔｅｒｔ－ブチル（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、２－エチルヘキシル（メタ）アクリレート、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、メチル（メタ）アクリレート、等があげられる。中でも、好ましくはアルキル基の炭素数が２～２０、特に好ましくは４～１８、更に好ましくは４～１０の（メタ）アクリル酸アルキルエステルがあげられ、特には、２－エチルヘキシル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレートが好ましく用いられる。 Examples of the monofunctional unsaturated compound (B3) include (meth) acrylic acid alkyl esters having an alkyl group having 1 to 30 carbon atoms, and specifically include ethyl (meth) acrylate, n-propyl ( (Meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, 2-ethylhexyl (meth) Examples include acrylate, nonyl (meth) acrylate, n-decyl (meth) acrylate, iso-decyl (meth) acrylate, methyl (meth) acrylate, and the like. Among them, preferred are (meth) acrylic acid alkyl esters having an alkyl group having 2 to 20 carbon atoms, particularly preferably 4 to 18, more preferably 4 to 10, particularly 2-ethylhexyl (meth) acrylate, n-Butyl (meth) acrylate is preferably used.
　また、単官能性不飽和化合物（Ｂ３）としては、上記の他、グリシジル（メタ）アクリレート、アリルグリシジル（メタ）アクリレート等のグリシジル基含有不飽和モノマー；ｔ－ブチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート等のアミノ基含有モノマー；２－（アセトアセトキシ）エチル（メタ）アクリレート、アリルアセトアセテート等のアセトアセチル基含有モノマー；２－メトキシエチル（メタ）アクリレート、３－メトキシエチル（メタ）アクリレート、メトキシジエチレングリコール（メタ）アクリレート等のアルコキシ（ポリ）アルキレングリコールモノ（メタ）アクリレート類；Ｎ－アクリルアミドメチルトリメチルアンモニウムクロライド、アリルトリメチルアンモニウムクロライド、ジメチルアリルビニルケトン等のアリル化合物類；Ｎ－（メタ）アクリロイルオキシメチレンスクシンイミド、Ｎ－（メタ）アクリロイル－２－オキシジメチレンスクシンイミド、Ｎ－（メタ）アクリロイル－３－オキシトリメチレンスクシンイミド、Ｎ－（メタ）アクリロイル－４－オキシテトラメチレンスクシンイミド、Ｎ－（メタ）アクリロイル－５－オキシペンタメチレンスクシンイミド、Ｎ－（メタ）アクリロイル－６－オキシヘキサメチレンスクシンイミド等のスクシンイミド類；Ｎ－ビニルピロリドン、プロピオン酸ビニル、ステアリン酸ビニル、塩化ビニル、塩化ビニリデン、酢酸ビニル、スチレン等のビニル系モノマー等を用いてもよい。
　これら単官能性不飽和化合物（Ｂ３）の中から、1種を単独で、あるいは２種以上を併用して用いればよい。 In addition to the above, the monofunctional unsaturated compound (B3) includes glycidyl group-containing unsaturated monomers such as glycidyl (meth) acrylate and allyl glycidyl (meth) acrylate; t-butylaminoethyl (meth) acrylate, diethylamino Amino group-containing monomers such as ethyl (meth) acrylate and dimethylaminoethyl (meth) acrylate; acetoacetyl group-containing monomers such as 2- (acetoacetoxy) ethyl (meth) acrylate and allyl acetoacetate; 2-methoxyethyl (meth) Alkoxy (poly) alkylene glycol mono (meth) acrylates such as acrylate, 3-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate; N-acrylamidomethyltrimethylammonium chloride Allyl compounds such as id, allyltrimethylammonium chloride and dimethylallyl vinyl ketone; N- (meth) acryloyloxymethylenesuccinimide, N- (meth) acryloyl-2-oxydimethylenesuccinimide, N- (meth) acryloyl-3- Succinimides such as oxytrimethylene succinimide, N- (meth) acryloyl-4-oxytetramethylene succinimide, N- (meth) acryloyl-5-oxypentamethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide Vinyl monomers such as N-vinylpyrrolidone, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, vinyl acetate, and styrene may be used.
Of these monofunctional unsaturated compounds (B3), one kind may be used alone, or two or more kinds may be used in combination.
　単官能性不飽和化合物（Ｂ）全体に対する、脂環式構造含有エチレン性不飽和化合物（Ｂ１）の含有割合としては、好ましくは０．５～７０重量％、特に好ましくは１～６０重量％、更に好ましくは３～５０重量％、殊に好ましくは５～４０重量％である。脂環式構造含有エチレン性不飽和化合物（Ｂ１）の含有割合が高すぎても低すぎても粘着力が低下する傾向がある。 The content of the alicyclic structure-containing ethylenically unsaturated compound (B1) with respect to the whole monofunctional unsaturated compound (B) is preferably 0.5 to 70% by weight, particularly preferably 1 to 60% by weight, More preferably, it is 3 to 50% by weight, particularly preferably 5 to 40% by weight. If the content of the alicyclic structure-containing ethylenically unsaturated compound (B1) is too high or too low, the adhesive strength tends to decrease.
　単官能性不飽和化合物（Ｂ）全体に対する、水酸基含有エチレン性不飽和化合物（Ｂ２）の含有割合としては、好ましくは１～７０重量％、特に好ましくは３～６０重量％、更に好ましくは５～５０重量％、殊に好ましくは７～４０重量％である。水酸基含有エチレン性不飽和化合物（Ｂ２）の含有割合が高すぎると、凝集力が高くなりすぎる傾向があり、低すぎると耐久性が低下する傾向がある。 The content ratio of the hydroxyl group-containing ethylenically unsaturated compound (B2) to the monofunctional unsaturated compound (B) is preferably 1 to 70% by weight, particularly preferably 3 to 60% by weight, and more preferably 5 to 5%. 50% by weight, particularly preferably 7 to 40% by weight. If the content ratio of the hydroxyl group-containing ethylenically unsaturated compound (B2) is too high, the cohesive force tends to be too high, and if it is too low, the durability tends to decrease.
　単官能性不飽和化合物（Ｂ）全体に対する、脂環式構造含有エチレン性不飽和化合物（Ｂ１）および水酸基含有エチレン性不飽和化合物（Ｂ２）の合計量の含有割合としては、好ましくは１０～７５重量％、特に好ましくは２０～７０重量％、更に好ましくは２５～６５重量％、殊に好ましくは３０～６０重量％である。脂環式構造含有エチレン性不飽和化合物（Ｂ１）および水酸基含有エチレン性不飽和化合物（Ｂ２）の合計量の含有割合が高すぎると、凝集力が高くなりすぎる傾向があり、低すぎると本発明の効果を充分に得られない傾向がある。 The total content of the alicyclic structure-containing ethylenically unsaturated compound (B1) and the hydroxyl group-containing ethylenically unsaturated compound (B2) with respect to the entire monofunctional unsaturated compound (B) is preferably 10 to 75. % By weight, particularly preferably 20 to 70% by weight, more preferably 25 to 65% by weight, particularly preferably 30 to 60% by weight. When the content ratio of the total amount of the alicyclic structure-containing ethylenically unsaturated compound (B1) and the hydroxyl group-containing ethylenically unsaturated compound (B2) is too high, the cohesive force tends to be too high. There is a tendency that sufficient effects cannot be obtained.
　脂環式構造含有エチレン性不飽和化合物（Ｂ１）と水酸基含有エチレン性不飽和化合物（Ｂ２）の含有割合（重量比）は、（Ｂ１）：（Ｂ２）＝１０：９０～９０：１０であることが好ましく、特に好ましくは（Ｂ１）：（Ｂ２）＝２０：８０～８０：２０、更に好ましくは（Ｂ１）：（Ｂ２）＝３０：７０～７０：３０である。水酸基含有エチレン性不飽和化合物（Ｂ２）に対する脂環式構造含有エチレン性不飽和化合物（Ｂ１）の含有割合が高すぎると凝集力が低下しやすい傾向があり、低すぎると粘着力が低下しやすい傾向がある。 The content ratio (weight ratio) of the alicyclic structure-containing ethylenically unsaturated compound (B1) and the hydroxyl group-containing ethylenically unsaturated compound (B2) is (B1) :( B2) = 10: 90 to 90:10. Preferably, (B1) :( B2) = 20: 80 to 80:20, more preferably (B1) :( B2) = 30: 70 to 70:30. If the content ratio of the alicyclic structure-containing ethylenically unsaturated compound (B1) to the hydroxyl group-containing ethylenically unsaturated compound (B2) is too high, the cohesive force tends to decrease, and if it is too low, the adhesive strength tends to decrease. Tend.
　単官能性不飽和化合物（Ｂ）の含有量は、アクリル系樹脂（Ａ）と単官能性不飽和化合物（Ｂ）の合計１００重量部に対して、５０～９５重量部であることが好ましく、特に好ましくは５５～９３重量部、更に好ましくは６０～９０重量部である。
　単官能性不飽和化合物（Ｂ）の含有量が多すぎると、粘度が低すぎて塗工しにくくなる傾向があり、低すぎると粘度が高く塗工しにくくなる傾向がある。 The content of the monofunctional unsaturated compound (B) is preferably 50 to 95 parts by weight with respect to 100 parts by weight in total of the acrylic resin (A) and the monofunctional unsaturated compound (B). The amount is particularly preferably 55 to 93 parts by weight, more preferably 60 to 90 parts by weight.
When there is too much content of a monofunctional unsaturated compound (B), there exists a tendency for a viscosity to be too low and to become difficult to apply, and when too low, there exists a tendency for a viscosity to become high and to become difficult to apply.
