WO2014163003A1 - Adhesive composition for optics, adhesive sheet for optics, and method for producing adhesive sheet for optics - Google Patents

Adhesive composition for optics, adhesive sheet for optics, and method for producing adhesive sheet for optics Download PDF

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Publication number
WO2014163003A1
WO2014163003A1 PCT/JP2014/059138 JP2014059138W WO2014163003A1 WO 2014163003 A1 WO2014163003 A1 WO 2014163003A1 JP 2014059138 W JP2014059138 W JP 2014059138W WO 2014163003 A1 WO2014163003 A1 WO 2014163003A1
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mass
sensitive adhesive
component
pressure
monomer
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PCT/JP2014/059138
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French (fr)
Japanese (ja)
Inventor
近藤　真
政一 清水
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綜研化学株式会社
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Priority to KR1020157031349A priority Critical patent/KR20150140719A/en
Priority to CN201480019780.2A priority patent/CN105073936A/en
Priority to JP2015510055A priority patent/JPWO2014163003A1/en
Publication of WO2014163003A1 publication Critical patent/WO2014163003A1/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
    • 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

Definitions

  • the present invention relates to an optical pressure-sensitive adhesive composition, an optical pressure-sensitive adhesive sheet, and a method for producing the same.
  • image display devices have been used under various applications and conditions. For example, they are often used not only under room temperature conditions but also under severe conditions such as high temperature and high temperature and humidity. .
  • high temperature or high temperature and humidity condition examples include use in a tropical region, use inside a vehicle, and inside an outdoor measuring instrument.
  • Some optical films that make up image display devices shrink under high temperature and high humidity to cause dimensional changes.
  • dimensional deformation occurs in the optical film, it is difficult to completely return to the original dimensions even if the temperature and humidity conditions are changed.
  • the pressure-sensitive adhesive layer is cracked, peeled off and floated due to the stress caused by the dimensional change of the optical film.
  • metal oxides such as an ITO layer used for transparent electrodes are often used in image display devices.
  • the adherend contains a metal oxide
  • the metal oxide is corroded by an acid component, causing a problem that the resistance value is increased.
  • the present invention provides an optical pressure-sensitive adhesive composition, an optical pressure-sensitive adhesive sheet, and a method for producing the same, which can exhibit excellent durability under high temperature and high humidity conditions and do not corrode an adherend.
  • the present inventors can obtain a pressure-sensitive adhesive layer having excellent durability and not corroding an adherend by using a pressure-sensitive adhesive composition having a predetermined component. I found out.
  • the optical pressure-sensitive adhesive composition according to one embodiment of the present invention includes (A) 100 parts by mass of an acrylic polymer substantially free of a carboxyl group, and (B) a molecular weight having two or more glycidyl groups in one molecule. 1,000 or less compounds 0.3 mass part or more and 20 mass parts or less are included.
  • an isocyanate-based crosslinking agent may be further included.
  • composition including the partial polymer (A 2 ) further includes (E) a polyfunctional monomer, and the (A) acrylic polymer is It can be obtained from the composition containing the partial polymer (A 2 ) and the (E) polyfunctional monomer.
  • optical pressure-sensitive adhesive composition according to any one of 2 to 5 above, wherein the monomer mixture may further contain (a3) a nitrogen atom-containing monomer in an amount of 0.1% by mass to 5% by mass. .
  • the gel fraction may be 20% or more and 95% or less.
  • optical pressure-sensitive adhesive composition according to any one of 1 to 7, which can be used for bonding members constituting a touch panel type input / output device.
  • the optical pressure-sensitive adhesive sheet according to another aspect of the present invention has a pressure-sensitive adhesive layer obtained from the optical pressure-sensitive adhesive composition described in any one of 1 to 7 above.
  • the manufacturing method of the optical adhesive sheet which concerns on the other aspect of this invention has (A) 100 mass parts of acrylic polymers which do not contain a carboxyl group substantially, and (B) 2 or more glycidyl groups in 1 molecule.
  • the pressure-sensitive adhesive composition may further include (C) an isocyanate-based crosslinking agent.
  • the method for producing an optical pressure-sensitive adhesive sheet includes (a1) (meth) acrylic acid alkyl ester monomer 60% by mass to 85% by mass and (a2) hydroxyl group-containing monomer 15% by mass. 100 parts by mass of a partially polymerized monomer mixture (A 2 ) containing 40% by mass or less (wherein (a1) (meth) acrylic acid alkyl ester monomer and (a2) hydroxyl group-containing monomer When the monomer mixture is 100% by mass, the total amount is 75% by mass or more and 100% by mass or less.) (B) Molecular weight 1,000 having two or more glycidyl groups in one molecule.
  • the optical pressure-sensitive adhesive composition according to any one of 1 to 8 above (A) 100 parts by mass of an acrylic polymer substantially free of carboxyl groups, and (B) a molecular weight of 1 having two or more glycidyl groups in one molecule. , 000 or less of the compound is contained in an amount of 0.3 to 20 parts by mass, has appropriate adhesiveness, does not corrode the adherend, and is excellent under high temperature conditions or high temperature and high humidity conditions. A coating liquid layer exhibiting high durability (wet heat durability) can be obtained.
  • the optical pressure-sensitive adhesive sheet described in 9 has a pressure-sensitive adhesive layer obtained from the optical pressure-sensitive adhesive composition described in any one of 1 to 7, the optical pressure-sensitive adhesive sheet has excellent durability, In addition, the adherend is not corroded. Therefore, the optical pressure-sensitive adhesive sheet can be suitably used for an image display device or an input / output device.
  • the method for producing an optical pressure-sensitive adhesive sheet described in 10 and 11 above includes (A) 100 parts by mass of an acrylic polymer that substantially does not contain a carboxyl group, and (B) two or more glycidyl groups in one molecule.
  • a step of obtaining a coating liquid layer by applying a pressure-sensitive adhesive composition containing 0.3 to 20 parts by mass of a compound having a molecular weight of 1,000 or less and optionally (C) an isocyanate-based crosslinking agent to the surface of the separator.
  • or 13 WHEREIN (a1) (meth) acrylic-acid alkylester monomer 60 mass%-85 mass% and (a2) hydroxyl-containing monomer 15 mass %
  • a 2 a partial mixture of a monomer mixture containing from 40% by weight to 40% by weight (wherein (a1) (meth) acrylic acid alkyl ester monomer and (a2) hydroxyl group-containing monomer)
  • the total amount of the body is 75% by mass or more and 100% by mass or less when the monomer mixture is 100% by mass.
  • B a molecular weight of 1 having 2 or more glycidyl groups in one molecule.
  • FIG. 1 is a cross-sectional view schematically showing a configuration of an input / output device (touch panel type input / output device) according to an embodiment of the present invention.
  • parts means “parts by mass” and “%” means “mass%” unless otherwise specified.
  • optical pressure-sensitive adhesive composition substantially contains (A) a carboxyl group.
  • Acrylic polymer hereinafter sometimes simply referred to as “component (A)” 100 parts by mass
  • component (B) a compound having a molecular weight of 1,000 or less having two or more glycidyl groups in one molecule ( Hereinafter, it may be simply described as “component (B).” Including 0.3 to 20 parts by mass.
  • the “acrylic polymer” includes at least one selected from acrylic acid, acrylic acid salt, acrylic acid ester, methacrylic acid, methacrylic acid salt, and methacrylic acid ester in a structural unit of 50% by mass or more.
  • the “acrylic acid ester monomer not containing a hydroxyl group” means an acrylic acid ester monomer having no hydroxyl group in the molecular structure.
  • the pressure-sensitive adhesive sheet formed using the pressure-sensitive adhesive composition according to the present embodiment can provide (B) the content of the component (A).
  • the content of the component is preferably 0.3 parts by mass or more and 15 parts by mass or less, and more preferably 0.3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the component (A). More preferred.
  • the durability when the content of the component (B) with respect to the content of the component (A) exceeds 20 parts by mass of the component (B) with respect to 100 parts by mass of the component (A), or 0 When the amount is less than 3 parts by mass, the durability may be inferior.
  • (A) component may contain the hydroxyl group. More specifically, when the monomer mixture that is the raw material of the component (A) contains a hydroxyl group-containing monomer, the component (A) can contain a hydroxyl group.
  • the component having a hydroxyl group for example, can be confirmed by the IR spectrum, the absorption in the range of 3400 cm -1 ⁇ 3200 cm -1 appear about the component (A).
  • the component (A) has a hydroxyl group, the hydroxyl group reacts with the later-described component (C), whereby durability can be improved.
  • a component can use (a1) (meth) acrylic acid alkyl ester monomer as a main monomer.
  • (meth) acrylic acid alkyl ester monomer as main monomer means (meth) acrylic acid alkyl ester among monomers contained in monomer mixture which is a raw material of component (A) The monomer content is the highest.
  • the first copolymer is a monomer mixture copolymer (A 1 ) containing a (meth) acrylic acid alkyl ester monomer as a main monomer
  • the second copolymer is (meth) acrylic. It is a partial copolymer (A 2 ) of a monomer mixture containing an acid alkyl ester monomer as a main monomer.
  • (A 1 ) component (A 1 ) component comprises (a1) (meth) acrylic acid alkyl ester monomer 60% by mass to 85% by mass (preferably 65% by mass to 84.9% by mass) and (a2 ) A copolymer (A 1 ) of a monomer mixture containing 15% by mass to 40% by mass (preferably 15% by mass to 35% by mass) of a hydroxyl group-containing monomer (wherein (a1) The total amount of the (meth) acrylic acid alkyl ester monomer and the (a2) hydroxyl group-containing monomer is 75% by mass or more and 100% by mass or less when the monomer mixture is 100% by mass. Can do.
  • the component (A 1 ) can be used, for example, when the optical pressure-sensitive adhesive composition according to this embodiment is used by being dissolved or dispersed in the (H) solvent (hereinafter referred to simply as “(H) component”. (The component (H) will be described in detail later.)
  • the optical pressure-sensitive adhesive composition according to this embodiment includes the component (A 1 ), the (C) isocyanate described later. It may further contain a system cross-linking agent (hereinafter sometimes simply referred to as “component (C)”).
  • the content of the component (A 1 ) in the pressure-sensitive adhesive composition according to the present embodiment is the same as that of the present embodiment. It can be 80 to 99.7 parts by mass, preferably 90 to 99.5 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive composition.
  • (A 2 ) component (A 2 ) component is (a1) (meth) acrylic acid alkyl ester monomer (hereinafter sometimes simply referred to as “(a1) component”) 60 mass% or more and 85 mass% (Preferably 65% by mass or more and 84.9% by mass or less) and (a2) a hydroxyl group-containing monomer (hereinafter sometimes simply referred to as “component (a2)”) 15% by mass or more and 40% by mass or less It is obtained from a composition containing a partial polymer (A 2 ) of a monomer mixture containing (preferably 15% by mass or more and 35% by mass or less) (wherein (a1) alkyl (meth) acrylate) The total amount of the ester monomer and the (a2) hydroxyl group-containing monomer can be 75% by mass or more and 100% by mass or less when the monomer mixture is 100% by mass.
  • the component (A 2 ) can be used, for example, when the optical pressure-sensitive adhesive composition according to this embodiment is applied in a state that does not substantially contain a solvent.
  • “coating the optical pressure-sensitive adhesive composition in a state containing substantially no solvent” means that the solvent content in the coating liquid containing the optical pressure-sensitive adhesive composition is 1% by mass or less. More specifically, it means a case where a solvent is not blended in the coating liquid.
  • a thick-film pressure-sensitive adhesive layer can be easily formed.
  • (A) if the component obtained from (A 2) component, the content of (A 2) component in the adhesive composition according to the present embodiment, the present embodiment It can be 80 mass parts or more and 99.7 mass parts or less with respect to 100 mass parts of adhesive compositions, and it is preferable that they are 90 mass parts or more and 99.5 mass parts or less.
  • (A 2) in terms of ingredients may have an appropriate viscosity, the proportion of residual monomers without polymerization of (A 2) content of the monomer in the component (monomers used ) Is preferably 30% by mass or more and 95% by mass or less, and more preferably 40% by mass or more and 80% by mass or less.
  • the polymer component contained in (A 2) component is preferably 5 mass% to 70 mass%, more preferably at most 20 mass% to 60 mass%.
  • the optical pressure-sensitive adhesive composition according to the present embodiment comprises (A 2) component described below (C) an isocyanate crosslinking agent (hereinafter, sometimes simply referred to as "component (C)".) May not be substantially included.
  • component (C) an isocyanate crosslinking agent
  • the optical pressure-sensitive adhesive composition does not substantially contain the component (C) means that the content of the component (C) in the optical pressure-sensitive adhesive composition is 0.1% by mass or less. More specifically, it refers to the case where the component (C) is not added to the optical pressure-sensitive adhesive composition.
  • the monomer mixture as the raw material of the component (A 2 ) is (a3) a nitrogen atom-containing monomer (hereinafter sometimes simply referred to as “(a3) component”) 0.1% by mass or more. 5 mass% or less can further be included.
  • the monomer mixture contains the component (a3), the whitening resistance of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention can be improved.
  • (A1) Component The (a1) component contained in the monomer mixture which is a raw material of the (A 1 ) component and the (A 2 ) component contributes to the adhesiveness and durability of the pressure-sensitive adhesive composition according to this embodiment. be able to.
  • (A1) (meth) acrylic acid alkyl ester monomers include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, n -Hexyl acrylate, n-hexyl methacrylate, n-pentyl acrylate, n-octyl acrylate, n-octyl methacrylate, n-nonyl acrylate, n-hexadecyl acrylate, n-hexadecyl methacrylate, stearyl acrylate, stearyl methacrylate, n-lauryl (Meth) acrylate alkyl ester having a linear alkyl group such as methacrylate, n-lauryl acrylate
  • Termonic monomers branched alkyl groups such as isopropyl acrylate, isobutyl acrylate, t-butyl acrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, isooctyl acrylate, isooctyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate (Meth) acrylic acid alkyl ester monomer having a cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate and the like (meth) acrylic acid alkyl ester monomer; Of these, one can be used alone or two or more can be used in combination.
  • the (a1) component is a (meth) acrylic acid alkyl ester linear or branched in that the pressure-sensitive adhesive sheet formed using the pressure-sensitive adhesive composition according to this embodiment is excellent in durability.
  • a (meth) acrylic acid alkyl ester monomer having an alkyl group is preferred, and a branched alkyl chain is more preferred.
  • the number of carbon atoms of the alkyl group is 1 or more and 20 or less (preferably 1 or more and 10 or less, preferably in terms of the durability of the pressure-sensitive adhesive sheet formed using the pressure-sensitive adhesive composition according to this embodiment. More preferably, it is 1 or more and 8 or less.
  • the component (a2) is contained in the monomer mixture which is the raw material of the component (a2) component (A 1 ) and the component (A 2 ), so that the component (A 1 ) and the component (A 2 ) contain a hydroxyl group. be able to.