　エチレン性不飽和基を２個以上含有するエチレン性不飽和化合物（Ｃ）（以下、「多官能性不飽和化合物（Ｃ）」と記すことがある。）としては、例えば、２官能の（メタ）アクリレート系モノマー、３官能以上の（メタ）アクリレート系モノマーや、ウレタン（メタ）アクリレート系化合物、エポキシ（メタ）アクリレート系化合物、ポリエステル（メタ）アクリレート系化合物を用いることができる。また、これらは単独でもしくは２種以上併せて用いることができる。 Examples of the ethylenically unsaturated compound (C) containing two or more ethylenically unsaturated groups (hereinafter sometimes referred to as “polyfunctional unsaturated compound (C)”) include bifunctional (meta ) Acrylate monomers, tri- or higher functional (meth) acrylate monomers, urethane (meth) acrylate compounds, epoxy (meth) acrylate compounds, and polyester (meth) acrylate compounds can be used. Moreover, these can be used individually or in combination of 2 or more types.
　２官能の（メタ）アクリレート系モノマーとしては、（メタ）アクリロイル基を２つ含有するモノマーであればよく、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エチレンオキサイド変性ビスフェノールＡ型ジ（メタ）アクリレート、プロピレンオキサイド変性ビスフェノールＡ型ジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールエチレンオキサイド変性ジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、エチレングリコールジグリシジルエーテルジ（メタ）アクリレート、ジエチレングリコールジグリシジルエーテルジ（メタ）アクリレート、フタル酸ジグリシジルエステルジ（メタ）アクリレート、ヒドロキシピバリン酸変性ネオペンチルグリコールジ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性ジアクリレート、２－（メタ）アクリロイルオキシエチルアシッドホスフェートジエステル等があげられる。 The bifunctional (meth) acrylate monomer may be any monomer containing two (meth) acryloyl groups. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, 1,6-hexa Diol di (meth) acrylate, 1,6-hexanediol ethylene oxide modified di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl Ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified diacrylate, 2- (meth) acryloyloxyethyl acid phosphate diester Etc.
　３官能以上の（メタ）アクリレート系モノマーとしては、（メタ）アクリロイル基を３つ以上含有するモノマーであればよく、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリ（メタ）アクリロイルオキシエトキシトリメチロールプロパン、グリセリンポリグリシジルエーテルポリ（メタ）アクリレート、イソシアヌル酸エチレンオキサイド変性トリ（メタ）アクリレート、エチレンオキサイド変性ジペンタエリスリトールペンタ（メタ）アクリレート、エチレンオキサイド変性ジペンタエリスリトールヘキサ（メタ）アクリレート、エチレンオキサイド変性ペンタエリスリトールトリ（メタ）アクリレート、エチレンオキサイド変性ペンタエリスリトールテトラ（メタ）アクリレート、コハク酸変性ペンタエリスリトールトリ（メタ）アクリレート等があげられる。 The trifunctional or higher functional (meth) acrylate monomer may be any monomer containing at least three (meth) acryloyl groups, such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, penta Erythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxy Trimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, ethylene oxide modified Dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, succinic acid modified pentaerythritol tri ( And (meth) acrylate.
　ウレタン（メタ）アクリレート系化合物としては、分子内にウレタン結合を有する（メタ）アクリレート系化合物であり、水酸基を含有する（メタ）アクリル系化合物と多価イソシアネート系化合物（必要に応じて、ポリオール系化合物）を、公知一般の方法により反応させて得られるものを用いればよく、その重量平均分子量としては、通常３００～４０００のものを用いればよい。 The urethane (meth) acrylate compound is a (meth) acrylate compound having a urethane bond in the molecule, a (meth) acrylic compound containing a hydroxyl group and a polyvalent isocyanate compound (if necessary, a polyol compound) What is necessary is just to use what is obtained by making a compound) react by a well-known general method, and what is usually used is 300-4000 as the weight average molecular weight.
　多官能性不飽和化合物（Ｃ）の含有量としては、アクリル系樹脂（Ａ）と単官能性不飽和化合物（Ｂ）の合計１００重量部に対して、０．００５～１５重量部であることが好ましく、特に好ましくは０．０１～１３重量部、更に好ましくは０．１～１０重量部である。
　多官能性不飽和化合物（Ｃ）の含有量が多すぎると、粘着力が低下しやすくなる傾向があり、少なすぎると凝集力が低下しやすくなる傾向がある。 The content of the polyfunctional unsaturated compound (C) is 0.005 to 15 parts by weight with respect to 100 parts by weight in total of the acrylic resin (A) and the monofunctional unsaturated compound (B). It is preferably 0.01 to 13 parts by weight, more preferably 0.1 to 10 parts by weight.
When there is too much content of a polyfunctional unsaturated compound (C), there exists a tendency for adhesive force to fall easily, and when too small, there exists a tendency for cohesion force to fall easily.
　光重合開始剤（Ｄ）としては、光等の活性エネルギー線の作用によりラジカルを発生するものであれば特に限定されず、分子内自己開裂型の光重合開始剤や水素引抜型の光重合開始剤が用いられる。 The photopolymerization initiator (D) is not particularly limited as long as it generates radicals by the action of active energy rays such as light. Intramolecular self-cleavage type photopolymerization initiator and hydrogen abstraction type photopolymerization start An agent is used.
　分子内自己開裂型の光重合開始剤としては、例えば、４－フェノキシジクロロアセトフェノン、４－ｔ－ブチル－ジクロロアセトフェノン、ジエトキシアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－（４－イソプロピレンフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、１－（４－ドデシルフェニル）－２－ヒドロキシ－２－メチルプロパン－１－オン、４－（２－ヒドロキシエトキシ）－フェニル（２－ヒドロキシ－２－プロピル）ケトン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－１－〔４－（メチルチオ）フェニル〕－２－モルホリノプロパン－１－オン、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインイソブチルエーテル、ベンジルジメチルケタール、α－アシロキシムエステル、アシルホスフィンオキサイド、メチルフェニルグリオキシレート、４－（２－ヒドロキシエトキシ）フェニル－（２－ヒドロキシ－２－プロピル）ケトン、４－ベンゾイル－４'－メチルジフェニルサルファイド等があげられ、中でも２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトンが好適である。 Examples of the intramolecular self-cleaving photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- (4-Isopropylenephenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2 -Hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, benzoin, Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Ter, benzoin isobutyl ether, benzyldimethyl ketal, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 4-benzoyl -4'-methyldiphenyl sulfide and the like. Among them, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexyl phenyl ketone are preferable.
　また、水素引抜型の光重合開始剤としては、例えば、ベンゾフェノン、４－フェニルベンゾフェノン、ヒドロキシベンゾフェノン、３，３'－ジメチル－４－メトキシベンゾフェノン、２，４，６－トリメチルベンゾフェノン、４－メチルベンゾフェノン、チオキサンソン、２－クロルチオキサンソン、２－メチルチオキサンソン、２，４－ジメチルチオキサンソン、イソプロピルチオキサンソン、カンファーキノン、ジベンゾスベロン、２－エチルアンスラキノン、３，３'，４，４'－テトラ（ｔ－ブチルパーオキシカルボニル）ベンゾフェノン、ベンジル、９，１０－フェナンスレンキノン等があげられ、中でもベンゾフェノン、メチルベンゾフェノン、２，４，６－トリメチルベンゾフェノンが好適である。これら光重合開始剤（Ｄ）は１種又は２種以上併用して用いられる。 Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, 4-phenylbenzophenone, hydroxybenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone. Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 3,3 ′, 4, Examples thereof include 4′-tetra (t-butylperoxycarbonyl) benzophenone, benzyl, 9,10-phenanthrenequinone, and among them, benzophenone, methylbenzophenone, and 2,4,6-trimethylbenzophenone are preferable. These photopolymerization initiators (D) are used alone or in combination of two or more.
　さらに、上述の光重合開始剤以外に、トリアジン系光重合開始剤を用いることにより、硬化後に良好な粘着物性を得るために必要な積算光量を少なくすることが可能となる。 Furthermore, by using a triazine photopolymerization initiator in addition to the above-mentioned photopolymerization initiator, it is possible to reduce the integrated light amount necessary for obtaining good adhesive properties after curing.
　トリアジン系光重合開始剤としては、例えば、下記の一般式（ａ）で表される２，４，６－三置換－ｓ－トリアジンがあげられる。 Examples of the triazine photopolymerization initiator include 2,4,6-trisubstituted-s-triazine represented by the following general formula (a).
Figure JPOXMLDOC01-appb-C000002
 〔上記式（ａ）において、Ｒ１、Ｒ２、およびＲ３は、それぞれアルキル基、置換アルキル基、アリール基、置換アリール基、アルケニル基またはアルコキシ基であり、互いに同じであっても異なっていてもよいが、少なくとも一つはモノハロゲン置換メチル基、ジハロゲン置換メチル基またはトリハロゲン置換メチル基である。〕
Figure JPOXMLDOC01-appb-C000002
 [In the above formula (a), R 1 , R 2 and R 3 are each an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group or an alkoxy group, and they may be the same or different from each other. However, at least one is a monohalogen-substituted methyl group, a dihalogen-substituted methyl group, or a trihalogen-substituted methyl group. ]
　上記アルキル基としては、例えば、炭素数１～１０のアルキル基、具体的には、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｎ－ヘキシル基等があげられる。また、上記置換アルキル基としては、ハロゲン原子により置換された炭素数１～１０のアルキル基、具体的には、トリクロロメチル基、トリブロモメチル基、α，α，β－トリクロロエチル基等があげられる。 Examples of the alkyl group include an alkyl group having 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-hexyl group, and the like. It is done. Examples of the substituted alkyl group include an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, specifically, a trichloromethyl group, a tribromomethyl group, an α, α, β-trichloroethyl group, and the like. It is done.
　そして、上記アリール基および置換アリール基としては、例えば、炭素数６～２０のもの、具体的には、フェニル基、ｐ－メトキシフェニル基、ｐ－メチルチオフェニル基、ｐ－クロロフェニル基、４－ビフェニリル基、ナフチル基、４－メトキシ－１－ナフチル基等があげられる。 Examples of the aryl group and substituted aryl group include those having 6 to 20 carbon atoms, such as a phenyl group, a p-methoxyphenyl group, a p-methylthiophenyl group, a p-chlorophenyl group, and 4-biphenylyl. Group, naphthyl group, 4-methoxy-1-naphthyl group and the like.
　また、上記アルケニル基としては、例えば、ビニル基、アリル基、２－フェニルエテニル基等の炭素数２～１２のものがあげられる。さらに、上記アルコキシ基としては、例えば、メトキシ基、エトキシ基、ブトキシ基等の炭素数１～１０のものがあげられる。 Examples of the alkenyl group include those having 2 to 12 carbon atoms such as a vinyl group, an allyl group, and a 2-phenylethenyl group. Furthermore, examples of the alkoxy group include those having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group.
　そして、上記モノハロゲン置換メチル基、ジハロゲン置換メチル基またはトリハロゲン置換メチル基としては、クロロメチル基、ブロモメチル基、ヨードメチル基、ジクロロメチル基、ジブロモメチル基、ジヨードメチル基、トリクロロメチル基、トリブロモメチル基、トリヨードメチル基があげられる。なかでも、塩素原子が置換したトリクロロメチル基が好適である。 The monohalogen-substituted methyl group, dihalogen-substituted methyl group or trihalogen-substituted methyl group includes chloromethyl group, bromomethyl group, iodomethyl group, dichloromethyl group, dibromomethyl group, diiodomethyl group, trichloromethyl group, tribromomethyl. Group and triiodomethyl group. Of these, a trichloromethyl group substituted with a chlorine atom is preferred.
　このような一般式（ａ）で表される２，４，６－三置換－ｓ－トリアジンは、例えば、Journal of American Chemical Society 第７２巻第３２５７～３５２８頁（１９５０年）、Journal of American Chemical Society 第７４巻第５６３３～５６３６頁（１９５２年）、Juatus Lieblgs Annalen der Chemie 第５７７巻第７７～９５頁（１９５２年）に記載された方法に従い合成することができる。 Such 2,4,6-trisubstituted-s-triazines represented by general formula (a) are, for example, JournalJof American Chemical Society Vol. 72, 3257-3528 (1950) It can be synthesized according to the methods described in Society ７４ 74, 5633-5636 (1952), Juatus Lieblgs Annalen der Chemie 577, 77-95 (1952).
　上記一般式（ａ）で表される２，４，６－三置換－ｓ－トリアジンとしては、具体的には、２，４，６－トリス（トリクロロメチル）－ｓ－トリアジン、２，４，６－トリス（トリブロモメチル）－ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－メチル－ｓ－トリアジン、２，４－ビス（トリブロモメチル）－６－メチル－ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－（ｐ－トリル）－ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－ｎ－プロピル－ｓ－トリアジン、２－（α，α，β－トリクロロエチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２，４，６－トリス（ジクロロメチル）－ｓ－トリアジン、２，４，６－トリス（ジブロモメチル）－ｓ－トリアジン、２，４，６－トリス（ブロモメチル）－ｓ－トリアジン、２，４，６－トリス（クロロメチル）－ｓ－トリアジン等の脂肪族系置換基のみを有する２，４，６－三置換－ｓ－トリアジン系光重合開始剤、２，４－ビス（トリクロロメチル）－６－フェニル－ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－（ｐ－メトキシフェニル）－ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－（ｐ－メチルチオフェニル）－ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－（ｐ－クロロフェニル）－ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－（２’，４’－ジクロロフェニル）－ｓ－トリアジン、２－（ｐ－ブロモフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２，４－ビス（トリブロモメチル）－６－フェニル－ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－スチリル－ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－［２－（ｐ－メトキシフェニル）エテニル］－ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－［２－（ｏ－メトキシフェニル）エテニル］－ｓ－トリアジン、２－［２－（ｐ－ブトキシフェニル）エテニル］－－ビス（トリクロロメチル）－ｓ－トリアジン、２－［２－（３，４－ジメトキシフェニル）エテニル］－２，４－ビス（トリクロロメチル）－ｓ－トリアジン、２－［２－（３，４，５－トリメトキシフェニル）エテニル］－２，４－ビス（トリクロロメチル）－ｓ－トリアジン、２－（１－ナフチル）－２，４－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－ビフェニリル）－２，４－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４′－メトキシ－１′－ナフチル）－２，４－ビス（トリクロロメチル）－ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－（ｐ－メトキシナフチル）－ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－（ピペロニル）－ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－（ｐ－メトキシスチリル）－ｓ－トリアジン等の芳香族系置換基を有する２，４，６－三置換－ｓ－トリアジン系光重合開始剤等をあげることができる。
　これらは単独でもしくは２種以上を併せて用いられる。 Specific examples of the 2,4,6-trisubstituted-s-triazine represented by the general formula (a) include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6 6-tris (tribromomethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-methyl-s-triazine, 2,4-bis (tribromomethyl) -6-methyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-tolyl) -s-triazine, 2,4-bis (trichloromethyl) -6-n-propyl-s-triazine, 2- (α, α, β -Trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine 2,4,6-tri 2,4,6-trisubstituted-s-triazine photoinitiators having only aliphatic substituents such as (bromomethyl) -s-triazine and 2,4,6-tris (chloromethyl) -s-triazine 2,4-bis (trichloromethyl) -6-phenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methoxyphenyl) -s-triazine, 2,4-bis (trichloromethyl) ) -6- (p-methylthiophenyl) -s-triazine, 2,4-bis (trichloromethyl) -6- (p-chlorophenyl) -s-triazine, 2,4-bis (trichloromethyl) -6- ( 2 ', 4'-dichlorophenyl) -s-triazine, 2- (p-bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (tribromomethyl)- 6-phenyl-s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2,4-bis (trichloromethyl) -6- [2- (p-methoxyphenyl) ethenyl]- s-triazine, 2,4-bis (trichloromethyl) -6- [2- (o-methoxyphenyl) ethenyl] -s-triazine, 2- [2- (p-butoxyphenyl) ethenyl] -bis (trichloro Methyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -2,4-bis (trichloromethyl) -s-triazine, 2- [2- (3,4,5-tri Methoxyphenyl) ethenyl] -2,4-bis (trichloromethyl) -s-triazine, 2- (1-naphthyl) -2,4-bis (trichloromethyl) -s-triazine, 2- (4 Biphenylyl) -2,4-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy-1'-naphthyl) -2,4-bis (trichloromethyl) -s-triazine, 2,4-bis (Trichloromethyl) -6- (p-methoxynaphthyl) -s-triazine, 2,4-bis (trichloromethyl) -6- (piperonyl) -s-triazine, 2,4-bis (trichloromethyl) -6- Examples thereof include 2,4,6-trisubstituted-s-triazine photopolymerization initiators having an aromatic substituent such as (p-methoxystyryl) -s-triazine.
These may be used alone or in combination of two or more.
　これらの中でも、上記トリアジン系光重合開始剤として、芳香族系置換基を有する２，４，６－三置換－ｓ－トリアジン系光重合開始剤を用いることが好ましく、更には塗膜の黄変が少ない、相溶性がよいという点から、２，４－ビス（トリクロロメチル）－６－（ｐ－メトキシフェニル）－ｓ－トリアジンを用いることが特に好ましい。 Among these, it is preferable to use a 2,4,6-trisubstituted-s-triazine photopolymerization initiator having an aromatic substituent as the triazine photopolymerization initiator, and further the yellowing of the coating film. It is particularly preferable to use 2,4-bis (trichloromethyl) -6- (p-methoxyphenyl) -s-triazine from the viewpoint of low compatibility and good compatibility.
　更に必要に応じて、光重合開始剤（Ｄ）の助剤として、例えば、トリエタノールアミン、トリイソプロパノールアミン、４，４'－ジメチルアミノベンゾフェノン（ミヒラーケトン）、４，４'－ジエチルアミノベンゾフェノン、２－ジメチルアミノエチル安息香酸、４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸（ｎ－ブトキシ）エチル、４－ジメチルアミノ安息香酸イソアミル、４－ジメチルアミノ安息香酸２－エチルヘキシル、２，４－ジエチルチオキサンソン、２，４－ジイソプロピルチオキサンソン等を併用することも可能である。 Further, if necessary, as an auxiliary of the photopolymerization initiator (D), for example, triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2- Dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethyl It is also possible to use thioxanthone, 2,4-diisopropylthioxanthone, etc. in combination.
　光重合開始剤（Ｄ）の含有量は、単官能性不飽和化合物（Ｂ）と多官能性不飽和化合物（Ｃ）との合計１００重量部に対して、０．１～２０重量部であることが好ましく、特に好ましくは０．５～１５重量部、更に好ましくは１～１０重量部である。
　光重合開始剤（Ｄ）の含有量が少なすぎると、紫外線等の活性エネルギー線照射による重合にばらつきができやすくなる傾向があり、多すぎると、一定以上の添加効果が得られず不経済となる傾向がある。 The content of the photopolymerization initiator (D) is 0.1 to 20 parts by weight with respect to 100 parts by weight in total of the monofunctional unsaturated compound (B) and the polyfunctional unsaturated compound (C). It is preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight.