  • a crosslinked structure can be formed by reacting the hydroxyl group contained in the (A 1 ) component and the (A 2 ) component with an isocyanate group contained in the later-described (C) component.
  • the component (a2) examples include hydroxyl group-containing compounds (eg, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, cyclohexane dimethanol monoacrylate).
  • hydroxyl group-containing compounds eg, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, cyclohexane dimethanol monoacrylate.
  • Acrylic acid ester monomers, N-methylol acrylamide, N-ethylol acrylamide and the like, and among them, one kind or a combination of two or more kinds can be used.
  • (A3) by the component (A 1) component and (A 2) to the raw material monomer mixture which is the component (a3) that contains component containing (A 1) component and (A 2) component is a nitrogen atom can do.
  • the component (a3) include a nitrogen atom-containing monomer containing at least one group selected from a nitrile group, an amino group, an imide group, an amide group, and the like.
  • examples of the component (a3) include amino group-containing monomers such as N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, Amides such as acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, acryloylmorpholine, N-methoxymethylacrylamide, N-butoxymethylacrylamide, Nt-butylacrylamide, N, N-dimethylaminopropylacrylamide A group containing monomer and acrylonitrile are mentioned, Among these, it can be used 1 type or in combination of 2 or more types. Of these, the component (a3) is more preferably an amide group-containing monomer from the viewpoint of improving the whitening resistance of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention.
  • Component (a4) The monomer mixture for obtaining the polymer as component (A) is a monomer other than components (a4), (a1), (a2) and (a3) (hereinafter, (It may be simply described as “component (a4)”).
  • component (a4) examples include vinyl acetate, styrene, macromonomer and the like.
  • the component (A 1 ) is used from the viewpoint that good adhesiveness and durability can be achieved more reliably.
  • the total amount of the component (a1), component (a2), and component (a3) in the monomer mixture for obtaining the component (A 2 ) (when the monomer mixture is 100% by mass) can be 90% by mass or more and 100% by mass or less, and preferably 95% by mass or more and 100% by mass or less.
  • the polymerization method of component (A 1 ) is not particularly limited and can be polymerized by a known method such as solution polymerization, emulsion polymerization, suspension polymerization, etc., but was obtained by polymerization.
  • a known method such as solution polymerization, emulsion polymerization, suspension polymerization, etc.
  • solution polymerization generally, a predetermined organic solvent, each monomer, a polymerization initiator, a chain transfer agent used as necessary, and the like are charged in a polymerization tank, under a nitrogen stream or a reflux temperature of the organic solvent, The reaction is carried out by heating for several hours with stirring.
  • the organic solvent include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, aromatic naphtha;
  • aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, aromatic naphtha
  • aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, isooctane, n-decane, dipentene, petroleum spirit, petroleum naphtha, turpentine oil;
  • Esters such as but
  • organic solvents for polymerization when polymerizing the component (A 1 ), it is preferable to use an organic solvent that hardly causes chain transfer during the polymerization reaction, for example, esters and ketones, and in particular, (A 1 ) From the viewpoints of solubility of components and ease of polymerization reaction, use of ethyl acetate, methyl ethyl ketone, acetone or the like is preferable.
  • organic peroxides and azo compounds that can be used in ordinary solution polymerization.
  • organic peroxides include t-butyl hydroperoxide, cumene hydroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, diisopropyl peroxydicarbonate, and di-2.
  • azo compound examples include 2,2′-azobis-isobutyronitrile and 2,2 ′.
  • the amount of these polymerization initiators used is usually 0.01 parts by mass or more and 2 parts by mass or less, and preferably 0.02 parts by mass or more and 1.0 parts by mass or less with respect to 100 parts by mass of the total monomer. .
  • a chain transfer agent can be used as necessary within a range that does not impair the purpose and effect of the present invention.
  • chain transfer agents examples include cyanoacetic acid; alkyl esters having 1 to 8 carbon atoms of cyanoacetic acid; bromoacetic acid; alkyl esters having 1 to 8 carbon atoms of bromoacetic acid; anthracene, phenanthrene, and fluorene.
  • Aromatic compounds such as 9-phenylfluorene; aromatic nitro compounds such as p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol and p-nitrotoluene; benzoquinone, 2,3, Benzoquinone derivatives such as 5,6-tetramethyl-p-benzoquinone; borane derivatives such as tributylborane; carbon tetrabromide, carbon tetrachloride, 1,1,2,2-tetrabromoethane, tribromoethylene, trichloroethylene, Bromotrichloromethane, tribromomethane, 3- Halogenated hydrocarbons such as Lolo-1-propene; Aldehydes such as chloral and furaldehyde: Alkyl mercaptans having 1 to 18 carbon atoms; Aromatic mercaptans such as thiophenol and toluene mercaptan; Carbon of
  • the polymerization temperature of the component (A 1 ) is generally about 30 ° C. or higher and 180 ° C. or lower, preferably 40 ° C. or higher and 150 ° C. or lower, more preferably 50 ° C. or higher and 100 ° C. or lower.
  • an unreacted monomer is contained in a polymer obtained by a solution polymerization method or the like, it can be purified by a reprecipitation method using methanol or the like in order to remove the monomer.
  • the partial polymer (A 2 ) component can be obtained by partial polymerization so as to have a viscosity that allows the monomer mixture to be applied.
  • the production of such a partial polymer is described, for example, in JP-A No. 2001-181589, and the component (A 2 ) can be produced by the method described in JP-A No. 2001-181589.
  • the monomer mixture is reacted substantially without using a solvent.
  • a specific polymerization initiator as shown below.
  • a polymerization initiator having a 10-hour half-life temperature of 41.0 ° C. or lower, preferably 20 ° C. or higher and 37.0 ° C. or lower is preferably used. Is done.
  • polymerization initiators examples include isobutyryl peroxide (10-hour half-life temperature: 32.7 ° C.), ⁇ , ⁇ ′-bis (neodecanoylperoxy) diisopropylbenzene (10-hour half-life temperature: 35.9 ° C.), cumyl peroxyneodecanoate (10 hour half-life temperature: 36.5 ° C.), di-n-propyl peroxydicarbonate (10 hour half-life temperature: 40.3 ° C.), diisopropyl per Oxydicarbonate (10-hour half-life temperature: 40.5 ° C), di-sec-butyl peroxydicarbonate (10-hour half-life temperature: 40.5 ° C), 1,1,3,3-tetramethylbutylper Oxyneodecanoate (10-hour half-life temperature: 40.7 ° C), bis (4-butylcyclohexyl) peroxydicarbonate (10-hour half-life temperature: 40.8 ) And 2,2'
  • polymerization initiators can be used alone or in combination.
  • isobutyryl peroxide (10-hour half-life temperature: 32.7 ° C.)
  • ⁇ , ⁇ ′-bis (neodecanoylperoxy) diisopropylbenzene (10-hour half-life temperature: 35.9 ° C.)
  • kumi Luperoxyneodecanoate (10-hour half-life temperature: 36.5 ° C)
  • 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (10-hour half-life temperature: 30.0 ° C)
  • the monomer mixture is heated or heated to a temperature at which the polymerization reaction can proceed when a polymerization initiator is blended, and the prescribed reaction initiator is added to the monomer mixture in the amount specified above. Then, the polymerization reaction proceeds.
  • the temperature of the monomer mixture when adding the polymerization initiator is usually in the range of 20 ° C. or higher and 80 ° C. or lower, preferably 35 ° C. or higher and 70 ° C. or lower, particularly preferably 40 ° C. or higher and 65 ° C. or lower.
  • the polymerization initiator is usually added with stirring to the monomer mixture thus heated or heated.
  • the Tg of the component (A 1 ) is preferably ⁇ 70 ° C. or more and 0 ° C. or less, from the viewpoint of more reliably achieving good adhesion and durability. More preferably ° C. or higher 0 °C or less, (a 2) components Tg ((Tg of a 2) polymer obtained by polymerizing a component) is preferably not more than 0 °C -70 ° C. or higher, - More preferably, it is 60 ° C. or more and 0 ° C. or less.
  • Tg of the components (A 1 ) and (A 2 ) is a value calculated by the following formula (1) (FOX formula).
  • Tg A W a1 / Tg a1 + W a2 / Tg a2 + W a3 / Tg a3 + W a4 / Tg a4 (1)
  • Tg A represents the glass transition temperature (K) of the component (A)
  • Tg a1 , Tg a2 , Tg a3 , and Tg a4 are the constituent monomers (a1), (a2), (a3)
  • the glass transition temperature (Tg (K)) of the homopolymer prepared from (a4) is shown, and W a1 , W a2 , W a3 and W a4 are each contained in the component (A), the constituent monomer (a1) , (A2), (a3), (a4) indicates the weight fraction.
  • Tg A is calculated as an absolute temperature (K) by the above formula (1), it is converted to a Celsius temperature (° C.) as necessary.
  • the glass transition temperatures of homopolymers prepared from typical monomers are shown in Table 1 below. More specifically, for example, Polymer Handbook 4th Edition (Polymer Handbook Third Edition, Wiley-Interscience, 2003) It is described in.
  • (A 1) component has a weight average molecular weight (Mw) of 100,000 or more 1,500,000
  • the molecular weight in the component (A 2 ) is preferably 10,000 to 1,000,000, and more preferably 10,000 to 1,000,000. More preferably, it is 500,000 or less.
  • the weight average molecular weights of the (A 1 ) component and the (A 2 ) component are obtained by obtaining the weight average molecular weight (Mw) in terms of standard polystyrene under the following conditions using GPC (gel permeation chromatography). is there.
  • ⁇ GPC measurement conditions Measuring device: HLC-8120GPC (manufactured by Tosoh Corporation) GPC column configuration: The following five columns (all manufactured by Tosoh Corporation) (1) TSK-GEL HXL-H (guard column) (2) TSK-GEL G7000HXL (3) TSK-GEL GMHXL (4) TSK-GEL GMHXL (5) TSK-GEL G2500HXL Diluted with tetrahydrofuran so that the sample concentration is 1.0 mg / cm 3 Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0 cm 3 / min Column temperature: 40 ° C.
  • Component (B) The durability which was more excellent by the adhesive sheet formed using the adhesive composition which concerns on this embodiment by constructing a crosslinked structure more reliably in the molecule
  • the number of glycidyl groups contained in one molecule of component (B) is preferably 2 or more and 8 or less, and preferably 2 or more and 6 or less.
  • the molecular weight of the component (B) is preferably 100 or more and 1000 or less, and may be 100 or more and 600 or less, for example. Moreover, when the molecular weight of the compound having two or more glycidyl groups in one molecule exceeds 1,000, the compatibility of the component (B) with the component (A) is deteriorated, and the density of the glycidyl groups is further reduced. As a result, the reaction between glycidyl groups is less likely to occur, and as a result, a crosslinked structure is hardly formed, resulting in poor durability.
  • Examples of the component (B) include 1,6-hexanediol glycidyl ether, 1,4-butanediol diglycidyl ether, and the like.
  • Examples of the commercially available component (B) include Tetrad C (Mitsubishi Gas Chemical Co., Ltd.), Tetrad X (Mitsubishi Gas Chemical Co., Ltd.), Denacol EX212L (Nagase ChemteX Corporation), and the like.
  • the isocyanate-based crosslinking agent that is the component (C) is not particularly limited as long as it is a crosslinking agent that can be crosslinked with the component (A) at room temperature or under heating.
  • isocyanate monomers such as xylylene diisocyanate, tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and divalent or higher divalents such as trimethylolpropane
  • isocyanate compound or an isocyanurate obtained by addition reaction with an alcohol compound or the like is exemplified.
  • C examples include Coronate L (Nippon Polyurethane Industry Co., Ltd.), Duranate 24A-100 (Asahi Kasei Co., Ltd.), Takenate D-120N (Mitsui Chemicals Co., Ltd.), Mytec NY260A (Mitsubishi Chemical Corporation). ) And the like.
  • urethane prepolymer type isocyanates obtained by addition reaction of isocyanate compounds with known polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, and the like can be mentioned. Of these, xylylene diisocyanate and its derivatives are preferably used.
  • the content of the component (C) in the pressure-sensitive adhesive composition according to this embodiment is 0 with respect to 100 parts by mass of the component (A) from the viewpoint of achieving a predetermined gel fraction (for example, 20% to 95%). It can be 1 part by mass or more and 5 parts by mass or less, and preferably 0.1 part by mass or more and 3 parts by mass or less.
  • Component (D) (D) a photoinitiator as component, described later (A 2) contained in the component and (B) PSA composition comprising the component, the formation of the pressure-sensitive adhesive sheet using the PSA composition It functions as a reaction initiator.
  • the content of the component (D) in the optical pressure-sensitive adhesive composition according to this embodiment is preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the component (A 2 ). More preferably, it is 1 part by mass or more and 3 parts by mass or less.
  • the component (D) is preferably, for example, an ultraviolet polymerization initiator that initiates polymerization by ultraviolet rays.
  • component (D) examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenylketone, 2-hydroxy-1- ⁇ 4- [4- (2- Hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2- Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,6-trimethylbenzoyldiphenylphosphine oxide, benzoin methyl ether , Benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl
  • component (E) is a monomer which has 2 or more of (meth) acryloyl groups.
  • the polyfunctional monomer as the component (E) can be contained in the pressure-sensitive adhesive composition containing the component (A 2 ) and the component (B).
  • the component (E) and the monomer in the component (A 2 ) react with the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition.
  • a pressure-sensitive adhesive sheet with superior durability can be obtained.
  • the content of the component (E) in the optical pressure-sensitive adhesive composition according to this embodiment is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the component (A 2 ). It is more preferable that the amount be 0.01 parts by mass or more and 5 parts by mass or less.
  • Examples of the component (E) include pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2-ethylene glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, divinylbenzene, urethane
  • Examples include acrylate, butyl di (meth) acrylate, hexyl di (meth) acrylate, and urethane acrylate. These can be used alone or in combination.
  • the optical pressure-sensitive adhesive composition according to this embodiment further includes components other than the (A) component, the (B) component, the (C) component, the (D) component, and the (E) component as necessary. Can be included.
  • the pressure-sensitive adhesive composition according to the present embodiment includes (F) a silane coupling agent (hereinafter sometimes simply referred to as “component (F)”), as long as the effects of the present invention are not impaired.
  • component (F) an ionic compound
  • (H) a solvent hereinafter sometimes simply referred to as “(H) component”
  • antioxidant antioxidant.
  • An agent, an ultraviolet absorber, a tackifier, a plasticizer, and the like may be blended.
  • (F) Silane coupling agent The pressure-sensitive adhesive layer formed using the optical pressure-sensitive adhesive composition according to the present embodiment by including the component (F) in the pressure-sensitive adhesive composition for optical films according to the present embodiment. Good adhesion to the adherend can be maintained.