If the content of the photopolymerization initiator (D) is too small, there is a tendency that the polymerization due to irradiation with active energy rays such as ultraviolet rays tends to be uneven. Tend to be.
　また、光重合開始剤（Ｄ）として上記トリアジン系光重合開始剤を単独で用いる場合は、単官能性不飽和化合物（Ｂ）と多官能性不飽和化合物（Ｃ）との合計１００重量部に対して、トリアジン系光重合開始剤を０．０１～０．５重量部含有させることが好ましく、特に好ましくは０．０５～０．４５重量部、更に好ましくは０．１～０．４重量部、殊に好ましくは０．１５～０．３５重量部である。 When the triazine photopolymerization initiator is used alone as the photopolymerization initiator (D), the total amount of the monofunctional unsaturated compound (B) and the polyfunctional unsaturated compound (C) is 100 parts by weight. On the other hand, the triazine photopolymerization initiator is preferably contained in an amount of 0.01 to 0.5 parts by weight, particularly preferably 0.05 to 0.45 parts by weight, more preferably 0.1 to 0.4 parts by weight. Particularly preferred is 0.15 to 0.35 parts by weight.
　かくして、アクリル系樹脂（Ａ）、単官能性不飽和化合物（Ｂ）、多官能性不飽和化合物（Ｃ）、および光重合開始剤（Ｄ）を含有してなる本発明の粘着剤組成物が得られるが、本発明の効果を損なわない範囲において、イソシアネート系、エポキシ系、金属塩、金属アルコシド、アルデヒド系化合物、非アミノ樹脂系アミノ化合物、尿素系、金属キレート系、メラミン系、アジリジン系等、一般的に使用される架橋剤、他の粘着剤、ウレタン樹脂、ロジン、ロジンエステル、水添ロジンエステル、フェノール樹脂、芳香族変性テルペン樹脂、脂肪族系石油樹脂、脂環族系石油樹脂、スチレン系樹脂、キシレン系樹脂等の粘着付与剤、公知の添加剤や紫外線あるいは放射線照射により呈色あるいは変色を起こすような化合物を配合することができる。また、上記配合剤の他にも、粘着剤組成物の構成成分の製造原料等に含まれる不純物等が少量含有されたものであってもよい。これら配合剤の配合量は所望する物性が得られるように適宜設定すればよい。 Thus, the pressure-sensitive adhesive composition of the present invention comprising the acrylic resin (A), the monofunctional unsaturated compound (B), the polyfunctional unsaturated compound (C), and the photopolymerization initiator (D). In the range that does not impair the effects of the present invention, isocyanate-based, epoxy-based, metal salt, metal alcoside, aldehyde-based compound, non-amino resin-based amino compound, urea-based, metal chelate-based, melamine-based, aziridine-based, etc. , Commonly used crosslinking agents, other adhesives, urethane resins, rosins, rosin esters, hydrogenated rosin esters, phenol resins, aromatic modified terpene resins, aliphatic petroleum resins, alicyclic petroleum resins, Mixing tackifiers such as styrene resins and xylene resins, known additives and compounds that cause coloration or discoloration upon irradiation with ultraviolet rays or radiation It can be. Further, in addition to the above-mentioned compounding agent, a small amount of impurities and the like contained in the raw materials for producing the constituent components of the pressure-sensitive adhesive composition may be contained. What is necessary is just to set suitably the compounding quantity of these compounding agents so that the desired physical property may be obtained.
　上記粘着剤組成物は、実質的に酸を含まないことが耐腐食性に優れる点で好ましく、実質的に酸を含まないとは、粘着剤組成物の酸価が、通常１ｍｇＫＯＨ／ｇ以下、好ましくは０．５ｍｇＫＯＨ／ｇ以下、特に好ましくは０であることを意味する。 The pressure-sensitive adhesive composition is preferably substantially free of acid from the viewpoint of excellent corrosion resistance, and substantially free of acid means that the acid value of the pressure-sensitive adhesive composition is usually 1 mgKOH / g or less, It means preferably 0.5 mgKOH / g or less, particularly preferably 0.
　本発明で得られる粘着剤組成物は、水、水性溶媒あるいは有機溶媒等の溶剤を実質的に含有しないことが好ましく、アクリル系樹脂（Ａ）、多官能性不飽和化合物（Ｃ）、光重合開始剤（Ｄ）、さらに必要に応じ配合される他の成分は、単官能性不飽和化合物（Ｂ）中に溶解もしくは均一に分散した状態となる。かかる粘着剤組成物は、アクリル系樹脂（Ａ）、単官能性不飽和化合物（Ｂ）、多官能性不飽和化合物（Ｃ）、光重合開始剤（Ｄ）、更に必要に応じて配合される他の成分を、常温あるいは、６０℃程度まで加温してから、混合することにより調製することができる。 The pressure-sensitive adhesive composition obtained in the present invention preferably contains substantially no solvent such as water, an aqueous solvent or an organic solvent, and is an acrylic resin (A), a polyfunctional unsaturated compound (C), photopolymerization. The initiator (D) and other components added as necessary are dissolved or uniformly dispersed in the monofunctional unsaturated compound (B). Such a pressure-sensitive adhesive composition is blended as necessary with acrylic resin (A), monofunctional unsaturated compound (B), polyfunctional unsaturated compound (C), photopolymerization initiator (D). Other components can be prepared by heating to room temperature or about 60 ° C. and then mixing.
　かくして、本発明の粘着剤組成物が得られるのであるが、かかる粘着剤組成物が、活性エネルギー線照射により硬化されて本発明の粘着剤が得られるのである。 Thus, although the pressure-sensitive adhesive composition of the present invention is obtained, the pressure-sensitive adhesive composition is cured by irradiation with active energy rays to obtain the pressure-sensitive adhesive of the present invention.
　活性エネルギー線としては、遠紫外線、紫外線、近紫外線、赤外線等の光線、Ｘ線、γ線等の電磁波の他、電子線、プロトン線、中性子線等が利用できるが、硬化速度、照射装置の入手のし易さ、価格等から紫外線照射による硬化が有利である。 As the active energy rays, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and γ rays, electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet irradiation is advantageous because of its availability and price.
　紫外線照射には、１５０～４５０ｎｍ波長域の光を発する高圧水銀ランプ、超高圧水銀灯、カーボンアーク灯、メタルハライドランプ、キセノンランプ、ケミカルランプ、無電極放電ランプ等を用いることができる。 For UV irradiation, a high-pressure mercury lamp, ultrahigh-pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp, or the like that emits light in the wavelength range of 150 to 450 nm can be used.
　活性エネルギー線の照射量としては、５００ｍＪ／ｃｍ2以上であることが好ましく、更には１０００ｍＪ／ｃｍ2以上、特には１５００ｍＪ／ｃｍ2以上であることが好ましい。かかる照射量が少なすぎると活性エネルギー線照射による重合にばらつきができやすくなる傾向がある。なお、照射量の上限は通常１００００ｍＪ／ｃｍ2であり、照射量が多すぎると装置及びコストの関係不経済となる傾向がある。 The irradiation amount of the active energy ray, is preferably 500 mJ / cm 2 or more, further 1000 mJ / cm 2 or more, and particularly preferably at 1500 mJ / cm 2 or more. If the amount of irradiation is too small, there is a tendency that the polymerization by irradiation with active energy rays tends to vary. The upper limit of the irradiation amount is usually 10,000 mJ / cm 2 , and if the irradiation amount is too large, the relationship between the apparatus and the cost tends to be uneconomical.
　本発明の粘着剤は、粘着シートとして用いることが好適である。
　粘着シートの製造方法としては、［Ｉ］粘着剤組成物を基材上に塗布し、活性エネルギー線を照射して粘着剤層とした後、離型シートを貼合する方法、［ＩＩ］粘着剤組成物を基材上に塗布し、離型シートを貼合した後、活性エネルギー線照射を行ない粘着剤層を形成する方法、［ＩＩＩ］粘着剤組成物を離型シート上に塗布し、活性エネルギー線を照射して粘着剤層とした後、基材もしくは離型シートを貼合する方法、［ＩＶ］粘着剤組成物を離型シート上に塗布し、基材もしくは離型シートを貼合した後、活性エネルギー線照射を行ない粘着剤層を形成する方法等が挙げられる。 The pressure-sensitive adhesive of the present invention is preferably used as a pressure-sensitive adhesive sheet.
As a method for producing the pressure-sensitive adhesive sheet, [I] a method in which a pressure-sensitive adhesive composition is applied on a substrate, irradiated with active energy rays to form a pressure-sensitive adhesive layer, and then a release sheet is bonded; [II] pressure-sensitive adhesive A method of applying an adhesive composition on a substrate and pasting a release sheet, and then irradiating active energy rays to form an adhesive layer, [III] applying an adhesive composition on the release sheet, A method of pasting a base material or a release sheet after irradiating an active energy ray to form an adhesive layer, [IV] Applying an adhesive composition on the release sheet, and pasting the base material or the release sheet After combining, there is a method of forming an adhesive layer by irradiating with active energy rays.
　なお、活性エネルギー線照射後に基材または離型シートを貼合する場合は、活性エネルギー線照射時の酸素による重合阻害要因を排除するため、不活性ガス雰囲気下において活性エネルギー線を照射することがより好ましいが、酸素による重合阻害要因を考慮して照射条件を調整し物性のバランスをとることも可能である。 In addition, when pasting a base material or a release sheet after irradiation with active energy rays, it is possible to irradiate active energy rays in an inert gas atmosphere in order to eliminate polymerization inhibition factors due to oxygen during irradiation with active energy rays. Although more preferable, it is possible to balance the physical properties by adjusting the irradiation conditions in consideration of the polymerization inhibition factor due to oxygen.
　基材としては、例えば、アルミニウム、銅、鉄等の金属箔；ポリエチレンナフタート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンテレフタレート／イソフタレート共重合体等のポリエステル系樹脂；ポリエチレン、ポリプロピレン、ポリメチルペンテン等のポリオレフィン系樹脂；ポリフッ化ビニル、ポリフッ化ビニリデン、ポリフッ化エチレン等のポリフッ化エチレン樹脂；ナイロン６、ナイロン６，６等のポリアミド；ポリ塩化ビニル、ポリ塩化ビニル／酢酸ビニル共重合体、エチレン－酢酸ビニル共重合体、エチレン－ビニルアルコール共重合体、ポリビニルアルコール、ビニロン等のビニル重合体；三酢酸セルロース、セロファン等のセルロース系樹脂；ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリアクリル酸エチル、ポリアクリル酸ブチル等のアクリル系樹脂；ポリスチレン、ポリカーボネート、ポリアリレート、ポリイミド等の合成樹脂フィルムまたはシート、上質紙、グラシン紙等の紙、硝子繊維、天然繊維、合成繊維等から選択される単層体または複層体があげられる。また、基材シートとして不織布やフォーム基材などを用いて、両面テープなどの用途に使用することも可能である。 Examples of the base material include metal foils such as aluminum, copper, and iron; polyester resins such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer; polyethylene, polypropylene, polymethylpentene, etc. Polyolefin resins such as polyvinyl fluoride, polyvinylidene fluoride, and polyfluorinated ethylene; polyamides such as nylon 6 and nylon 6, 6; polyvinyl chloride, polyvinyl chloride / vinyl acetate copolymer, ethylene Vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, vinyl polymers such as polyvinyl alcohol and vinylon; cellulose resins such as cellulose triacetate and cellophane; polymethyl methacrylate, polymethacryl Acrylic resins such as ethyl, polyethyl acrylate, and polybutyl acrylate; synthetic resin films or sheets such as polystyrene, polycarbonate, polyarylate, polyimide, paper such as fine paper, glassine paper, glass fibers, natural fibers, synthetic fibers A monolayer or a multi-layer selected from the above. Moreover, it can also be used for uses, such as a double-sided tape, using a nonwoven fabric, a foam base material, etc. as a base material sheet.
　上記基材の厚さは、特に限定されないが、通常５００μｍ以下、好ましくは５～３００μｍ、更に好ましくは１０～２００μｍであればよい。 The thickness of the substrate is not particularly limited, but is usually 500 μm or less, preferably 5 to 300 μm, more preferably 10 to 200 μm.
　離型シートとしては、例えば、上記支持基材で例示した各種合成樹脂シート、紙、布、不織布等に離型処理したものを使用することができる。 As the release sheet, it is possible to use, for example, various synthetic resin sheets exemplified in the support base material, paper, cloth, non-woven fabric, and the like subjected to release treatment.
　粘着剤組成物の塗工方法としては、一般的な塗工方法であれば特に限定されることなく、例えば、ロールコーティング、ダイコーティング、グラビアコーティング、コンマコーティング、スクリーン印刷等の方法があげられる。 The coating method of the pressure-sensitive adhesive composition is not particularly limited as long as it is a general coating method, and examples thereof include roll coating, die coating, gravure coating, comma coating, and screen printing.
　また、活性エネルギー線照射後に基材上に形成される上記粘着剤層の厚みは、用途に応じて適宜設定されるものであるが、通常５～３００μｍであり、好ましくは１０～２５０μｍである。粘着剤層の厚みが薄すぎると、貼着物性が安定しにくい傾向があり、厚すぎると糊残りを起こしやすくなる傾向がある。 The thickness of the pressure-sensitive adhesive layer formed on the substrate after irradiation with active energy rays is appropriately set depending on the application, but is usually 5 to 300 μm, preferably 10 to 250 μm. If the thickness of the pressure-sensitive adhesive layer is too thin, the adhesive physical properties tend to be difficult to stabilize, and if it is too thick, adhesive residue tends to occur.
　本発明における粘着シートの利用に際し、被着体の種類として、例えば、各種金属面を有する物品；ポリエチレンナフタート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンテレフタレート／イソフタレート共重合体等のポリエステル系樹脂；ポリエチレン、ポリプロピレン、ポリメチルペンテン等のポリオレフィン系樹脂；ポリフッ化ビニル、ポリフッ化ビニリデン、ポリフッ化エチレン等のポリフッ化エチレン樹脂；ナイロン６、ナイロン６，６等のポリアミド；ポリ塩化ビニル、ポリ塩化ビニル／酢酸ビニル共重合体、エチレン－酢酸ビニル共重合体、エチレン－ビニルアルコール共重合体、ポリビニルアルコール、ビニロン等のビニル重合体；三酢酸セルロース、セロファン等のセルロース系樹脂；ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリアクリル酸エチル、ポリアクリル酸ブチル等のアクリル系樹脂；ポリスチレン、ポリカーボネート、ポリアリレート、ポリイミド等の合成樹脂フィルム、シートまたは板等があげられる。 In the use of the pressure-sensitive adhesive sheet in the present invention, as the type of adherend, for example, articles having various metal surfaces; polyester resins such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate copolymer; Polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; Polyfluorinated ethylene resins such as polyvinyl fluoride, polyvinylidene fluoride, and polyfluorinated ethylene; Polyamides such as nylon 6, nylon 6, and 6; Polyvinyl chloride, Polyvinyl chloride / Vinyl acetate copolymers, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, vinyl polymers such as polyvinyl alcohol and vinylon; cellulose resins such as cellulose triacetate and cellophane; Methyl methacrylate, polyethyl methacrylate, polyethyl acrylate, acrylic resins such as polybutyl acrylate; polystyrene, polycarbonate, polyarylate, synthetic resin films such as polyimide, a sheet or a plate, and the like.
　上記金属面を有する物品としては、金属面を有しており、この金属面に、直接、上記粘着シートが、少なくとも部分的にまたは全面的に貼り合わせられているものがある。このような金属面を有する物品において、上記粘着シートが貼り合わせられる被着体（「金属面含有被着体」と称する場合がある）としては、少なくとも部分的に金属面を有していれば特に制限されない。このような金属面含有被着体において、金属面が形成されている部位は、上記粘着シートを直接貼付することが可能な部位であれば特に制限されず、外側の面であってもよく、また、内側の面等であってもよい。なお、１つの金属面含有被着体に金属面が複数形成されている場合、これらの複数の金属面は同一の金属材料により形成された面であってもよく、異なる金属材料により形成された面であってもよい。 The article having the metal surface includes a metal surface, and the pressure-sensitive adhesive sheet is directly or at least partially bonded to the metal surface. In an article having such a metal surface, the adherend to which the pressure-sensitive adhesive sheet is bonded (sometimes referred to as a “metal face-containing adherend”) has at least a partial metal face. There is no particular limitation. In such a metal surface-containing adherend, the part where the metal surface is formed is not particularly limited as long as it is a part where the adhesive sheet can be directly attached, and may be an outer surface, Further, it may be an inner surface or the like. When a plurality of metal surfaces are formed on one metal surface-containing adherend, these plurality of metal surfaces may be surfaces formed of the same metal material or formed of different metal materials. It may be a surface.
　上記金属面含有被着体における金属面は、金属材料により形成された金属面含有被着体の表面であってもよく、また各種材料により形成された基材（または構造体）の表面に形成された金属層表面（特に、金属薄膜層表面）であってもよい。上記金属面は、いずれにせよ、金属材料による表面であればよい。 The metal surface in the metal surface-containing adherend may be the surface of a metal surface-containing adherend formed of a metal material, or formed on the surface of a substrate (or structure) formed of various materials. It may be the surface of the metal layer (particularly, the surface of the metal thin film layer). In any case, the metal surface may be a surface made of a metal material.
　上記金属薄膜層等の金属層は、各種材料により構成された基材（または構造体）の表面の所定の部位に形成することができる。このような金属層において、金属薄膜層の厚みとしては、金属面含有被着体の種類に応じて適宜選択することができ、例えば、０．１μｍ以上であってもよい。なお、金属薄膜層の厚みの上限としては、一般的に薄膜層とみなされる厚みであれば特に制限されない。 The metal layer such as the metal thin film layer can be formed at a predetermined site on the surface of the base material (or structure) made of various materials. In such a metal layer, the thickness of the metal thin film layer can be appropriately selected according to the type of the metal surface-containing adherend, and may be, for example, 0.1 μm or more. The upper limit of the thickness of the metal thin film layer is not particularly limited as long as it is generally regarded as a thin film layer.
　上記金属面を形成するための金属材料としては、例えば、アルミニウム、銀、金、銅、鉄、チタン、白金、ニッケル等の金属単体による金属材料；金合金（例えば、金－銅合金等）、銅合金〔例えば、銅－亜鉛合金（真鍮）、銅－アルミニウム合金等〕、アルミニウム合金（例えば、アルミニウム－モリブデン合金、アルミニウム－タンタル合金、アルミニウム－コバルト合金、アルミニウム－クロム合金、アルミニウム－チタン合金、アルミニウム－白金合金等）、ニッケル合金（例えば、ニッケル－クロム合金、銅－ニッケル合金、亜鉛－ニッケル合金等）、スズ合金、ステンレス等の各種合金による金属材料等があげられる。これら金属材料は、単独でまたは２種以上組み合わせて使用することができる。 Examples of the metal material for forming the metal surface include metal materials made of simple metals such as aluminum, silver, gold, copper, iron, titanium, platinum and nickel; gold alloys (for example, gold-copper alloys), Copper alloys (eg, copper-zinc alloy (brass), copper-aluminum alloy, etc.), aluminum alloys (eg, aluminum-molybdenum alloy, aluminum-tantalum alloy, aluminum-cobalt alloy, aluminum-chromium alloy, aluminum-titanium alloy, Aluminum-platinum alloy, etc.), nickel alloys (eg, nickel-chromium alloy, copper-nickel alloy, zinc-nickel alloy, etc.), tin alloys, metal materials made of various alloys such as stainless steel, and the like. These metal materials can be used alone or in combination of two or more.