  • Component (F) is, for example, a polymerizable unsaturated group-containing silicon compound such as vinyltrimethoxysilane, vinyltriethoxysilane, or methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Silicon compounds having an epoxy structure such as methyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane And amino group-containing silicon compounds such as N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; and 3-chloropropyltrimethoxysilane; oligomer-type silane coupling agents, etc.
  • the content of the component (F) in the optical film pressure-sensitive adhesive composition according to the present embodiment is 0.000 parts by weight with respect to 100 parts by weight of the component (A) from the viewpoint of maintaining good adhesion to the adherend. It can be from 01 parts by weight to 1 part by weight, and is preferably from 0.05 parts by weight to 1 part by weight.
  • the adhesive composition which concerns on this embodiment may contain the ionic compound (G).
  • the component (G) include ionic compounds that are liquid or solid at 25 ° C., which are composed of an anion and a cation. Specific examples include alkali metal salts, ionic liquids (liquid at 25 ° C. Shape), surfactants and the like.
  • alkali metal salt examples include compounds comprising an alkali metal cation such as lithium, sodium and potassium and an anion.
  • cation constituting the ionic liquid piperidinium cation, pyrrolidinium cation, cation having pyrroline skeleton, cation having pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, pyra Zolium cation, pyrazolinium cation, tetraalkylammonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation and the like.
  • anions constituting the ionic liquid include Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4.
  • ionic compound it is comprised from these cations and anions, and a liquid ionic compound is mentioned at 25 degreeC.
  • ionic compounds include 2-methyl-1-pyrroline tetrafluoroborate, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, and 1-ethyl.
  • Carbazole tetrafluoroborate 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazole Lithium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl-3-methylimidazolium dicyanamide, 1 Ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulf
  • any of nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants can be used.
  • nonionic surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene alkylphenyls such as polyoxyethylene octylphenyl ether and polyoxyethylene nonielphenyl ether.
  • Sorbitan higher fatty acid esters such as ethers, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene monolaurate, poly Polyoxyethylene higher fatty acid esters such as oxyethylene monostearate; for example, oleic acid monoglyceride, stearic acid monoglyceride Glycerine higher fatty acid esters such as id, polyoxyethylene, polyoxypropylene, polyoxyalkylenes and their block copolymers of polyoxybutylene and the like.
  • cationic surfactant examples include alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, benzalkonium chloride, alkyldimethylammonium ethosulphate and the like.
  • anionic surfactant examples include sodium laurate, sodium oleate, N-acyl-N-methylglycine sodium salt, sodium carboxylate such as sodium polyoxyethylene lauryl ether carboxylate, sodium dodecylbenzenesulfonate, dialkylsulfosuccinate.
  • amphoteric surfactant examples include carboxybetaine surfactants, aminocarboxylates, imidazolinium petines, lecithins, and alkylamine oxides.
  • conductive polymers, conductive carbon, ammonium chloride, aluminum chloride, copper chloride, iron chloride, ammonium sulfate, and the like can be used.
  • the optical pressure-sensitive adhesive composition according to this embodiment preferably has a gel fraction of 20% or more and 95% or less, from the viewpoint of being able to form a pressure-sensitive adhesive sheet that is more excellent in adhesion and durability. More preferably, it is 95% or less.
  • the gel fraction is, for example, the type and amount of component (a2) in the monomer mixture used when preparing the pressure-sensitive adhesive composition, and (C ) It can be adjusted according to the type of component and the amount used.
  • the gel fraction 0.1 g (dry weight (1)) of the crosslinked adhesive was collected in a sample bottle, and 30 cc of ethyl acetate was further added to the sample bottle and shaken for 24 hours. After that, the contents of the sample bottle were filtered with a 200 mesh stainless steel wire mesh, the residue on the wire mesh was dried at 100 ° C. for 2 hours, and the dry weight (dry weight (2)) was measured. 2).
  • Gel fraction (%) (dry weight (2) / dry weight (1)) ⁇ 100 (2)
  • the 1st manufacturing method concerning one embodiment of the present invention is a manufacturing method of an adhesive sheet using the 1st adhesive composition, and applies the 1st adhesive composition on the surface of a separator, and dries. Obtained. More specifically, the first production method includes a step of applying the first pressure-sensitive adhesive composition to the surface of the separator to obtain a coating liquid layer, removing the solvent from the coating liquid layer, and aging. And obtaining an optical pressure-sensitive adhesive sheet. That is, the 1st manufacturing method differs from the 2nd manufacturing method, and manufactures an adhesive sheet using the adhesive composition containing (H) solvent.
  • the first pressure-sensitive adhesive composition includes, for example, 100 parts by mass of (A 1 ) component, 0.3 part by mass to 20 parts by mass of (B) component, and 0.1 part by mass to 5 parts by mass of (C) component. Part or less and (H) 50 parts by mass or more and 300 parts by mass or less of the solvent.
  • the component (A 1 ) of the first pressure-sensitive adhesive composition contains a hydroxyl group
  • the component (A 2 ) and the component (C) Since a cross-linked structure can be formed by reaction with the isocyanate group therein, a pressure-sensitive adhesive layer having superior durability can be obtained.
  • the 2nd manufacturing method which concerns on one Embodiment of this invention is a manufacturing method of the adhesive sheet using the 2nd adhesive composition. Unlike a 1st manufacturing method, a 2nd manufacturing method manufactures an adhesive sheet using the adhesive composition which does not contain a solvent substantially. That is, the second pressure-sensitive adhesive composition contains, for example, 100 parts by mass of the (A 2 ) component and 0.3 parts by mass or more and 20 parts by mass or less of the (B) component, and does not substantially contain (H) the solvent. Is.
  • the second pressure-sensitive adhesive composition contains 100 parts by mass of the (A 2 ) component, 0.3 parts by mass or more and 20 parts by mass or less of the (B) component, and does not substantially contain (H) a solvent.
  • the pressure-sensitive adhesive layer can be formed in a state where substantially no is present.
  • the (A 2 ) component of the first pressure-sensitive adhesive composition contains a hydroxyl group
  • the addition of the (C) component in the (A 2 ) component Since the crosslinked structure of the hydroxyl group of this and the isocyanate group in (C) component can be formed, the adhesive layer excellent in durability can be obtained.
  • the second production method comprises (a1) (meth) acrylic acid alkyl ester monomer 60% by mass to 85% by mass and (a2) hydroxyl group-containing monomer 15% by mass to 40% by mass.
  • the total amount of the (a1) (meth) acrylic acid alkyl ester monomer and the (a2) hydroxyl group-containing monomer is 100% by mass of the (A) acrylic polymer.
  • a 2 100 parts by mass of a partial copolymer (A 2 ) of 75% by mass or more and 100% by mass or less), (B) component 0.3 part by mass or more and 20 parts by mass or less, (D) component, A step of applying a coating liquid containing a liquid to the surface of the separator to obtain a coating liquid layer, and a step of irradiating the coating liquid layer with light (for example, ultraviolet rays) to obtain an optical pressure-sensitive adhesive sheet.
  • a step of applying a coating liquid containing a liquid to the surface of the separator to obtain a coating liquid layer and a step of irradiating the coating liquid layer with light (for example, ultraviolet rays) to obtain an optical pressure-sensitive adhesive sheet.
  • the coating liquid may be prepared by adding the component (D) to the second pressure-sensitive adhesive composition.
  • the coating solution may be substantially free of a solvent.
  • “the coating solution contains substantially no solvent” means that the content of the solvent contained in the coating solution is 1% by mass or less. Specifically, the coating solution contains a solvent. Means not blended.
  • the coating liquid contains the component (A 2 ), the component (B), and the component (D) and does not substantially contain a solvent.
  • the coating solution may further include (E) component and / or (C) component. That is, in this case, the second pressure-sensitive adhesive composition is prepared by adding (E) component and (C) component or any one of them.
  • the coating liquid layer obtained by applying the coating liquid to the surface of the separator is irradiated with light such as ultraviolet rays to polymerize the polymerizable component in the coating liquid layer. That is, when (A) component and (C) component or any one of the monomers contained in (A 2 ) component are included, (E) component and (C) component or any one and ).
  • the irradiation time of light such as ultraviolet rays is usually from 1 second to 300 seconds, preferably from 1 second to 180 seconds.
  • the monomer in the component (A 2 ) is polymerized, and the glycidyl groups in the component (B) react with each other (further, the component (A 2 ) contains a hydroxyl group, When the component (C) is further included, the hydroxyl group reacts with the isocyanate group of the component (C).
  • the component (E) is included, the reaction between the monomer in the component (A 2 ) and the component (E) ), A cross-linked structure is formed, and thus a pressure-sensitive adhesive sheet having excellent durability can be obtained.
  • the said 2nd adhesive composition does not contain a solvent substantially, when manufacturing an adhesive sheet using this composition, the light irradiation process with respect to the coating liquid layer formed using this composition Therefore, the film thickness of the obtained pressure-sensitive adhesive sheet can be predicted in advance.
  • the optical pressure-sensitive adhesive composition according to this embodiment can be used for bonding members constituting a touch panel type input / output device.
  • the member to be bonded using the optical pressure-sensitive adhesive composition according to this embodiment is an optical member (for example, a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a brightness enhancement film, a light diffusion film).
  • the optical pressure-sensitive adhesive composition according to this embodiment can be suitably used for bonding members constituting a touch panel type input / output device.
  • FIG. 1 is a cross-sectional view schematically showing a configuration of an input / output device (touch panel type input / output device 100) according to an embodiment of the present invention.
  • the touch panel type input / output device 100 includes a liquid crystal display device (LCD) 10, a touch panel unit 20, and an adhesive layer 30 provided between the LCD 10 and the touch panel unit 20.
  • the pressure-sensitive adhesive layer 30 bonds the LCD 10 and the touch panel unit 20 together.
  • the pressure-sensitive adhesive layer 30 is obtained, for example, by applying the first optical pressure-sensitive adhesive composition according to this embodiment on the surface of a separator (not shown) and drying according to the first manufacturing method according to this embodiment.
  • the obtained pressure-sensitive adhesive sheet is peeled off from the separator and installed between the LCD 10 and the touch panel 20.
  • the pressure-sensitive adhesive layer 30 is prepared by adding the component (D) (and, if necessary, (E) to the second optical pressure-sensitive adhesive composition according to the present embodiment, for example, according to the second production method according to the present embodiment.
  • the coating liquid to which the component and the component (C) or any one of them is added is applied to the surface of a separator (not shown) to form a coating liquid layer, and light (for example, ultraviolet rays) is applied to the coating liquid layer.
  • light for example, ultraviolet rays
  • the LCD 10 is configured by laminating a polarizing plate 11, an adhesive layer 12, a liquid crystal panel 13, an adhesive layer 14, and a polarizing plate 15 in this order.
  • the pressure-sensitive adhesive layer 12 bonds the polarizing plate 11 and the liquid crystal panel 13, and the pressure-sensitive adhesive layer 14 bonds the liquid crystal panel 13 and the polarizing plate 15.
  • the touch panel unit 20 is configured by a scattering prevention film 16, an adhesive layer 17, an ITO layer 18, and a glass panel 19 laminated in this order.
  • the pressure-sensitive adhesive layer 17 bonds the scattering prevention film 16 and the ITO layer 18.
  • the pressure-sensitive adhesive layers 12, 14, and 17 are manufactured by the first manufacturing method or the second manufacturing method using the optical pressure-sensitive adhesive composition according to this embodiment, like the pressure-sensitive adhesive layer 30.
  • the optical pressure-sensitive adhesive composition according to this embodiment includes (A) component 100 parts by mass and (B) component 0.3 parts by mass or more and 20 parts by mass or less.
  • the glycidyl groups in the component (B) react with each other (in addition, when the component (A) includes a hydroxyl group, Since the isocyanate group of component C) reacts to form a crosslinked structure, the pressure-sensitive adhesive sheet is less likely to float or peel off under high humidity conditions and is excellent in durability.
  • the optical pressure-sensitive adhesive composition according to this embodiment does not have a property of corroding a metal because the component (A) does not substantially contain a carboxyl group, a touch panel type input containing a metal such as ITO is used. It can be suitably used for bonding members constituting the output device.
  • the pressure-sensitive adhesive sheet (optical pressure-sensitive adhesive sheet) according to this embodiment can be obtained, for example, by using the first pressure-sensitive adhesive composition or the second pressure-sensitive adhesive composition by the first manufacturing method or the second manufacturing method. it can.
  • the thickness of the pressure-sensitive adhesive sheet is usually from 10 ⁇ m to 500 ⁇ m, preferably from about 20 ⁇ m to 300 ⁇ m.
  • the first pressure-sensitive adhesive composition is applied on a substrate with a gravure coater, Mayer bar coater, air knife coater, roll coater, etc., and dried by normal temperature or heating as necessary.
  • the adhesive sheet which concerns on a form can be produced.
  • a coating liquid containing the second pressure-sensitive adhesive composition is applied by a gravure coater, a Mayer bar coater, an air knife coater, a roll coater, etc., and the coating liquid layer is irradiated with light, thereby relating to the present embodiment.
  • An adhesive sheet can be produced.
  • the pressure-sensitive adhesive sheet according to the present embodiment it is formed using the pressure-sensitive adhesive composition (the first pressure-sensitive adhesive composition or the second pressure-sensitive adhesive composition) according to the above-described embodiment, thereby improving adhesion and durability. Since it is excellent, the occurrence of floating and peeling under high humidity conditions is reduced, and it does not have the property of corroding metals. Therefore, the pressure-sensitive adhesive sheet according to this embodiment can be suitably used for bonding optical members, and more specifically, can be suitably used for bonding members constituting the touch panel type input / output device.
  • An image display device includes the optical pressure-sensitive adhesive sheet according to the above-described embodiment.
  • An example of the image display device according to the present embodiment is a liquid crystal display device.
  • an input / output device includes the optical pressure-sensitive adhesive sheet according to the above-described embodiment.
  • examples of the input / output device include a capacitive touch panel type input / output device.
  • Example 1 Production of pressure-sensitive adhesive sheet by the first production method using a pressure-sensitive adhesive composition containing the component (A 1 )) 4.1.1.
  • Preparation Example 1 Preparation of acrylic polymer
  • a monomer mixture having the blending ratio shown in Table 2 below was charged, and then an equal amount of ethyl acetate and toluene were added to the monomer. The blending amount was 30% by mass of the mixture.
  • Example 2 Production of pressure-sensitive adhesive sheet by the second production method using a pressure-sensitive adhesive composition containing the component (A 2 )) 4.2.1.
  • Preparation Example 2 Preparation of acrylic polymer
  • a monomer mixture having a blending ratio shown in Table 4 below, and normal dodecyl mercaptan, which is a chain transfer agent, are used for polymers 6, 7, and 9.
  • a monomer mixture having a blending ratio shown in Table 4 below, and normal dodecyl mercaptan, which is a chain transfer agent are used for polymers 6, 7, and 9.