　なお、金属材料は、金属元素のみを含有する金属材料であってもよく、金属元素とともに非金属元素を含有する金属材料〔例えば、金属の酸化物、水酸化物、ハロゲン化物（塩化物等）、オキソ酸塩（硝酸塩、硫酸塩、リン酸塩、炭酸塩等）等の金属系化合物〕であってもよい。 The metal material may be a metal material containing only a metal element, or a metal material containing a non-metal element together with a metal element [eg, metal oxide, hydroxide, halide (chloride, etc.) And metal compounds such as oxo acid salts (nitrates, sulfates, phosphates, carbonates, etc.).
　具体的には、上記金属面含有被着体としては、例えば、少なくとも部分的に金属面（金属薄膜層面等）を有している窓材またはこの窓材を構成するための部材や、金属薄膜層により形成された電磁波シールド層を有する光学的製品またはこの光学的製品を構成するための部材等があげられる。上記電磁波シールド層を有する光学的製品としては、例えば、電子ディスプレイ（プラズマディスプレイ等）等の光学機器や、デジタル万能ディスク等の光学的に記録可能なディスク（光学的記録ディスク）等があげられる。 Specifically, as the metal surface-containing adherend, for example, a window material having a metal surface (such as a metal thin film layer surface) at least partially, a member for constituting the window material, or a metal thin film Examples thereof include an optical product having an electromagnetic wave shielding layer formed of layers, or a member for constituting the optical product. Examples of the optical product having the electromagnetic wave shielding layer include optical devices such as an electronic display (plasma display and the like), optically recordable discs (optical recording discs) such as a digital universal disc, and the like.
　以下、実施例をあげて本発明をさらに具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。なお、例中、「部」、「％」とあるのは、重量基準を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the examples, “parts” and “%” mean weight basis.
〔アクリル系樹脂（Ａ）の製造〕
　撹拌機を備えたガラス製の４ッ口丸底フラスコに水３００部を入れ、分散安定剤としてポリビニルアルコール０．７部を溶解し、撹拌翼により３００ｒｐｍで撹拌しつつ、ｎ－ブチルアクリレート（ａ１）８７．８部、アクリロニトリル（ａ３）７．２部、２－ヒドロキシエチルメタクリレート（ａ２）５部からなる単量体混合物と、重合開始剤としてＮ，Ｎ′－アゾビスイソブチロニトリル０．９部を一括投入し、懸濁液を作製した。 [Manufacture of acrylic resin (A)]
In a glass four-necked round-bottom flask equipped with a stirrer, 300 parts of water was dissolved, 0.7 parts of polyvinyl alcohol was dissolved as a dispersion stabilizer, and n-butyl acrylate (a1) was stirred with a stirring blade at 300 rpm. ) 87.8 parts, acrylonitrile (a3) 7.2 parts, 2-hydroxyethyl methacrylate (a2) 5 parts monomer mixture, N, N'-azobisisobutyronitrile 0. Nine parts were charged together to prepare a suspension.
　この懸濁液を、撹拌継続下に反応系内を６８℃まで昇温させ、４時間一定に保って反応させた。その後、室温（約２５℃）まで冷却した。次いで、反応物を固液分離し、水で充分に洗浄した後、乾燥機を用いて７０℃で１２時間乾燥し、塊状のアクリル系樹脂（Ａ－１）を得た。得られたアクリル系樹脂（Ａ－１）の重量平均分子量（Ｍｗ）は１３０万、分散度（Ｍｗ／Ｍｎ）は４．６、ガラス転移温度は－４７℃であった。 The suspension was heated to 68 ° C. while stirring and kept constant for 4 hours. Then, it cooled to room temperature (about 25 degreeC). Next, the reaction product was separated into solid and liquid, thoroughly washed with water, and then dried at 70 ° C. for 12 hours using a dryer to obtain a bulk acrylic resin (A-1). The resulting acrylic resin (A-1) had a weight average molecular weight (Mw) of 1.3 million, a dispersity (Mw / Mn) of 4.6, and a glass transition temperature of −47 ° C.
〔アクリル系樹脂（Ａ－２）の製造〕
　撹拌機を備えたガラス製の４ッ口丸底フラスコに水３００部を入れ、分散安定剤としてポリビニルアルコール０．７部を溶解し、撹拌翼により３００ｒｐｍで撹拌しつつ、ｎ－ブチルアクリレート（ａ１）５１部、イソボルニルアクリレート（ａ１）４４部、２－ヒドロキシエチルメタクリレート（ａ２）５部からなる単量体混合物と、重合開始剤としてＮ，Ｎ′－アゾビスイソブチロニトリル０．９部を一括投入し、懸濁液を作製した。 [Manufacture of acrylic resin (A-2)]
In a glass four-necked round-bottom flask equipped with a stirrer, 300 parts of water was dissolved, 0.7 parts of polyvinyl alcohol was dissolved as a dispersion stabilizer, and n-butyl acrylate (a1) was stirred with a stirring blade at 300 rpm. ) 51 parts, 44 parts of isobornyl acrylate (a1), 5 parts of 2-hydroxyethyl methacrylate (a2) and 0.9, N, N′-azobisisobutyronitrile as a polymerization initiator All the parts were put together to prepare a suspension.
　この懸濁液を、撹拌継続下に反応系内を６８℃まで昇温させ、４時間一定に保って反応させた。その後、室温（約２５℃）まで冷却した。次いで、反応物を固液分離し、水で充分に洗浄した後、乾燥機を用いて７０℃で１２時間乾燥し、塊状のアクリル系樹脂（Ａ－２）を得た。得られたアクリル系樹脂（Ａ－２）の重量平均分子量（Ｍｗ）は９５万、分散度（Ｍｗ／Ｍｎ）は３．５、ガラス転移温度は－５℃であった。 The suspension was heated to 68 ° C. while stirring and kept constant for 4 hours. Then, it cooled to room temperature (about 25 degreeC). Next, the reaction product was separated into solid and liquid, thoroughly washed with water, and then dried at 70 ° C. for 12 hours using a dryer to obtain a bulk acrylic resin (A-2). The resulting acrylic resin (A-2) had a weight average molecular weight (Mw) of 950,000, a dispersity (Mw / Mn) of 3.5, and a glass transition temperature of −5 ° C.
〔実施例１〕
　アクリル系樹脂（Ａ）として、アクリル系樹脂（Ａ－１）１２部、単官能性不飽和化合物（Ｂ）として、４－ヒドロキシブチルアクリレート（ＨＢＡ：（Ｂ２））１８部、シクロヘキシルアクリレート（ＣＨＡ：（Ｂ１））２０部、２－エチルヘキシルアクリレート（２ＥＨＡ：（Ｂ３））５０部、多官能性不飽和化合物（Ｃ）として、トリメチロールプロパントリアクリレート（ＴＭＰＴＡ）０．３部を撹拌機のついた容器に入れ、２４時間撹拌混合し溶解した。この溶液に、光重合開始剤（Ｄ）として２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン（商品名：「ダロキュア１１７３」；チバ・スペシャリティ・ケミカルズ（株）社製）（ＨＭＰＰ）１部を混合することにより粘着剤組成物を得た。 [Example 1]
As acrylic resin (A), 12 parts of acrylic resin (A-1), as monofunctional unsaturated compound (B), 18 parts of 4-hydroxybutyl acrylate (HBA: (B2)), cyclohexyl acrylate (CHA: (B1)) 20 parts, 2-ethylhexyl acrylate (2EHA: (B3)) 50 parts, and polyfunctional unsaturated compound (C) 0.3 parts of trimethylolpropane triacrylate (TMPTA) were equipped with a stirrer. The mixture was placed in a container and stirred for 24 hours to dissolve. To this solution, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: “Darocur 1173”; manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator (D) ( A pressure-sensitive adhesive composition was obtained by mixing 1 part of HMPP).
　上記で得られた粘着剤組成物を、厚みが１００μｍのポリエチレンテレフタレート（ＰＥＴ）基材上に１３０μｍの厚みになるように塗工した。さらに離型処理されたＰＥＴ基材を用い、離型処理面が上記塗工面に接するようにして塗工面を被膜した。その後、下記に示す紫外線照射装置を用い、照射強度が２００ｍＷ／ｃｍ２となるように調整した高圧水銀ランプより、積算光量が２４００ｍＪ／ｃｍ２となるように紫外線を照射することにより、粘着剤組成物が硬化させて得られる粘着剤層を有する粘着シートを得た。
＜紫外線照射装置＞
　アイグランデージＥＣＳ－３０１Ｇ１型（アイグラフィックス社）
＜照射条件＞
　８０Ｗ／ｃｍ（高圧水銀ランプ）×１８ｃｍＨ、照射強度２００ｍＷ／ｃｍ２ The pressure-sensitive adhesive composition obtained above was coated on a polyethylene terephthalate (PET) substrate having a thickness of 100 μm so as to have a thickness of 130 μm. Furthermore, the coated surface was coated so that the release-treated surface was in contact with the coated surface, using a PET substrate that had been subjected to a release treatment. Then, using the ultraviolet irradiation apparatus shown below, the pressure-sensitive adhesive composition is irradiated with ultraviolet rays so that the integrated light amount becomes 2400 mJ / cm 2 from a high-pressure mercury lamp adjusted so that the irradiation intensity becomes 200 mW / cm 2. A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer obtained by curing the product was obtained.