  • each adhesive sheet the wet heat durability shown in the said Table 3 and Table 5 and metal corrosivity were evaluated with the following method. Moreover, the gel fraction of each adhesive composition was measured. Moreover, about the adhesive sheet of Example 2, it evaluated about the haze change after a wet heat test. The fact that acrylic polymers 1 to 4 and 6 to 8 have a hydroxyl group was confirmed by, for example, the appearance of absorption at 3400-3200 cm ⁇ 1 in the IR spectrum for each of acrylic polymers 1 to 4 and 6 to 8. .
  • the test plate was removed from the test environment and allowed to stand in a 23 ° C./50% RH atmosphere for 1 hour, and then the wet heat cycle test (durability) of the adhesive layer was visually evaluated according to the following evaluation criteria. .
  • Metal corrosive pressure-sensitive adhesive sheets obtained by using the compositions of Examples 1 to 14 and Comparative Examples 1 to 5 obtained in Production Example 1 on an ITO vapor-deposited PET film cut to 10 mm x 100 mm, to 10 mm x 60 mm Cut and pasted and autoclaved at 50 ° C. ⁇ 5 atm for 20 minutes. Next, after standing at room temperature for 1 hour, placing it in an environment of 60 ° C. and 90% RH for 500 hours, standing at 23 ° C. and humidity of 65% RH for 1 hour, then the resistance of the ITO deposited film The value was measured and compared with the resistance value before the test measured in advance, and the rate of change of the resistance value with respect to the resistance value before the test was obtained.
  • compositions of Examples 1 to 10 above are included in the component (B) by including (A) component 100 parts by mass and (B) component 0.3 parts by mass to 20 parts by mass.
  • the glycidyl group reacts within and / or between the molecules, and a cross-linked structure is formed by the reaction between the hydroxyl group contained in the component (A) and the isocyanate group contained in the component (C).
  • the pressure-sensitive adhesive sheet formed using is less likely to float or peel off under high humidity conditions, and can achieve high adhesion and excellent durability.
  • (A) component does not have a carboxyl group substantially, it does not have a property which corrodes a metal.
  • the ratio of the component (B) is not in the range of 0.3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the component (A).
  • the pressure-sensitive adhesive sheet formed using the composition is inferior in durability because it floats or peels off when it is rapidly changed from a high-temperature and high-humidity condition to a high-temperature and low-humidity condition.
  • composition of the said comparative example 3 has two or more glycidyl groups in 1 molecule, since the compound exceeding molecular weight 1,000 was used, it originates in the density of the glycidyl group in (B) component being small. Thus, crosslinking by glycidyl groups is unlikely to occur, and as a result, it is estimated that the durability is poor.
  • Comparative Example 4 used an acrylic polymer that does not have a hydroxyl group but has a carboxyl group in place of the component (A), the (B) component within and / or between the molecules. Since the glycidyl group in the component (B) and the carboxyl group in the component (A) react excessively in preference to the reaction, the cross-linking becomes too dense and inferior in durability, and the presence of the carboxyl group It is estimated that the metal has corrosive properties.
  • the glycidyl group contained in the component (B) reacts within and / or between the molecules, and by containing the component (E), the monomer in the component (A 2 ) reacts with the component (E), Since the cross-linked structure is formed, the pressure-sensitive adhesive sheet formed using the composition is less likely to float or peel off under high humidity conditions, and can achieve high adhesiveness and excellent durability.
  • the component (A) since the component (A) has substantially no carboxyl group, it does not have the property of corroding metals. Furthermore, since the compositions of Examples 11 to 19 are substantially free of a solvent, when a pressure-sensitive adhesive sheet is produced using a coating liquid containing the composition, a coating formed using the coating liquid is used. Since the film thickness does not substantially change before and after the light irradiation process for the working liquid layer, the film thickness of the obtained pressure-sensitive adhesive sheet can be predicted in advance.
  • compositions of Comparative Examples 5 and 6 have a ratio of the component (B) that is not in the range of 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the component (A).
  • the pressure-sensitive adhesive sheet formed using the material is floated or peeled off under high humidity conditions, and is inferior in durability.
  • composition of the said comparative example 7 has two or more glycidyl groups in 1 molecule, since the compound exceeding molecular weight 1,000 was used, it originates in the density of the glycidyl group in (B) component being small. Thus, crosslinking by glycidyl groups is unlikely to occur, and as a result, it is estimated that the durability is poor.
  • Comparative Example 8 used an acrylic polymer that does not have a hydroxyl group but has a carboxyl group in place of the component (A), the intramolecular and / or intermolecular components of the component (B) Since the glycidyl group in the component (B) and the carboxyl group in the component (A) react excessively in preference to the reaction, the cross-linking becomes too dense and inferior in durability, and the presence of the carboxyl group It is estimated that the metal has corrosive properties.

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Abstract

This adhesive composition for optics contains: 100 parts by mass of an acrylic polymer that contains substantially no carboxyl groups; and (B) 0.3-20 parts by mass of a compound which has two or more glycidyl groups per molecule and which has a molecular weight of at most 1,000.

Description

光学用粘着剤組成物、光学用粘着シートおよびその製造方法Optical pressure-sensitive adhesive composition, optical pressure-sensitive adhesive sheet and method for producing the same
　本発明は、光学用粘着剤組成物、光学用粘着シートおよびその製造方法に関する。 The present invention relates to an optical pressure-sensitive adhesive composition, an optical pressure-sensitive adhesive sheet, and a method for producing the same.
　画像表示装置は、近年、様々な用途や条件下において使用されており、例えば、室温条件下のみならず、高温、さらには高温多湿といった過酷な条件下においても使用されることも多くなっている。高温または高温多湿条件での使用としては、例えば、熱帯地域における使用、車両内部や野外計測機器の内部での使用が挙げられる。 In recent years, image display devices have been used under various applications and conditions. For example, they are often used not only under room temperature conditions but also under severe conditions such as high temperature and high temperature and humidity. . Examples of the use under a high temperature or high temperature and humidity condition include use in a tropical region, use inside a vehicle, and inside an outdoor measuring instrument.
　画像表示装置を構成する光学フィルムは高温や多湿環境下で収縮して、寸法変化を生じるものがある。該光学フィルムに寸法変形が生じた場合、たとえ、温度条件や湿度条件と変えたとしても、元の寸法には完全に戻ることは困難である。その結果、該光学フィルムの寸法変化によって生じた応力の影響で粘着剤層にひび割れ、剥がれ、浮きが生じるという問題が生じる。 Some optical films that make up image display devices shrink under high temperature and high humidity to cause dimensional changes. When dimensional deformation occurs in the optical film, it is difficult to completely return to the original dimensions even if the temperature and humidity conditions are changed. As a result, there arises a problem that the pressure-sensitive adhesive layer is cracked, peeled off and floated due to the stress caused by the dimensional change of the optical film.
　また、近年、画像表示装置には、例えば透明電極に使用されるＩＴＯ層等の金属酸化物が多く用いられている。被着体が金属酸化物を含む場合、金属酸化物が酸成分により腐食され、抵抗値が高くなるという問題が生じる。 In recent years, for example, metal oxides such as an ITO layer used for transparent electrodes are often used in image display devices. When the adherend contains a metal oxide, the metal oxide is corroded by an acid component, causing a problem that the resistance value is increased.
特開２００７－１６９３２９号公報JP 2007-169329 A
　本発明は、高温および多湿条件下で優れた耐久性を発揮でき、かつ、被着体を腐食しない光学用粘着剤組成物、光学用粘着シートおよびその製造方法を提供する。 The present invention provides an optical pressure-sensitive adhesive composition, an optical pressure-sensitive adhesive sheet, and a method for producing the same, which can exhibit excellent durability under high temperature and high humidity conditions and do not corrode an adherend.
　本発明者らは、このような課題を解決すべく、所定の成分を有する粘着剤組成物を用いて、優れた耐久性を有し、かつ、被着体を腐食しない粘着剤層が得られることを見出した。 In order to solve such problems, the present inventors can obtain a pressure-sensitive adhesive layer having excellent durability and not corroding an adherend by using a pressure-sensitive adhesive composition having a predetermined component. I found out.
　１．本発明の一態様に係る光学用粘着剤組成物は、（Ａ）カルボキシル基を実質的に含有しないアクリル系ポリマー１００質量部と、（Ｂ）１分子中にグリシジル基を２個以上有する、分子量１，０００以下の化合物０．３質量部以上２０質量部以下と、を含む。 1. The optical pressure-sensitive adhesive composition according to one embodiment of the present invention includes (A) 100 parts by mass of an acrylic polymer substantially free of a carboxyl group, and (B) a molecular weight having two or more glycidyl groups in one molecule. 1,000 or less compounds 0.3 mass part or more and 20 mass parts or less are included.
　２．上記１に記載の光学用粘着剤組成物において、前記（Ａ）アクリル系ポリマーは、（ａ１）（メタ）アクリル酸アルキルエステル単量体６０質量％以上８５質量％以下および（ａ２）水酸基含有単量体１５質量％以上４０質量％以下を含む単量体混合物の共重合体（Ａ１）である（ここで、前記（ａ１）（メタ）アクリル酸アルキルエステル単量体および前記（ａ２）水酸基含有単量体の合計量は、前記単量体混合物１００質量％とした場合、７５質量％以上１００質量％以下である。）ことができる。 2. 2. The optical pressure-sensitive adhesive composition as described in 1 above, wherein the (A) acrylic polymer comprises (a1) (meth) acrylic acid alkyl ester monomer of 60% by mass to 85% by mass and (a2) a hydroxyl group-containing monomer. It is a copolymer (A 1 ) of a monomer mixture containing 15% by mass to 40% by mass of a monomer (wherein (a1) (meth) acrylic acid alkyl ester monomer and (a2) hydroxyl group The total amount of the contained monomers can be 75% by mass or more and 100% by mass or less when the monomer mixture is 100% by mass.
　３．上記１または２に記載の光学用粘着剤組成物において、（Ｃ）イソシアネート系架橋剤をさらに含むことができる。 3. In the optical pressure-sensitive adhesive composition described in 1 or 2 above, (C) an isocyanate-based crosslinking agent may be further included.
　４．上記１に記載の光学用粘着剤組成物において、前記（Ａ）アクリル系ポリマーは、（ａ１）（メタ）アクリル酸アルキルエステル単量体６０質量％以上８５質量％以下および（ａ２）水酸基含有単量体１５質量％以上４０質量％以下を含む単量体混合物の部分重合物（Ａ２）である（ここで、前記（ａ１）（メタ）アクリル酸アルキルエステル単量体および前記（ａ２）水酸基含有単量体の合計量は、前記単量体混合物１００質量％とした場合、７５質量％以上１００質量％以下である。）ことができる。 4). 2. The optical pressure-sensitive adhesive composition as described in 1 above, wherein the (A) acrylic polymer comprises (a1) (meth) acrylic acid alkyl ester monomer of 60% by mass to 85% by mass and (a2) a hydroxyl group-containing monomer. It is a partial polymer (A 2 ) of a monomer mixture containing 15% by mass to 40% by mass of a monomer (wherein (a1) (meth) acrylic acid alkyl ester monomer and (a2) hydroxyl group The total amount of the contained monomers can be 75% by mass or more and 100% by mass or less when the monomer mixture is 100% by mass.
　５．上記４に記載の光学用粘着剤組成物において、前記部分重合物（Ａ２）を含む前記組成物は、（Ｅ）多官能性単量体をさらに含み、前記（Ａ）アクリル系ポリマーは、前記部分重合物（Ａ２）および前記（Ｅ）多官能性単量体を含む前記組成物より得られるものであることができる。 5. 5. The optical pressure-sensitive adhesive composition according to 4 above, wherein the composition including the partial polymer (A 2 ) further includes (E) a polyfunctional monomer, and the (A) acrylic polymer is It can be obtained from the composition containing the partial polymer (A 2 ) and the (E) polyfunctional monomer.
　６．上記２ないし５のいずれかに記載の光学用粘着剤組成物において、前記単量体混合物は、（ａ３）窒素原子含有単量体０．１質量％以上５質量％以下をさらに含むことができる。 6. 6. The optical pressure-sensitive adhesive composition according to any one of 2 to 5 above, wherein the monomer mixture may further contain (a3) a nitrogen atom-containing monomer in an amount of 0.1% by mass to 5% by mass. .
　７．上記１ないし６のいずれかに記載の光学用粘着剤組成物において、ゲル分率が２０％以上９５％以下であることができる。 7. In the optical pressure-sensitive adhesive composition according to any one of 1 to 6, the gel fraction may be 20% or more and 95% or less.
　８．上記１ないし７のいずれかに記載の光学用粘着剤組成物において、タッチパネル式入出力装置を構成する部材の貼り合わせに用いられることができる。 8. 8. The optical pressure-sensitive adhesive composition according to any one of 1 to 7, which can be used for bonding members constituting a touch panel type input / output device.
　９．本発明の別の態様にかかる光学用粘着シートは、上記１ないし７のいずれかに記載の光学用粘着剤組成物より得られる粘着剤層を有する。 9. The optical pressure-sensitive adhesive sheet according to another aspect of the present invention has a pressure-sensitive adhesive layer obtained from the optical pressure-sensitive adhesive composition described in any one of 1 to 7 above.
　１０．本発明の他の態様に係る光学用粘着シートの製造方法は、（Ａ）カルボキシル基を実質的に含有しないアクリル系ポリマー１００質量部と、（Ｂ）１分子中にグリシジル基を２個以上有する、分子量１，０００以下の化合物０．３質量部以上２０質量部以下とを含む粘着剤組成物をセパレータの表面に塗布して、塗工液層を得る工程と、前記塗工液層から溶剤を除去し、熟成して、光学用粘着シートを得る工程と、を含む。 10. The manufacturing method of the optical adhesive sheet which concerns on the other aspect of this invention has (A) 100 mass parts of acrylic polymers which do not contain a carboxyl group substantially, and (B) 2 or more glycidyl groups in 1 molecule. A step of applying a pressure-sensitive adhesive composition containing 0.3 to 20 parts by mass of a compound having a molecular weight of 1,000 or less to the surface of the separator to obtain a coating liquid layer, and a solvent from the coating liquid layer And aging to obtain an optical pressure-sensitive adhesive sheet.
　１１．上記１０の光学用粘着シートの製造方法において、前記粘着剤組成物は、（Ｃ）イソシアネート系架橋剤をさらに含むことができる。 11. In the method for producing an optical pressure-sensitive adhesive sheet according to 10 above, the pressure-sensitive adhesive composition may further include (C) an isocyanate-based crosslinking agent.
　１２．本発明の他の態様に係る光学用粘着シートの製造方法は、（ａ１）（メタ）アクリル酸アルキルエステル単量体６０質量％以上８５質量％以下および（ａ２）水酸基含有単量体１５質量％以上４０質量％以下を含む単量体混合物の部分重合物（Ａ２）１００質量部（ここで、前記（ａ１）（メタ）アクリル酸アルキルエステル単量体および前記（ａ２）水酸基含有単量体の合計量は、前記単量体混合物１００質量％とした場合、７５質量％以上１００質量％以下である。）と、（Ｂ）１分子中にグリシジル基を２個以上有する、分子量１，０００以下の化合物０．３質量部以上２０質量部以下と、（Ｄ）光重合開始剤と、を含む塗工液をセパレータの表面に塗布して、塗工液層を得る工程と、前記塗工液層に光を照射して、光学用粘着シートを得る工程と、を含む。 12 The method for producing an optical pressure-sensitive adhesive sheet according to another aspect of the present invention includes (a1) (meth) acrylic acid alkyl ester monomer 60% by mass to 85% by mass and (a2) hydroxyl group-containing monomer 15% by mass. 100 parts by mass of a partially polymerized monomer mixture (A 2 ) containing 40% by mass or less (wherein (a1) (meth) acrylic acid alkyl ester monomer and (a2) hydroxyl group-containing monomer When the monomer mixture is 100% by mass, the total amount is 75% by mass or more and 100% by mass or less.) (B) Molecular weight 1,000 having two or more glycidyl groups in one molecule. Applying the coating liquid containing 0.3 to 20 parts by mass of the following compound and (D) a photopolymerization initiator to the surface of the separator to obtain a coating liquid layer; Irradiate the liquid layer with light to create an optical adhesive sheet. And a step of obtaining a.
　１３．上記１２に記載の光学用粘着シートの製造方法において、前記塗工液は、（Ｅ）多官能性単量体をさらに含むことができる。 13. 13. The method for producing an optical pressure-sensitive adhesive sheet according to the above 12, wherein the coating liquid can further contain (E) a polyfunctional monomer.
　上記１ないし８に記載の光学用粘着剤組成物が（Ａ）カルボキシル基を実質的に含有しないアクリル系ポリマー１００質量部と、（Ｂ）１分子中にグリシジル基を２個以上有する、分子量１，０００以下の化合物０．３質量部以上２０質量部以下と、を含むことにより、適度な接着性を有し、被着体を腐食せず、かつ、高温条件下あるいは高温多湿条件下で優れた耐久性（湿熱耐久性）を発揮する塗工液層を得ることができる。 The optical pressure-sensitive adhesive composition according to any one of 1 to 8 above (A) 100 parts by mass of an acrylic polymer substantially free of carboxyl groups, and (B) a molecular weight of 1 having two or more glycidyl groups in one molecule. , 000 or less of the compound is contained in an amount of 0.3 to 20 parts by mass, has appropriate adhesiveness, does not corrode the adherend, and is excellent under high temperature conditions or high temperature and high humidity conditions. A coating liquid layer exhibiting high durability (wet heat durability) can be obtained.
　また、上記９に記載の光学用粘着シートは、上記１ないし７のいずれかに記載の光学用粘着剤組成物より得られる粘着剤層を有しているため、優れた耐久性を有し、かつ、被着体を腐食しない。よって、上記光学用粘着シートは、画像表示装置または出入力装置に好適に用いることができる。 Moreover, since the optical pressure-sensitive adhesive sheet described in 9 has a pressure-sensitive adhesive layer obtained from the optical pressure-sensitive adhesive composition described in any one of 1 to 7, the optical pressure-sensitive adhesive sheet has excellent durability, In addition, the adherend is not corroded. Therefore, the optical pressure-sensitive adhesive sheet can be suitably used for an image display device or an input / output device.
　上記１０および１１に記載の光学用粘着シートの製造方法は、（Ａ）カルボキシル基を実質的に含有しないアクリル系ポリマー１００質量部と、（Ｂ）１分子中にグリシジル基を２個以上有する、分子量１，０００以下の化合物０．３質量部以上２０質量部以下と、任意で（Ｃ）イソシアネート系架橋剤を含む粘着剤組成物をセパレータの表面に塗布して、塗工液層を得る工程と、前記塗工液層から溶剤を除去し、熟成して、光学用粘着シートを得る工程と、を含むことにより、分子内および／または分子間でのグリシジル基同士の反応が進行することで、優れた耐久性を有し、かつ、被着体を腐食しない光学用粘着シートを得ることができる。 The method for producing an optical pressure-sensitive adhesive sheet described in 10 and 11 above includes (A) 100 parts by mass of an acrylic polymer that substantially does not contain a carboxyl group, and (B) two or more glycidyl groups in one molecule. A step of obtaining a coating liquid layer by applying a pressure-sensitive adhesive composition containing 0.3 to 20 parts by mass of a compound having a molecular weight of 1,000 or less and optionally (C) an isocyanate-based crosslinking agent to the surface of the separator. And a step of removing the solvent from the coating liquid layer and aging to obtain an optical pressure-sensitive adhesive sheet, whereby the reaction between glycidyl groups within the molecule and / or between the molecules proceeds. It is possible to obtain an optical pressure-sensitive adhesive sheet that has excellent durability and does not corrode the adherend.
　また、上記１２ないし１３に記載の光学用粘着シートの製造方法は、（ａ１）（メタ）アクリル酸アルキルエステル単量体６０質量％以上８５質量％以下および（ａ２）水酸基含有単量体１５質量％以上４０質量％以下を含む単量体混合物の部分重合物（Ａ２）１００質量部（ここで、前記（ａ１）（メタ）アクリル酸アルキルエステル単量体および前記（ａ２）水酸基含有単量体の合計量は、前記単量体混合物１００質量％とした場合、７５質量％以上１００質量％以下である。）と、（Ｂ）１分子中にグリシジル基を２個以上有する、分子量１，０００以下の化合物０．３質量部以上２０質量部以下と、（Ｄ）光開始剤と、を含む混合物をセパレータの表面に塗布して、塗工液層を得る工程と、前記塗工液層に光を照射して、光学用粘着シート工程と、を含むことにより、分子内および／または分子間でのグリシジル基同士の反応が進行することで、優れた耐久性を有し、かつ、被着体を腐食しない光学用粘着シートを得ることができる。 Moreover, the manufacturing method of the optical adhesive sheet of said 12 thru | or 13 WHEREIN: (a1) (meth) acrylic-acid alkylester monomer 60 mass%-85 mass% and (a2) hydroxyl-containing monomer 15 mass % By weight of a partial mixture (A 2 ) of a monomer mixture containing from 40% by weight to 40% by weight (wherein (a1) (meth) acrylic acid alkyl ester monomer and (a2) hydroxyl group-containing monomer) The total amount of the body is 75% by mass or more and 100% by mass or less when the monomer mixture is 100% by mass.) And (B) a molecular weight of 1 having 2 or more glycidyl groups in one molecule. 000 or less compound 0.3 parts by mass or more and 20 parts by mass or less and (D) a photoinitiator is applied to the surface of the separator to obtain a coating liquid layer, and the coating liquid layer Irradiate the An optical pressure-sensitive adhesive sheet that has excellent durability and does not corrode the adherend by allowing the reaction between glycidyl groups in the molecule and / or between the molecules to proceed. Obtainable.
図１は、本発明の一実施形態に係る出入力装置（タッチパネル式入出力装置）の構成を模式的に示す断面図である。FIG. 1 is a cross-sectional view schematically showing a configuration of an input / output device (touch panel type input / output device) according to an embodiment of the present invention.
　以下、図面を参照しつつ、本発明を詳細に説明する。なお、本発明において、格別に断らない限り、「部」は「質量部」を意味し、「％」は「質量％」を意味する。 Hereinafter, the present invention will be described in detail with reference to the drawings. In the present invention, “parts” means “parts by mass” and “%” means “mass%” unless otherwise specified.
　１．光学用粘着剤組成物
　本発明の一実施形態に係る光学用粘着剤組成物（以下、単に「粘着剤組成物」と記載する場合もある。）は、（Ａ）カルボキシル基を実質的に含有しないアクリル系ポリマー（以下、単に「（Ａ）成分」と記載する場合もある。）１００質量部と、（Ｂ）１分子中にグリシジル基を２個以上有する、分子量１，０００以下の化合物（以下、単に「（Ｂ）成分」と記載する場合もある。）０．３質量部以上２０質量部以下と、を含む。 1. Optical pressure-sensitive adhesive composition The optical pressure-sensitive adhesive composition according to an embodiment of the present invention (hereinafter sometimes simply referred to as “pressure-sensitive adhesive composition”) substantially contains (A) a carboxyl group. Acrylic polymer (hereinafter sometimes simply referred to as “component (A)”) 100 parts by mass, and (B) a compound having a molecular weight of 1,000 or less having two or more glycidyl groups in one molecule ( Hereinafter, it may be simply described as “component (B).” Including 0.3 to 20 parts by mass.
　本発明において、「アクリル系ポリマー」とは、アクリル酸、アクリル酸塩、アクリル酸エステル、メタクリル酸、メタクリル酸塩、およびメタクリル酸エステルから選ばれる少なくとも１種を構成単位中に５０質量％以上含むポリマーをいう。また、「水酸基を含有しないアクリル酸エステル単量体」とは、分子構造中に水酸基を有さないアクリル酸エステル単量体をいう。 In the present invention, the “acrylic polymer” includes at least one selected from acrylic acid, acrylic acid salt, acrylic acid ester, methacrylic acid, methacrylic acid salt, and methacrylic acid ester in a structural unit of 50% by mass or more. A polymer. The “acrylic acid ester monomer not containing a hydroxyl group” means an acrylic acid ester monomer having no hydroxyl group in the molecular structure.
　本実施形態に係る粘着剤組成物を用いて形成される粘着シートにより優れた耐久性を付与できる観点で、本実施形態に係る粘着剤組成物において、（Ａ）成分の含有量に対する（Ｂ）成分の含有量は、（Ａ）成分１００質量部に対して（Ｂ）成分０．３質量部以上１５質量部以下であることが好ましく、０．３質量部以上１０質量部以下であることがより好ましい。 In the pressure-sensitive adhesive composition according to the present embodiment, the pressure-sensitive adhesive sheet formed using the pressure-sensitive adhesive composition according to the present embodiment can provide (B) the content of the component (A). The content of the component is preferably 0.3 parts by mass or more and 15 parts by mass or less, and more preferably 0.3 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the component (A). More preferred.
　本実施形態に係る粘着剤組成物において、（Ａ）成分の含有量に対する（Ｂ）成分の含有量が、（Ａ）成分１００質量部に対して（Ｂ）成分２０質量部を超える場合または０．３質量部未満である場合、耐久性に劣ることがある。 In the pressure-sensitive adhesive composition according to this embodiment, when the content of the component (B) with respect to the content of the component (A) exceeds 20 parts by mass of the component (B) with respect to 100 parts by mass of the component (A), or 0 When the amount is less than 3 parts by mass, the durability may be inferior.
　１．１．（Ａ）成分
　本発明において、「カルボキシル基を実質的に含有しない」とは、酸価が１以下であることをいい、より具体的には、（Ａ）成分の原料である単量体混合物にカルボキシル基含有単量体を含まない（（Ａ）成分の原料である単量体混合物におけるカルボキシル基含有単量体の含有量が０．１質量％以下（好ましくは０質量％）である。）ことをいう。 1.1. (A) Component In the present invention, “substantially does not contain a carboxyl group” means that the acid value is 1 or less, more specifically, a monomer mixture that is a raw material of the component (A). The content of the carboxyl group-containing monomer in the monomer mixture which is a raw material of the component (A) is 0.1% by mass or less (preferably 0% by mass). )
　（Ａ）成分がカルボキシル基を実質的に含有しないことにより、被着体への腐食性を有さない。特に、ＩＴＯ等の金属を含む被着体を腐食しないため、例えば、画像表示装置やタッチパネル等の出入力装置において、ＩＴＯ等の金属を含む被着体を腐食しない点で有用である。 (A) It does not have corrosiveness to a to-be-adhered body because a component does not contain a carboxyl group substantially. In particular, since an adherend containing a metal such as ITO is not corroded, it is useful in that an adherend containing a metal such as ITO is not corroded in an input / output device such as an image display device or a touch panel.
　また、（Ａ）成分は水酸基を含有していてもよい。より具体的には、（Ａ）成分の原料である単量体混合物が水酸基含有単量体を含む場合、（Ａ）成分が水酸基を含有することができる。（Ａ）成分が水酸基を有することは、例えば、（Ａ）成分に関するＩＲスペクトルにおいて、３４００ｃｍ－１～３２００ｃｍ－１の範囲に吸収が現れることによって確認することができる。（Ａ）成分が水酸基を有することにより、該水酸基が後述の（Ｃ）成分と反応することで、耐久性の向上を図ることができる。 Moreover, (A) component may contain the hydroxyl group. More specifically, when the monomer mixture that is the raw material of the component (A) contains a hydroxyl group-containing monomer, the component (A) can contain a hydroxyl group. (A) the component having a hydroxyl group, for example, can be confirmed by the IR spectrum, the absorption in the range of 3400 cm -1 ~ 3200 cm -1 appear about the component (A). When the component (A) has a hydroxyl group, the hydroxyl group reacts with the later-described component (C), whereby durability can be improved.
　（Ａ）成分は、（ａ１）（メタ）アクリル酸アルキルエステル単量体を主モノマーとすることができる。ここで、「（メタ）アクリル酸アルキルエステル単量体を主モノマーとする」とは、（Ａ）成分の原料である単量体混合物に含まれる単量体のうち（メタ）アクリル酸アルキルエステル単量体の含量が最も多いことをいう。 (A) A component can use (a1) (meth) acrylic acid alkyl ester monomer as a main monomer. Here, “(meth) acrylic acid alkyl ester monomer as main monomer” means (meth) acrylic acid alkyl ester among monomers contained in monomer mixture which is a raw material of component (A) The monomer content is the highest.
　また、（Ａ）成分として、第１の共重合体および第２の共重合体あるいはいずれか一方を使用することができる。第１の共重合体は、（メタ）アクリル酸アルキルエステル単量体を主モノマーとして含む単量体混合物の共重合体（Ａ１）であり、第２の共重合体は、（メタ）アクリル酸アルキルエステル単量体を主モノマーとして含む単量体混合物の部分共重合物（Ａ２）である。 Moreover, a 1st copolymer and a 2nd copolymer, or any one can be used as (A) component. The first copolymer is a monomer mixture copolymer (A 1 ) containing a (meth) acrylic acid alkyl ester monomer as a main monomer, and the second copolymer is (meth) acrylic. It is a partial copolymer (A 2 ) of a monomer mixture containing an acid alkyl ester monomer as a main monomer.