<Ultraviolet irradiation device>
Eye Grandage ECS-301G1 (I Graphics)
<Irradiation conditions>
80 W / cm (high pressure mercury lamp) × 18 cmH, irradiation intensity 200 mW / cm 2
〔実施例２～８〕
　実施例１において、４－ヒドロキシブチルアクリレート（ＨＢＡ）、シクロヘキシルアクリレート（ＣＨＡ）および２－エチルヘキシルアクリレート（２ＥＨＡ）の配合割合を下記表１のとおりに変更した以外は、実施例１と同様にして粘着剤組成物および粘着シートを得た。 [Examples 2 to 8]
In Example 1, adhesion was performed in the same manner as in Example 1 except that the blending ratio of 4-hydroxybutyl acrylate (HBA), cyclohexyl acrylate (CHA) and 2-ethylhexyl acrylate (2EHA) was changed as shown in Table 1 below. An agent composition and an adhesive sheet were obtained.
〔実施例９〕
　実施例1において、アクリル系樹脂（Ａ－１）の代わりにアクリル系樹脂（Ａ－２)を用いて、その他成分の配合割合を下記表２のとおりに変更した以外は、実施例１と同様にして粘着剤組成物および粘着シートを得た。 Example 9
Example 1 is the same as Example 1 except that acrylic resin (A-2) is used instead of acrylic resin (A-1) and the blending ratio of other components is changed as shown in Table 2 below. Thus, a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet were obtained.
〔比較例１～３〕
　実施例１において、４－ヒドロキシブチルアクリレート（ＨＢＡ）、シクロヘキシルアクリレート（ＣＨＡ）および２－エチルヘキシルアクリレート（２ＥＨＡ）の配合割合を下記表１のとおりに変更した以外は、実施例１と同様にして粘着剤組成物および粘着シートを得た。 [Comparative Examples 1 to 3]
In Example 1, adhesion was performed in the same manner as in Example 1 except that the blending ratio of 4-hydroxybutyl acrylate (HBA), cyclohexyl acrylate (CHA) and 2-ethylhexyl acrylate (2EHA) was changed as shown in Table 1 below. An agent composition and an adhesive sheet were obtained.
〔比較例４〕
　実施例１において、粘着剤組成物の組成をアクリル系樹脂（Ａ－１）１４．６部、２－エチルヘキシルアクリレート（２ＥＨＡ）３９．４部、ブチルアクリレート（ＢＡ）３９．４部、アクリル酸（ＡＡｃ）６．６部、トリメチロールプロパントリアクリレート（ＴＭＰＴＡ）０．３部、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン（商品名：「ダロキュア１１７３」；チバ・スペシャリティ・ケミカルズ（株）製）（ＨＭＰＰ）１部とした以外は、実施例１と同様にして粘着剤組成物および粘着シートを得た。 [Comparative Example 4]
In Example 1, the pressure-sensitive adhesive composition was composed of 14.6 parts acrylic resin (A-1), 39.4 parts 2-ethylhexyl acrylate (2EHA), 39.4 parts butyl acrylate (BA), acrylic acid ( AAc) 6.6 parts, trimethylolpropane triacrylate (TMPTA) 0.3 part, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: “Darocur 1173”; Ciba Specialty) A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet were obtained in the same manner as in Example 1, except that 1 part of Chemicals Co., Ltd. (HMPP) was used.
　上記実施例および比較例で用いた粘着剤組成物について、上記各成分材料の配合割合を後記の表１に示す。 For the pressure-sensitive adhesive compositions used in the above Examples and Comparative Examples, the blending ratios of the above component materials are shown in Table 1 below.
　上記の実施例および比較例で得られた粘着シートについて、下記の方法により、粘着剤層のゲル分率、粘着力、保持力（凝集力）、耐腐食性を測定・評価し、その結果を併せて後記の表２に示す。 For the pressure-sensitive adhesive sheets obtained in the above examples and comparative examples, the gel fraction, pressure-sensitive adhesive force, holding power (cohesive force), and corrosion resistance of the pressure-sensitive adhesive layer were measured and evaluated by the following methods. The results are also shown in Table 2 below.
＜ゲル分率＞
　得られた粘着シートを５０ｍｍ×５０ｍｍに切断した後、この粘着シートの粘着剤層側を、６０×１００ｍｍのＳＵＳメッシュシート（２００メッシュ）の長手方向の中央部を避けてメッシュシートに貼り合わせ、ついで、メッシュシートを中央部から折り返して粘着シートを包み込み、試験片を作製した。その試験片を、トルエン１８０ｇの入った密封容器中に、２３℃×２４時間浸漬し、メッシュシート中に残存した不溶解の粘着剤成分の重量％をゲル分率とする。この際、基材の重量は差し引いておく。 <Gel fraction>
After the obtained pressure-sensitive adhesive sheet was cut into 50 mm × 50 mm, the pressure-sensitive adhesive layer side of this pressure-sensitive adhesive sheet was bonded to the mesh sheet while avoiding the central portion in the longitudinal direction of the 60 × 100 mm SUS mesh sheet (200 mesh), Next, the mesh sheet was folded from the center to wrap the adhesive sheet, and a test piece was prepared. The test piece is immersed in a sealed container containing 180 g of toluene at 23 ° C. for 24 hours, and the weight percentage of the insoluble adhesive component remaining in the mesh sheet is defined as the gel fraction. At this time, the weight of the substrate is subtracted.
＜粘着力＞
　ＪＩＳ　Ｚ－０２７３に準じ粘着力を測定した。すなわち、得られた粘着シートを２５ｍｍ×１００ｍｍに切断した後、これを、被着体としてのステンレス板（ＳＵＳ３０４ＢＡ板）に、２３℃、相対湿度５０％の雰囲気下で２ｋｇゴムローラーを用いて２往復させることにより圧着し、試験片を作製した。この試験片を、同雰囲気下で、３０分放置した後、剥離速度０．３ｍ／分により、１８０度剥離試験を行ない、粘着力（Ｎ／２５ｍｍ）を測定した。
（評価基準）
　　○・・・１０Ｎ／２５ｍｍ以上
　　×・・・１０Ｎ／２５ｍｍ未満 <Adhesive strength>
The adhesive strength was measured according to JIS Z-0273. That is, after the obtained pressure-sensitive adhesive sheet was cut into 25 mm × 100 mm, this was applied to a stainless steel plate (SUS304BA plate) as an adherend using a 2 kg rubber roller in an atmosphere of 23 ° C. and 50% relative humidity. A test piece was prepared by pressure bonding by reciprocating. The test piece was allowed to stand for 30 minutes in the same atmosphere, and then subjected to a 180 ° peel test at a peel rate of 0.3 m / min, and the adhesive strength (N / 25 mm) was measured.
(Evaluation criteria)
○ ・ ・ ・ 10N / 25mm or more × ・ ・ ・ less than 10N / 25mm
＜保持力（凝集力）＞
　得られた粘着シートをＪＩＳ　Ｚ－０２７３に準じ、ＳＵＳ３０４を被着体とし、貼付面積２５ｍｍ×２５ｍｍで貼り付けた後、８０℃で２０分間放置したものについて１ｋｇの荷重をかけて測定し、評価した。
（評価基準）
　　○・・・２４時間放置後でも落下しなかった
　　△・・・２４時間放置後のズレが１ｍｍ以内
　　×・・・２４時間放置後のズレが１ｍｍ以上又は落下 <Retention force (cohesive force)>
According to JIS Z-0273, the obtained pressure-sensitive adhesive sheet was measured by applying a load of 1 kg on a SUS304 adherend, pasted at a pasting area of 25 mm × 25 mm, and then left at 80 ° C. for 20 minutes. did.
(Evaluation criteria)
○ ・ ・ ・ Did not fall even after 24 hours left △ ・ ・ ・ Deviation within 24 mm after left for 24 hours × ・ ・ ・ Deviation more than 1 mm after 24 hours left or dropped
＜耐腐食性＞
　得られた粘着シートを銅箔（厚さ：１３０μｍ）に貼り合わせた後、６０℃×９０％ＲＨの雰囲気下に２５０時間保存した。その後、目視で、ポリエチレンテレフタレート製フィルム側から銅箔の表面を観察して、粘着シートが貼り合わせられている銅箔の表面の腐食の有無を確認した。
（評価基準）
　　○・・・腐食無し
　　×・・・腐食有り  <Corrosion resistance>
The obtained pressure-sensitive adhesive sheet was bonded to a copper foil (thickness: 130 μm) and then stored in an atmosphere of 60 ° C. × 90% RH for 250 hours. Thereafter, the surface of the copper foil was visually observed from the polyethylene terephthalate film side to confirm the presence or absence of corrosion on the surface of the copper foil to which the adhesive sheet was bonded.
(Evaluation criteria)
○ ・ ・ ・ No corrosion × ・ ・ ・ Corrosion
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　脂環式構造含有エチレン性不飽和化合物と水酸基含有エチレン性不飽和化合物の両方を含有する粘着剤組成物からなる実施例１～９の粘着剤は、粘着力と凝集力（保持力）にバランスよく優れるものであり、また、酸を含まないため耐腐食性にも優れることがわかる。 The adhesives of Examples 1 to 9 consisting of an adhesive composition containing both an alicyclic structure-containing ethylenically unsaturated compound and a hydroxyl group-containing ethylenically unsaturated compound balance the adhesive force and cohesive strength (holding power). It can be seen that it is excellent and also has excellent corrosion resistance because it does not contain acid.