　１．１．１．（Ａ１）成分
　（Ａ１）成分は、（ａ１）（メタ）アクリル酸アルキルエステル単量体６０質量％以上８５質量％以下（好ましくは６５質量％以上８４．９質量％以下）および（ａ２）水酸基含有単量体１５質量％以上４０質量％以下（好ましくは１５質量％以上３５質量％以下）を含む単量体混合物の共重合体（Ａ１）である（ここで、前記（ａ１）（メタ）アクリル酸アルキルエステル単量体および前記（ａ２）水酸基含有単量体の合計量は、前記単量体混合物１００質量％とした場合、７５質量％以上１００質量％以下である。）ことができる。 1.1.1. (A 1 ) component (A 1 ) component comprises (a1) (meth) acrylic acid alkyl ester monomer 60% by mass to 85% by mass (preferably 65% by mass to 84.9% by mass) and (a2 ) A copolymer (A 1 ) of a monomer mixture containing 15% by mass to 40% by mass (preferably 15% by mass to 35% by mass) of a hydroxyl group-containing monomer (wherein (a1) The total amount of the (meth) acrylic acid alkyl ester monomer and the (a2) hydroxyl group-containing monomer is 75% by mass or more and 100% by mass or less when the monomer mixture is 100% by mass. Can do.
　（Ａ１）成分は例えば、本実施形態に係る光学用粘着剤組成物が（Ｈ）溶媒中に溶解または分散させて用いる場合に使用することができる（（以下、単に「（Ｈ）成分」と記載する場合もある。（Ｈ）成分については後で詳述する。）。また、本実施形態に係る光学用粘着剤組成物が（Ａ１）成分を含む場合、後述する（Ｃ）イソシアネート系架橋剤（以下、単に「（Ｃ）成分」と記載する場合もある。）をさらに含むことができる。 The component (A 1 ) can be used, for example, when the optical pressure-sensitive adhesive composition according to this embodiment is used by being dissolved or dispersed in the (H) solvent (hereinafter referred to simply as “(H) component”. (The component (H) will be described in detail later.) In addition, when the optical pressure-sensitive adhesive composition according to this embodiment includes the component (A 1 ), the (C) isocyanate described later. It may further contain a system cross-linking agent (hereinafter sometimes simply referred to as “component (C)”).
　本実施形態に係る粘着剤組成物において、（Ａ）成分として（Ａ１）成分を使用する場合、本実施形態に係る粘着剤組成物における（Ａ１）成分の含有量は、本実施形態に係る粘着剤組成物１００質量部に対して８０質量部以上９９．７質量部以下であることができ、９０質量部以上９９．５質量部以下であることが好ましい。 In the pressure-sensitive adhesive composition according to the present embodiment, when the component (A 1 ) is used as the component (A), the content of the component (A 1 ) in the pressure-sensitive adhesive composition according to the present embodiment is the same as that of the present embodiment. It can be 80 to 99.7 parts by mass, preferably 90 to 99.5 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive composition.
　１．１．２．（Ａ２）成分
　（Ａ２）成分は、（ａ１）（メタ）アクリル酸アルキルエステル単量体（以下、単に「（ａ１）成分」と記載する場合もある。）６０質量％以上８５質量％以下（好ましくは６５質量％以上８４．９質量％以下）および（ａ２）水酸基含有単量体（以下、単に「（ａ２）成分」と記載する場合もある。）１５質量％以上４０質量％以下（好ましくは１５質量％以上３５質量％以下）を含む単量体混合物の部分重合物（Ａ２）を含む組成物より得られるものである（ここで、前記（ａ１）（メタ）アクリル酸アルキルエステル単量体および前記（ａ２）水酸基含有単量体の合計量は、前記単量体混合物１００質量％とした場合、７５質量％以上１００質量％以下である。）ことができる。 1.1.2. (A 2 ) component (A 2 ) component is (a1) (meth) acrylic acid alkyl ester monomer (hereinafter sometimes simply referred to as “(a1) component”) 60 mass% or more and 85 mass% (Preferably 65% by mass or more and 84.9% by mass or less) and (a2) a hydroxyl group-containing monomer (hereinafter sometimes simply referred to as “component (a2)”) 15% by mass or more and 40% by mass or less It is obtained from a composition containing a partial polymer (A 2 ) of a monomer mixture containing (preferably 15% by mass or more and 35% by mass or less) (wherein (a1) alkyl (meth) acrylate) The total amount of the ester monomer and the (a2) hydroxyl group-containing monomer can be 75% by mass or more and 100% by mass or less when the monomer mixture is 100% by mass.
　（Ａ２）成分は例えば、本実施形態に係る光学用粘着剤組成物を、溶媒を実質的に含まない状態で塗工する場合に使用することができる。本発明において、「光学用粘着剤組成物を溶媒を実質的に含まない状態で塗工する」とは、光学用粘着剤組成物を含有する塗工液における溶媒の含有量が１質量％以下である場合をいい、より具体的には、塗工液に溶媒を配合しない場合をいう。本実施形態に係る光学用粘着剤組成物を含有する塗工液が溶媒を実質的に含まないことにより、厚膜の粘着剤層を容易に形成することができる。 The component (A 2 ) can be used, for example, when the optical pressure-sensitive adhesive composition according to this embodiment is applied in a state that does not substantially contain a solvent. In the present invention, “coating the optical pressure-sensitive adhesive composition in a state containing substantially no solvent” means that the solvent content in the coating liquid containing the optical pressure-sensitive adhesive composition is 1% by mass or less. More specifically, it means a case where a solvent is not blended in the coating liquid. When the coating liquid containing the optical pressure-sensitive adhesive composition according to this embodiment does not substantially contain a solvent, a thick-film pressure-sensitive adhesive layer can be easily formed.
　本実施形態に係る粘着剤組成物において、（Ａ）成分を（Ａ２）成分より得る場合、本実施形態に係る粘着剤組成物における（Ａ２）成分の含有量は、本実施形態に係る粘着剤組成物１００質量部に対して８０質量部以上９９．７質量部以下であることができ、９０質量部以上９９．５質量部以下であることが好ましい。 In the pressure-sensitive adhesive composition according to the present embodiment, (A) if the component obtained from (A 2) component, the content of (A 2) component in the adhesive composition according to the present embodiment, the present embodiment It can be 80 mass parts or more and 99.7 mass parts or less with respect to 100 mass parts of adhesive compositions, and it is preferable that they are 90 mass parts or more and 99.5 mass parts or less.
　また、（Ａ２）成分が適度な粘度を有することができる観点で、（Ａ２）成分における単量体の含有量（使用した単量体のうち重合せずに残存する単量体の割合）は３０質量％以上９５質量％以下であることが好ましく、４０質量％以上８０質量％以下であることがより好ましい。また、（Ａ２）成分に含まれるポリマー分は、５質量％以上７０質量％以下であることが好ましく、２０質量％以上６０質量％以下であることがより好ましい。 Further, (A 2) in terms of ingredients may have an appropriate viscosity, the proportion of residual monomers without polymerization of (A 2) content of the monomer in the component (monomers used ) Is preferably 30% by mass or more and 95% by mass or less, and more preferably 40% by mass or more and 80% by mass or less. The polymer component contained in (A 2) component is preferably 5 mass% to 70 mass%, more preferably at most 20 mass% to 60 mass%.
　また、本実施形態に係る光学用粘着剤組成物が（Ａ２）成分を含む場合、後述する（Ｃ）イソシアネート系架橋剤（以下、単に「（Ｃ）成分」と記載する場合もある。）を実質的に含まなくてもよい。本発明において、「光学用粘着剤組成物が（Ｃ）成分を実質的に含まない」とは、光学用粘着剤組成物における（Ｃ）成分の含有量が０．１質量％以下である場合をいい、より具体的には、光学用粘着剤組成物に（Ｃ）成分を配合しない場合をいう。 Also, if the optical pressure-sensitive adhesive composition according to the present embodiment comprises (A 2) component described below (C) an isocyanate crosslinking agent (hereinafter, sometimes simply referred to as "component (C)".) May not be substantially included. In the present invention, “the optical pressure-sensitive adhesive composition does not substantially contain the component (C)” means that the content of the component (C) in the optical pressure-sensitive adhesive composition is 0.1% by mass or less. More specifically, it refers to the case where the component (C) is not added to the optical pressure-sensitive adhesive composition.
　また、（Ａ２）成分の原料である単量体混合物は、（ａ３）窒素原子含有単量体（以下、単に「（ａ３）成分」と記載する場合もある。）０．１質量％以上５質量％以下をさらに含むことができる。前記単量体混合物が（ａ３）成分を含むことにより、本発明の粘着剤組成物より形成される粘着剤層の耐白化性を向上させることができる。 In addition, the monomer mixture as the raw material of the component (A 2 ) is (a3) a nitrogen atom-containing monomer (hereinafter sometimes simply referred to as “(a3) component”) 0.1% by mass or more. 5 mass% or less can further be included. When the monomer mixture contains the component (a3), the whitening resistance of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention can be improved.
　１．１．３．（ａ１）成分
　（Ａ１）成分および（Ａ２）成分の原料である単量体混合物に含まれる（ａ１）成分は、本実施形態に係る粘着剤組成物の接着性および耐久性に寄与することができる。 1.1.3. (A1) Component The (a1) component contained in the monomer mixture which is a raw material of the (A 1 ) component and the (A 2 ) component contributes to the adhesiveness and durability of the pressure-sensitive adhesive composition according to this embodiment. be able to.
　（ａ１）（メタ）アクリル酸アルキルエステル単量体として、例えば、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ｎ－プロピルアクリレート、ｎ－プロピルメタクリレート、ｎ－ブチルアクリレート、ｎ－ブチルメタクリレート、ｎ－ヘキシルアクリレート、ｎ－ヘキシルメタクリレート、ｎ－ペンチルアクリレート、ｎ－オクチルアクリレート、ｎ－オクチルメタクリレート、ｎ－ノニルアクリレート、ｎ－ヘキサデシルアクリレート、ｎ－ヘキサデシルメタクリレート、ステアリルアクリレート、ステアリルメタクリレート、ｎ－ラウリルメタクリレート、ｎ－ラウリルアクリレート、ｎ－テトラデシルメタクリレート、等の直鎖状アルキル基を有する（メタ）アクリル酸アルキルエステル単量体；イソプロピルアクリレート、イソブチルアクリレート、ｔ－ブチルアクリレート、イソプロピルメタクリレート、イソブチルメタクリレート、ｔ－ブチルメタクリレート、イソオクチルアクリレート、イソオクチルメタクリレート、２－エチルヘキシルアクリレート、２－エチルヘキシルメタクリレート等の分岐状アルキル基を有する（メタ）アクリル酸アルキルエステル単量体；シクロヘキシルアクリレート、シクロヘキシルメタクリレート、イソボルニルアクリレート、イソボルニルメタクリレート等の脂環基を有する（メタ）アクリル酸アルキルエステル単量体；が挙げられ、このうち１種を単独でまたは２種以上を組み合わせて使用することができる。このうち、本実施形態に係る粘着剤組成物を用いて形成された粘着シートの耐久性に優れている点で、（ａ１）成分は、（メタ）アクリル酸アルキルエステル直鎖状または分岐状のアルキル基を有する（メタ）アクリル酸アルキルエステル単量体であることが好ましく、分岐状のアルキル鎖を有することがより好ましい。この場合、本実施形態に係る粘着剤組成物を用いて形成された粘着シートの耐久性により優れている点で、前記アルキル基の炭素原子数は１以上２０以下（好ましくは１以上１０以下、さらに好ましくは１以上８以下）であることがさらに好ましい。 (A1) (meth) acrylic acid alkyl ester monomers include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, n -Hexyl acrylate, n-hexyl methacrylate, n-pentyl acrylate, n-octyl acrylate, n-octyl methacrylate, n-nonyl acrylate, n-hexadecyl acrylate, n-hexadecyl methacrylate, stearyl acrylate, stearyl methacrylate, n-lauryl (Meth) acrylate alkyl ester having a linear alkyl group such as methacrylate, n-lauryl acrylate, n-tetradecyl methacrylate, etc. Termonic monomers; branched alkyl groups such as isopropyl acrylate, isobutyl acrylate, t-butyl acrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, isooctyl acrylate, isooctyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate (Meth) acrylic acid alkyl ester monomer having a cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate and the like (meth) acrylic acid alkyl ester monomer; Of these, one can be used alone or two or more can be used in combination. Among these, the (a1) component is a (meth) acrylic acid alkyl ester linear or branched in that the pressure-sensitive adhesive sheet formed using the pressure-sensitive adhesive composition according to this embodiment is excellent in durability. A (meth) acrylic acid alkyl ester monomer having an alkyl group is preferred, and a branched alkyl chain is more preferred. In this case, the number of carbon atoms of the alkyl group is 1 or more and 20 or less (preferably 1 or more and 10 or less, preferably in terms of the durability of the pressure-sensitive adhesive sheet formed using the pressure-sensitive adhesive composition according to this embodiment. More preferably, it is 1 or more and 8 or less.
　１．１．４．（ａ２）成分
　（Ａ１）成分および（Ａ２）成分の原料である単量体混合物に（ａ２）成分が含まれることにより、（Ａ１）成分および（Ａ２）成分が水酸基を含有することができる。この場合、（Ａ１）成分および（Ａ２）成分に含まれる水酸基が後述の（Ｃ）成分に含まれるイソシアネート基と反応することにより、架橋構造を形成することができる。 1.1.4. The component (a2) is contained in the monomer mixture which is the raw material of the component (a2) component (A 1 ) and the component (A 2 ), so that the component (A 1 ) and the component (A 2 ) contain a hydroxyl group. be able to. In this case, a crosslinked structure can be formed by reacting the hydroxyl group contained in the (A 1 ) component and the (A 2 ) component with an isocyanate group contained in the later-described (C) component.
　（ａ２）成分としては、例えば、２－ヒドロキシエチルアクリレート、２－ヒドロキシエチルメタクリレート、２－ヒドロキシプロピルアクリレート、２－ヒドロキシプロピルメタクリレート、４－ヒドロキシブチルアクリレート、シクロヘキサンジメタノールモノアクリレート等の水酸基含有（メタ）アクリル酸エステル単量体や、Ｎ－メチロールアクリルアミド、Ｎ－エチロールアクリルアミド等が挙げられ、このうち、１種または２種以上を組み合わせて使用することができる。なかでも、炭素原子数が１以上４以下のヒドロキシアルキル基を有する（メタ）アクリル酸エステル単量体であることが好ましい。 Examples of the component (a2) include hydroxyl group-containing compounds (eg, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, cyclohexane dimethanol monoacrylate). ) Acrylic acid ester monomers, N-methylol acrylamide, N-ethylol acrylamide and the like, and among them, one kind or a combination of two or more kinds can be used. Especially, it is preferable that it is a (meth) acrylic acid ester monomer which has a C1-C4 hydroxyalkyl group.
　１．１．５．（ａ３）成分
　（Ａ１）成分および（Ａ２）成分の原料である単量体混合物に（ａ３）成分が含まれることにより、（Ａ１）成分および（Ａ２）成分が窒素原子を含有することができる。（ａ３）成分としては、例えば、ニトリル基、アミノ基、イミド基およびアミド基等から選ばれる少なくとも１種の基を含む窒素原子含有単量体が挙げられる。 1.1.5. (A3) by the component (A 1) component and (A 2) to the raw material monomer mixture which is the component (a3) that contains component containing (A 1) component and (A 2) component is a nitrogen atom can do. Examples of the component (a3) include a nitrogen atom-containing monomer containing at least one group selected from a nitrile group, an amino group, an imide group, an amide group, and the like.
　より具体的には、（ａ３）成分としては、例えば、Ｎ，Ｎ－ジメチルアミノエチルアクリレート、Ｎ，Ｎ－ジメチルアミノエチルメタクリレート、Ｎ，Ｎ－ジエチルアミノエチルメタクリレート等のアミノ基含有単量体や、アクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジエチルアクリルアミド、アクリロイルモルフォリン、Ｎ－メトキシメチルアクリルアミド、Ｎ－ブトキシメチルアクリルアミド、Ｎ－ｔ－ブチルアクリルアミド、Ｎ，Ｎ－ジメチルアミノプロピルアクリルアミド等のアミド基含有単量体や、アクリロニトリルが挙げられ、このうち、１種または２種以上を組み合わせて使用することができる。このうち、本発明の粘着剤組成物より形成される粘着剤層の耐白化性向上の点で、（ａ３）成分は、アミド基含有単量体であることがより好ましい。 More specifically, examples of the component (a3) include amino group-containing monomers such as N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, Amides such as acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, acryloylmorpholine, N-methoxymethylacrylamide, N-butoxymethylacrylamide, Nt-butylacrylamide, N, N-dimethylaminopropylacrylamide A group containing monomer and acrylonitrile are mentioned, Among these, it can be used 1 type or in combination of 2 or more types. Of these, the component (a3) is more preferably an amide group-containing monomer from the viewpoint of improving the whitening resistance of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention.
　１．１．６．（ａ４）成分
　また、（Ａ）成分である重合体を得るための前記単量体混合物は、（ａ４）（ａ１）成分、（ａ２）成分および（ａ３）成分以外の単量体（以下、単に「（ａ４）成分」と記載する場合もある。）をさらに含むことができる。（ａ４）成分としては、例えば、酢酸ビニル、スチレン、マクロモノマー等が挙げられる。 1.1.6. Component (a4) The monomer mixture for obtaining the polymer as component (A) is a monomer other than components (a4), (a1), (a2) and (a3) (hereinafter, (It may be simply described as “component (a4)”). Examples of the component (a4) include vinyl acetate, styrene, macromonomer and the like.
　１．１．７．（ａ１）成分、（ａ２）成分、および（ａ３）成分の合計量
　本実施形態に係る粘着剤組成物では、良好な接着性および耐久性をより確実に達成できる観点から、（Ａ１）成分または（Ａ２）成分を得るための前記単量体混合物中における前記（ａ１）成分、（ａ２）成分、および（ａ３）成分の合計量（前記単量体混合物を１００質量％とした場合）が９０質量％以上１００質量％以下であることができ、９５質量％以上１００質量％以下であることが好ましい。 1.1.7. The total amount of the component (a1), the component (a2), and the component (a3) In the pressure-sensitive adhesive composition according to the present embodiment, the component (A 1 ) is used from the viewpoint that good adhesiveness and durability can be achieved more reliably. Or the total amount of the component (a1), component (a2), and component (a3) in the monomer mixture for obtaining the component (A 2 ) (when the monomer mixture is 100% by mass) Can be 90% by mass or more and 100% by mass or less, and preferably 95% by mass or more and 100% by mass or less.
　１．１．８．（Ａ１）成分の重合方法
　（Ａ１）成分の重合方法は、特に制限されるものではなく、溶液重合、乳化重合、懸濁重合などの公知の方法により重合できるが、重合により得られた共重合体の混合物を用いて、本発明の粘着剤組成物を製造するにあたり、処理工程が比較的簡単でかつ短時間で行える観点から、溶液重合により重合することが好ましい。 1.1.8. Polymerization method of component (A 1 ) The polymerization method of component (A 1 ) is not particularly limited and can be polymerized by a known method such as solution polymerization, emulsion polymerization, suspension polymerization, etc., but was obtained by polymerization. In producing the pressure-sensitive adhesive composition of the present invention using a mixture of copolymers, it is preferable to perform polymerization by solution polymerization from the viewpoint that the treatment process is relatively simple and can be performed in a short time.
　溶液重合は、一般に、重合槽内に所定の有機溶媒、各単量体、重合開始剤、および必要に応じて用いられる連鎖移動剤等を仕込み、窒素気流または有機溶媒の還流温度の下で、撹拌しながら数時間加熱反応させることにより行われる。 In solution polymerization, generally, a predetermined organic solvent, each monomer, a polymerization initiator, a chain transfer agent used as necessary, and the like are charged in a polymerization tank, under a nitrogen stream or a reflux temperature of the organic solvent, The reaction is carried out by heating for several hours with stirring.
　なお、この場合において、有機溶媒、単量体および／または重合開始剤の少なくとも一部を逐次添加してもよい。有機溶媒としては、例えば、ベンゼン、トルエン、エチルベンゼン、ｎ－プロピルベンゼン、ｔ－ブチルベンゼン、ｏ－キシレン、ｍ－キシレン、ｐ－キシレン、テトラリン、デカリン、芳香族ナフサなどの芳香族炭化水素類；例えば、ｎ－ヘキサン、ｎ－ヘプタン、ｎ－オクタン、イソオクタン、ｎ－デカン、ジペンテン、石油スピリット、石油ナフサ、テレピン油などの脂肪系もしくは脂環族系炭化水素類；例えば、酢酸エチル、酢酸ｎ－ブチル、酢酸ｎ－アミル、酢酸２－ヒドロキシエチル、酢酸２－ブトキシエチル、酢酸３－メトキシブチル、安息香酸メチルなどのエステル類；例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、イソホロン、シクロヘキサノン、メチルシクロヘキサノンなどのケトン類；例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテルなどのグリコールエーテル類；例えば、メチルアルコール、エチルアルコール、ｎ－プロピルアルコール、イソプロピルアルコール、ｎ－ブチルアルコール、イソブチルアルコール、ｓ－ブチルアルコール、ｔ－ブチルアルコールなどのアルコール類；などを挙げることができる。これらの有機溶媒はそれぞれ単独で、または２種以上混合して用いることができる。 In this case, at least a part of the organic solvent, the monomer and / or the polymerization initiator may be sequentially added. Examples of the organic solvent include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, n-propylbenzene, t-butylbenzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, aromatic naphtha; For example, aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, isooctane, n-decane, dipentene, petroleum spirit, petroleum naphtha, turpentine oil; Esters such as butyl, n-amyl acetate, 2-hydroxyethyl acetate, 2-butoxyethyl acetate, 3-methoxybutyl acetate, methyl benzoate; for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, methylcyclohexanone Ketones such as; Glycol ethers such as tylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and alcohols such as n-butyl alcohol, isobutyl alcohol, s-butyl alcohol, and t-butyl alcohol. These organic solvents can be used alone or in combination of two or more.
　これら重合用有機溶媒のうち、（Ａ１）成分の重合に際しては、重合反応中に連鎖移動を生じにくい有機溶媒、例えば、エステル類、ケトン類を使用することが好ましく、特に、（Ａ１）成分の溶解性、重合反応の容易さなどの点から、酢酸エチル、メチルエチルケトン、アセトンなどの使用が好ましい。 Among these organic solvents for polymerization, when polymerizing the component (A 1 ), it is preferable to use an organic solvent that hardly causes chain transfer during the polymerization reaction, for example, esters and ketones, and in particular, (A 1 ) From the viewpoints of solubility of components and ease of polymerization reaction, use of ethyl acetate, methyl ethyl ketone, acetone or the like is preferable.
　前記重合開始剤としては、通常の溶液重合で使用できる有機過酸化物、アゾ化合物などを使用することが可能である。このような有機過酸化物としては、例えば、ｔ－ブチルハイドロパーオキサイド、クメンハイドロオキサイド、ジクミルパーオキサイド、ベンゾイルパーオキシド、ラウロイルパーオキシド、カプロイルパーオキシド、ジイソプロピルパーオキシジカーボネート、ジ－２－エチルヘキシルパーオキシジカーボネート、ｔ－ブチルパーオキシビバレート、２，２－ビス（４，４－ジ－ｔ－ブチルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジ－ｔ－アミルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジ－ｔ－オクチルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジ－α－クミルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジ－ｔ－ブチルパーオキシシクロヘキシル）ブタン、２，２－ビス（４，４－ジ－ｔ－オクチルパーオキシシクロヘキシル）ブタンなどが挙げられ、アゾ化合物としては、例えば、２，２´－アゾビス－イソブチロニトリル、２，２´－アゾビス－２，４－ジメチルバレロニトリル、２，２´－アゾビス－４－メトキシ－２，４－ジメチルバレロニトリルなどを挙げることができる。 As the polymerization initiator, it is possible to use organic peroxides and azo compounds that can be used in ordinary solution polymerization. Examples of such organic peroxides include t-butyl hydroperoxide, cumene hydroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, diisopropyl peroxydicarbonate, and di-2. -Ethylhexyl peroxydicarbonate, t-butylperoxybivalate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 2,2-bis (4,4-di-t- Amylperoxycyclohexyl) propane, 2,2-bis (4,4-di-t-octylperoxycyclohexyl) propane, 2,2-bis (4,4-di-α-cumylperoxycyclohexyl) propane, 2 , 2-Bis (4,4-di-t-butylperoxycyclohexyl Examples include butane and 2,2-bis (4,4-di-t-octylperoxycyclohexyl) butane. Examples of the azo compound include 2,2′-azobis-isobutyronitrile and 2,2 ′. -Azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and the like.
　これら重合開始剤の使用量は、通常、単量体合計１００質量部に対して０．０１質量部以上２質量部以下であり、好ましくは０．０２質量部以上１．０質量部以下である。 The amount of these polymerization initiators used is usually 0.01 parts by mass or more and 2 parts by mass or less, and preferably 0.02 parts by mass or more and 1.0 parts by mass or less with respect to 100 parts by mass of the total monomer. .
　また、本発明の粘着剤組成物に含まれる（Ａ１）成分の製造に際しては、本発明の目的および効果を損なわない範囲で、必要に応じて連鎖移動剤を使用することが可能である。 Further, in the production of the component (A 1 ) contained in the pressure-sensitive adhesive composition of the present invention, a chain transfer agent can be used as necessary within a range that does not impair the purpose and effect of the present invention.
　このような連鎖移動剤としては、例えば、シアノ酢酸；シアノ酢酸の炭素数１以上８以下のアルキルエステル類；ブロモ酢酸；ブロモ酢酸の炭素数１以上８以下のアルキルエステル類；アントラセン、フェナントレン、フルオレン、９－フェニルフルオレンなどの芳香族化合物類；ｐ－ニトロアニリン、ニトロベンゼン、ジニトロベンゼン、ｐ－ニトロ安息香酸、ｐ－ニトロフェノール、ｐ－ニトロトルエンなどの芳香族ニトロ化合物類；ベンゾキノン、２，３，５，６－テトラメチル－ｐ－ベンゾキノンなどのベンゾキノン誘導体類；トリブチルボランなどのボラン誘導体；四臭化炭素、四塩化炭素、１，１，２，２－テトラブロモエタン、トリブロモエチレン、トリクロロエチレン、ブロモトリクロロメタン、トリブロモメタン、３－クロロ－１－プロペンなどのハロゲン化炭化水素類；クロラール、フラルデヒドなどのアルデヒド類：炭素数１～１８のアルキルメルカプタン類；チオフェノール、トルエンメルカプタンなどの芳香族メルカプタン類；メルカプト酢酸、メルカプト酢酸の炭素数１以上１０以下のアルキルエステル類；炭素数１以上１２以下のヒドロキシアルキルメルカプタン類；ピネン、ターピノレンなどのテルペン類；などを挙げることができる。 Examples of such chain transfer agents include cyanoacetic acid; alkyl esters having 1 to 8 carbon atoms of cyanoacetic acid; bromoacetic acid; alkyl esters having 1 to 8 carbon atoms of bromoacetic acid; anthracene, phenanthrene, and fluorene. Aromatic compounds such as 9-phenylfluorene; aromatic nitro compounds such as p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol and p-nitrotoluene; benzoquinone, 2,3, Benzoquinone derivatives such as 5,6-tetramethyl-p-benzoquinone; borane derivatives such as tributylborane; carbon tetrabromide, carbon tetrachloride, 1,1,2,2-tetrabromoethane, tribromoethylene, trichloroethylene, Bromotrichloromethane, tribromomethane, 3- Halogenated hydrocarbons such as Lolo-1-propene; Aldehydes such as chloral and furaldehyde: Alkyl mercaptans having 1 to 18 carbon atoms; Aromatic mercaptans such as thiophenol and toluene mercaptan; Carbon of mercaptoacetic acid and mercaptoacetic acid Examples thereof include alkyl esters having 1 to 10 carbon atoms; hydroxyalkyl mercaptans having 1 to 12 carbon atoms; and terpenes such as pinene and terpinolene.
　（Ａ１）成分の重合温度としては、一般に約３０℃以上１８０℃以下であり、好ましくは４０℃以上１５０℃以下であり、より好ましくは５０℃以上１００℃以下の範囲である。なお、溶液重合法などで得られた重合物中に未反応の単量体が含まれる場合は、該単量体を除くために、メタノールなどによる再沈澱法で精製することも可能である。 The polymerization temperature of the component (A 1 ) is generally about 30 ° C. or higher and 180 ° C. or lower, preferably 40 ° C. or higher and 150 ° C. or lower, more preferably 50 ° C. or higher and 100 ° C. or lower. When an unreacted monomer is contained in a polymer obtained by a solution polymerization method or the like, it can be purified by a reprecipitation method using methanol or the like in order to remove the monomer.
　１．１．９．（Ａ２）成分の重合方法
　（Ａ２）成分である部分重合物は、単量体混合物を塗工できる粘度になるように部分的に重合することにより得ることができる。このような部分重合物の製造は例えば、特開２００１－１８１５８９号公報に記載されており、（Ａ２）成分は特開２００１－１８１５８９号公報に記載の方法によって製造することができる。 1.1.9. (A 2 ) Component Polymerization Method The partial polymer (A 2 ) component can be obtained by partial polymerization so as to have a viscosity that allows the monomer mixture to be applied. The production of such a partial polymer is described, for example, in JP-A No. 2001-181589, and the component (A 2 ) can be produced by the method described in JP-A No. 2001-181589.