　一方、脂環式構造含有エチレン性不飽和化合物と水酸基含有エチレン性不飽和化合物の両方を含有しない比較例１の粘着剤は粘着力と凝集力（保持力）の両方に劣るものであり、脂環式構造含有エチレン性不飽和化合物を含有しない比較例２の粘着剤は粘着力に劣り、水酸基含有エチレン性不飽和化合物を含有しない比較例３の粘着剤は凝集力（保持力）に劣るものであった。
　また、酸性基を有するアクリル酸が配合された粘着剤組成物からなる比較例４の粘着剤は、粘着力と凝集力（保持力）には優れるものの、耐腐食性に劣るものであった。 On the other hand, the pressure-sensitive adhesive of Comparative Example 1 that does not contain both the alicyclic structure-containing ethylenically unsaturated compound and the hydroxyl group-containing ethylenically unsaturated compound is inferior in both adhesive strength and cohesive strength (holding power). The adhesive of Comparative Example 2 that does not contain a cyclic structure-containing ethylenically unsaturated compound is inferior in adhesive strength, and the adhesive of Comparative Example 3 that does not contain a hydroxyl group-containing ethylenically unsaturated compound is inferior in cohesive strength (holding power). Met.
Moreover, although the adhesive of the comparative example 4 which consists of an adhesive composition with which the acrylic acid which has an acidic group was mix | blended was excellent in adhesive force and cohesion force (holding force), it was inferior to corrosion resistance.
　また、実施例９の粘着シートについて、下記の方法により透明性（ヘイズ）を測定した。その結果を表３に示す。 In addition, the transparency (haze) of the pressure-sensitive adhesive sheet of Example 9 was measured by the following method. The results are shown in Table 3.
＜ヘイズ＞
・ヘイズ測定用サンプルの製造
得られた粘着シートを３ｃｍ×４ｃｍに切り抜き、剥離離型シートを剥離して、粘着剤層側を無アルカリガラス板（コーニング社製、イーグルＸＧ）に押圧した後、オートクレーブ（５０℃、０．５ＭＰａ×２０ｍｉｎ）処理し、ヘイズ測定用サンプルを得た。
・ヘイズ値の測定
　上記ヘイズ測定用サンプルのヘイズを下記の各条件で測定した。
　・初期ヘイズ　：ヘイズ測定用サンプル作成後に測定。
　・湿熱ヘイズ１：ヘイズ測定用サンプル作成後、６０℃×９０％ＲＨ条件下で１００時間静置後に測定。
　・湿熱ヘイズ２：ヘイズ測定用サンプル作成後、６０℃×９０％ＲＨ条件下で１００時間静置後、さらに室温で３時間静置後に測定。
ヘイズは、拡散透過率及び全光線透過率を、ＨＡＺＥ　ＭＡＴＥＲ　ＮＤＨ２０００（日本電色工業社製）を用いて測定した。なお、本機はＪＩＳ　Ｋ７３６１－１に準拠している。
　得られた拡散透過率と全光線透過率の値を下記式に代入して、ヘイズを算出した。
ヘイズ値（％）＝（拡散透過率／全光線透過率）×１００ <Haze>
-Manufacture of sample for haze measurement Cut out the obtained adhesive sheet to 3 cm x 4 cm, peel off the release release sheet, and press the adhesive layer side against an alkali-free glass plate (Corning Corp., Eagle XG), The sample was subjected to autoclave (50 ° C., 0.5 MPa × 20 min) to obtain a sample for haze measurement.
-Measurement of haze value The haze of the sample for haze measurement was measured under the following conditions.
-Initial haze: Measured after creating a sample for haze measurement.
-Humid heat haze 1: Measured after preparation of a sample for haze measurement and standing at 60 ° C. × 90% RH for 100 hours.
Humid heat haze 2: Measured after preparing a sample for haze measurement, after standing at 60 ° C. × 90% RH for 100 hours, and then standing at room temperature for 3 hours.
For haze, the diffuse transmittance and total light transmittance were measured using HAZE MATER NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.). This machine conforms to JIS K7361-1.
The values of the obtained diffuse transmittance and total light transmittance were substituted into the following formula to calculate haze.
Haze value (%) = (diffuse transmittance / total light transmittance) × 100
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　脂環式構造含有（メタ）アクリル酸エステル系モノマーを共重合して得られるアクリル系樹脂（Ａ－２）を用いた粘着剤組成物からなる実施例９の粘着剤は、湿熱条件下でもヘイズの変化が少なく、耐湿熱性にも優れることがわかる。 The pressure-sensitive adhesive composition of Example 9 comprising a pressure-sensitive adhesive composition using an acrylic resin (A-2) obtained by copolymerizing an alicyclic structure-containing (meth) acrylic acid ester-based monomer has a haze even under wet heat conditions. It can be seen that there is little change in the resistance to heat and heat resistance.
　本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
　本出願は、２０１０年１２月６日出願の日本特許出願（特願２０１０‐２７１６５３）に基づくものであり、その内容はここに参照として取り込まれる。 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2010-271653) filed on Dec. 6, 2010, the contents of which are incorporated herein by reference.
　本発明の粘着剤組成物からなる粘着剤は、強固な接着力と優れた凝集力を有するために高温環境下でも基材からの剥がれが生じにくく、特に光学部材貼合わせ用の粘着剤、粘着シートとして有用であり、更には粘着剤中に酸をさせなくても粘着物性を満足させることができるため、金属や金属酸化物等に対して耐腐食性が要求される電子ディスプレイ等の光学機器や、デジタル万能ディスク等の光学的記録ディスク（光学的記録媒体）を貼合わせるための光学用粘着シートとして有用である。 The pressure-sensitive adhesive composed of the pressure-sensitive adhesive composition of the present invention has strong adhesive force and excellent cohesive force, and therefore hardly peels off from the substrate even in a high-temperature environment. Optical equipment such as an electronic display that is useful as a sheet, and that is capable of satisfying adhesive properties without causing acid in the adhesive, and that requires corrosion resistance against metals and metal oxides. It is also useful as an optical pressure-sensitive adhesive sheet for laminating an optical recording disk (optical recording medium) such as a digital universal disk.

Claims (8)

  1. 　アクリル系樹脂（Ａ）、エチレン性不飽和基を１個有するエチレン性不飽和化合物（Ｂ）、エチレン性不飽和基を２個以上有するエチレン性不飽和化合物（Ｃ）、および光重合開始剤（Ｄ）を含有する粘着剤組成物であって、
    エチレン性不飽和基を１個有するエチレン性不飽和化合物（Ｂ）として、脂環式構造含有エチレン性不飽和化合物（Ｂ１）、及び水酸基含有エチレン性不飽和化合物（Ｂ２）を含有することを特徴とする粘着剤組成物。     An acrylic resin (A), an ethylenically unsaturated compound (B) having one ethylenically unsaturated group, an ethylenically unsaturated compound (C) having two or more ethylenically unsaturated groups, and a photopolymerization initiator ( A pressure-sensitive adhesive composition containing D),
    It contains an alicyclic structure-containing ethylenically unsaturated compound (B1) and a hydroxyl group-containing ethylenically unsaturated compound (B2) as the ethylenically unsaturated compound (B) having one ethylenically unsaturated group. A pressure-sensitive adhesive composition.
  2. 　アクリル系樹脂（Ａ）が、懸濁重合により得られたドライレジンであることを特徴とする請求項１記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the acrylic resin (A) is a dry resin obtained by suspension polymerization.
  3. 　アクリル系樹脂（Ａ）が、脂環式構造含有（メタ）アクリル酸エステル系モノマーを含有する共重合成分を共重合させてなるアクリル系樹脂であることを特徴とする請求項１または２記載の粘着剤組成物。 The acrylic resin (A) is an acrylic resin obtained by copolymerizing a copolymer component containing an alicyclic structure-containing (meth) acrylic acid ester monomer. Adhesive composition.
  4. 　エチレン性不飽和基を１個有するエチレン性不飽和化合物（Ｂ）中における脂環式構造含有エチレン性不飽和化合物（Ｂ１）及び水酸基含有エチレン性不飽和化合物（Ｂ２）の合計量の含有割合が、１０～７０重量％であることを特徴とする請求項１～３のいずれか一項に記載の粘着剤組成物。 The content ratio of the total amount of the alicyclic structure-containing ethylenically unsaturated compound (B1) and the hydroxyl group-containing ethylenically unsaturated compound (B2) in the ethylenically unsaturated compound (B) having one ethylenically unsaturated group is The pressure-sensitive adhesive composition according to any one of claims 1 to 3, wherein the pressure-sensitive adhesive composition is 10 to 70% by weight.
  5. 　実質的に酸を含まないことを特徴とする請求項１～４のいずれか一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, which is substantially free of an acid.
  6. 　溶剤を含有しないことを特徴とする請求項１～５のいずれか一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, which does not contain a solvent.
  7. 　請求項１～６のいずれか一項に記載の粘着剤組成物が、活性エネルギー線照射により硬化されてなることを特徴とする粘着剤。 A pressure-sensitive adhesive, wherein the pressure-sensitive adhesive composition according to any one of claims 1 to 6 is cured by irradiation with active energy rays.
  8. 　基材と、請求項７記載の粘着剤からなる粘着剤層を含有することを特徴とする粘着シート。 A pressure-sensitive adhesive sheet comprising a base material and a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive according to claim 7.
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