　より具体的には、（Ａ２）成分の製造には、塊状重合を用いることが好ましい。（Ａ２）成分である部分重合物を製造するための塊状重合では、実質的に溶媒を使用せずに単量体混合物を反応させる。この場合、塊状重合では、以下に示すような特定の重合開始剤を使用して重合させることが好ましい。ここで使用される重合開始剤としては、以下に示すように、１０時間半減期温度が４１．０℃以下、好ましくは２０℃以上３７．０℃以下の範囲内にある重合開始剤が好ましく使用される。 More specifically, it is preferable to use bulk polymerization for the production of the component (A 2 ). In the bulk polymerization for producing the partial polymer as the component (A 2 ), the monomer mixture is reacted substantially without using a solvent. In this case, in bulk polymerization, it is preferable to perform polymerization using a specific polymerization initiator as shown below. As the polymerization initiator used here, as shown below, a polymerization initiator having a 10-hour half-life temperature of 41.0 ° C. or lower, preferably 20 ° C. or higher and 37.0 ° C. or lower is preferably used. Is done.
　このような重合開始剤の例としては、イソブチリルパーオキサイド（１０時間半減期温度：３２．７℃）、α，α’－ビス（ネオデカノイルパーオキシ）ジイソプロピルベンゼン（１０時間半減期温度：３５．９℃）、クミルパーオキシネオデカノエート（１０時間半減期温度：３６．５℃）、ジ－ｎ－プロピルパーオキシジカーボネート（１０時間半減期温度：４０．３℃）、ジイソプロピルパーオキシジカーボネート（１０時間半減期温度：４０．５℃）、ジ－ｓｅｃ－ブチルパーオキシジカーボネート（１０時間半減期温度:４０．５℃）、１，１，３，３－テトラメチルブチルパーオキシネオデカノエート（１０時間半減期温度:４０．７℃）、ビス(4-ブチルシクロヘキシル)パーオキシジカーボネート（１０時間半減期温度:４０．８℃）および２，２’－アゾビス(４－メトキシ－２，４－ジメチルバレロニトリル)（１０時間半減期温度:３０．０℃）を挙げることができる。これらの重合開始剤単独であるいは組み合わせて使用することができる。これらの中でも、イソブチリルパーオキサイド（１０時間半減期温度:３２．７℃）、α，α’－ビス（ネオデカノイルパーオキシ）ジイソプロピルベンゼン（１０時間半減期温度:３５．９℃）、クミルパーオキシネオデカノエート（１０時間半減期温度:３６．５℃）、２，２’－アゾビス(４－メトキシ－２，４－ジメチルバレロニトリル)（１０時間半減期温度:３０．０℃）を使用することが好ましい。 Examples of such polymerization initiators include isobutyryl peroxide (10-hour half-life temperature: 32.7 ° C.), α, α′-bis (neodecanoylperoxy) diisopropylbenzene (10-hour half-life temperature: 35.9 ° C.), cumyl peroxyneodecanoate (10 hour half-life temperature: 36.5 ° C.), di-n-propyl peroxydicarbonate (10 hour half-life temperature: 40.3 ° C.), diisopropyl per Oxydicarbonate (10-hour half-life temperature: 40.5 ° C), di-sec-butyl peroxydicarbonate (10-hour half-life temperature: 40.5 ° C), 1,1,3,3-tetramethylbutylper Oxyneodecanoate (10-hour half-life temperature: 40.7 ° C), bis (4-butylcyclohexyl) peroxydicarbonate (10-hour half-life temperature: 40.8 ) And 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (10-hour half-life temperature: 30.0 ° C.) can be mentioned. These polymerization initiators can be used alone or in combination. Among these, isobutyryl peroxide (10-hour half-life temperature: 32.7 ° C.), α, α′-bis (neodecanoylperoxy) diisopropylbenzene (10-hour half-life temperature: 35.9 ° C.), kumi Luperoxyneodecanoate (10-hour half-life temperature: 36.5 ° C), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (10-hour half-life temperature: 30.0 ° C) Is preferably used.
　こうした方法では、重合開始剤を配合したときに重合反応が進行しうる温度に単量体混合物を加熱あるいは加温し、この単量体混合物中に上記所定の反応開始剤を上記規定する量添加して重合反応を進行させる。重合開始剤を添加する際の単量体混合物の温度は通常は２０℃以上８０℃以下、好ましくは３５℃以上７０℃以下、特に好ましくは４０℃以上６５℃以下の範囲内にある。こうして加熱あるいは加温した単量体混合物に重合開始剤を、通常は攪拌下に加える。 In such a method, the monomer mixture is heated or heated to a temperature at which the polymerization reaction can proceed when a polymerization initiator is blended, and the prescribed reaction initiator is added to the monomer mixture in the amount specified above. Then, the polymerization reaction proceeds. The temperature of the monomer mixture when adding the polymerization initiator is usually in the range of 20 ° C. or higher and 80 ° C. or lower, preferably 35 ° C. or higher and 70 ° C. or lower, particularly preferably 40 ° C. or higher and 65 ° C. or lower. The polymerization initiator is usually added with stirring to the monomer mixture thus heated or heated.
　このように反応させることにより、仕込みの単量体混合物中の単量体の５質量％以上７０質量％以下が重合した部分共重合体が得られる。 By reacting in this way, a partial copolymer in which 5% by mass or more and 70% by mass or less of the monomer in the charged monomer mixture is polymerized can be obtained.
　１．１．１０．Ｔｇ
　本実施形態に係る粘着剤組成物では、良好な接着性および耐久性をより確実に達成できる観点から、（Ａ１）成分のＴｇは－７０℃以上０℃以下であることが好ましく、－６０℃以上０℃以下であることがより好ましく、（Ａ２）成分のＴｇ（（Ａ２）成分を重合して得られるポリマーのＴｇ）は－７０℃以上０℃以下であることが好ましく、－６０℃以上０℃以下であることがより好ましい。 1.1.10. Tg
In the pressure-sensitive adhesive composition according to this embodiment, the Tg of the component (A 1 ) is preferably −70 ° C. or more and 0 ° C. or less, from the viewpoint of more reliably achieving good adhesion and durability. more preferably ° C. or higher 0 ℃ or less, (a 2) components Tg ((Tg of a 2) polymer obtained by polymerizing a component) is preferably not more than 0 ℃ -70 ° C. or higher, - More preferably, it is 60 ° C. or more and 0 ° C. or less.
　なお、本発明において、（Ａ１）成分および（Ａ２）成分のＴｇは、下記式（１）（ＦＯＸの式）により算出された値である。 In the present invention, Tg of the components (A 1 ) and (A 2 ) is a value calculated by the following formula (1) (FOX formula).
　１／ＴｇＡ＝Ｗａ１／Ｔｇａ１＋Ｗａ２／Ｔｇａ２＋Ｗａ３／Ｔｇａ３＋Ｗａ４／Ｔｇａ４　・・・・（１）
　（式中、ＴｇＡは、（Ａ）成分のガラス転移温度（Ｋ）を示し、Ｔｇａ１，Ｔｇａ２，Ｔｇａ３，Ｔｇａ４はそれぞれ、構成モノマー（ａ１），（ａ２），（ａ３），（ａ４）から調製されたホモポリマーのガラス転移温度（Ｔｇ（Ｋ））を示し、Ｗａ１，Ｗａ２，Ｗａ３，Ｗａ４はそれぞれ、（Ａ）成分中に含まれる、構成モノマー（ａ１），（ａ２），（ａ３），（ａ４）の重量分率を示す。）
　なお、上記式（１）により、ＴｇＡは、絶対温度（Ｋ）として算出されるので、必要に応じて摂氏温度（℃）に換算される。 1 / Tg A = W a1 / Tg a1 + W a2 / Tg a2 + W a3 / Tg a3 + W a4 / Tg a4 (1)
(In the formula, Tg A represents the glass transition temperature (K) of the component (A), and Tg a1 , Tg a2 , Tg a3 , and Tg a4 are the constituent monomers (a1), (a2), (a3), and The glass transition temperature (Tg (K)) of the homopolymer prepared from (a4) is shown, and W a1 , W a2 , W a3 and W a4 are each contained in the component (A), the constituent monomer (a1) , (A2), (a3), (a4) indicates the weight fraction.)
In addition, since Tg A is calculated as an absolute temperature (K) by the above formula (1), it is converted to a Celsius temperature (° C.) as necessary.
　また、代表的なモノマーから調製されたホモポリマーのガラス転移温度は、下記表１に示されるが、より具体的には、たとえば、ポリマーハンドブック４版（Polymer Handbook Third Edition, Wiley-Interscience,2003）などに記載されている。 The glass transition temperatures of homopolymers prepared from typical monomers are shown in Table 1 below. More specifically, for example, Polymer Handbook 4th Edition (Polymer Handbook Third Edition, Wiley-Interscience, 2003) It is described in.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　１．１．１１．重量平均分子量（Ｍｗ）
　また、本実施形態に係る粘着剤組成物において、良好な接着性および耐久性をより確実に達成できる観点から、（Ａ１）成分は、重量平均分子量（Ｍｗ）が１０万以上１５０万以下であることが好ましく、２０万以上１００万以下であることがより好ましく、（Ａ２）成分中のポリマー分は、重量平均分子量（Ｍｗ）が１万以上１００万以下であることが好ましく、３万以上５０万以下であることがより好ましい。ここで、（Ａ１）成分および（Ａ２）成分の重量平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）を用い、下記の条件で標準ポリスチレン換算による重量平均分子量（Ｍｗ）を求めたものである。 1.1.11. Weight average molecular weight (Mw)
Further, in the pressure-sensitive adhesive composition according to the present embodiment, from the viewpoint of more reliably achieving good adhesion and durability, (A 1) component has a weight average molecular weight (Mw) of 100,000 or more 1,500,000 Preferably, the molecular weight in the component (A 2 ) is preferably 10,000 to 1,000,000, and more preferably 10,000 to 1,000,000. More preferably, it is 500,000 or less. Here, the weight average molecular weights of the (A 1 ) component and the (A 2 ) component are obtained by obtaining the weight average molecular weight (Mw) in terms of standard polystyrene under the following conditions using GPC (gel permeation chromatography). is there.
　＜ＧＰＣ測定条件＞
測定装置：ＨＬＣ－８１２０ＧＰＣ（東ソー社製）
ＧＰＣカラム構成：以下の５連カラム（すべて東ソー社製）
　（１）ＴＳＫ－ＧＥＬ　ＨＸＬ－Ｈ（ガードカラム）
　（２）ＴＳＫ－ＧＥＬ　Ｇ７０００ＨＸＬ
　（３）ＴＳＫ－ＧＥＬ　ＧＭＨＸＬ
　（４）ＴＳＫ－ＧＥＬ　ＧＭＨＸＬ
　（５）ＴＳＫ－ＧＥＬ　Ｇ２５００ＨＸＬ
サンプル濃度：１．０ｍｇ／ｃｍ３となるように、テトラヒドロフランで希釈
移動相溶媒：テトラヒドロフラン
流量：１．０ｃｍ３／分
カラム温度：４０℃ <GPC measurement conditions>
Measuring device: HLC-8120GPC (manufactured by Tosoh Corporation)
GPC column configuration: The following five columns (all manufactured by Tosoh Corporation)
(1) TSK-GEL HXL-H (guard column)
(2) TSK-GEL G7000HXL
(3) TSK-GEL GMHXL
(4) TSK-GEL GMHXL
(5) TSK-GEL G2500HXL
Diluted with tetrahydrofuran so that the sample concentration is 1.0 mg / cm 3 Mobile phase solvent: Tetrahydrofuran Flow rate: 1.0 cm 3 / min Column temperature: 40 ° C.
　１．２．（Ｂ）成分
　（Ｂ）成分の分子内および／または分子間で架橋構造をより確実に構築することによって、本実施形態に係る粘着剤組成物を用いて形成される粘着シートにより優れた耐久性を付与できる観点で、（Ｂ）成分１分子中に含まれるグリシジル基の数は２個以上８個以下であることが好ましく、２個以上６個以下であることが好ましい。 1.2. (B) Component (B) The durability which was more excellent by the adhesive sheet formed using the adhesive composition which concerns on this embodiment by constructing a crosslinked structure more reliably in the molecule | numerator of a component, and / or between molecules. The number of glycidyl groups contained in one molecule of component (B) is preferably 2 or more and 8 or less, and preferably 2 or more and 6 or less.
　また、（Ｂ）成分の分子量は１００以上１０００以下であることが好ましく、例えば、１００以上６００以下であってもよい。また、１分子中にグリシジル基を２個以上有する化合物の分子量が１，０００を超えると、（Ｂ）成分の（Ａ）成分との相溶性が悪化し、さらにはグリシジル基の密度が小さくなることに起因して、グリシジル基同士の反応が起こりにくくなる結果、架橋構造が形成されにくくなるため、耐久性が劣る。 The molecular weight of the component (B) is preferably 100 or more and 1000 or less, and may be 100 or more and 600 or less, for example. Moreover, when the molecular weight of the compound having two or more glycidyl groups in one molecule exceeds 1,000, the compatibility of the component (B) with the component (A) is deteriorated, and the density of the glycidyl groups is further reduced. As a result, the reaction between glycidyl groups is less likely to occur, and as a result, a crosslinked structure is hardly formed, resulting in poor durability.
　（Ｂ）成分としては、例えば、１，６－ヘキサンジオールグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル等が挙げられる。市販の（Ｂ）成分としては、例えば、テトラッドＣ（三菱瓦斯化学株式会社）、テトラッドＸ（三菱瓦斯化学株式会社）、デナコールＥＸ２１２Ｌ（ナガセケムテックス株式会社）等が挙げられる。 Examples of the component (B) include 1,6-hexanediol glycidyl ether, 1,4-butanediol diglycidyl ether, and the like. Examples of the commercially available component (B) include Tetrad C (Mitsubishi Gas Chemical Co., Ltd.), Tetrad X (Mitsubishi Gas Chemical Co., Ltd.), Denacol EX212L (Nagase ChemteX Corporation), and the like.
　１．３．（Ｃ）成分
　本実施形態に係る粘着剤組成物において、（Ｃ）成分であるイソシアネート系架橋剤は、常温または加熱下で（Ａ）成分と架橋し得る架橋剤であれば特に限定されないが、例えば、キシリレンジイソシアネート、トリレンジイソシアネート、クロルフェニレンジイソシアネート、ヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、イソホロンジイソシアネート、ジフェニルメタンジイソシアネート、水添されたジフェニルメタンジイソシアネートなどのイソシアネートモノマーや、それらをトリメチロールプロパンなどの２価以上のアルコール化合物等に付加反応させたイソシアネート化合物やイソシアヌレート化物等が例示される。市販の（Ｃ）成分としては、例えば、コロネートＬ（日本ポリウレタン工業株式会社）、デュラネート２４Ａ－１００（旭化成株式会社）、タケネートＤ－１２０Ｎ(三井化学株式会社)、マイテックＮＹ２６０Ａ（三菱化学株式会社）等が挙げられる。 1.3. Component (C) In the pressure-sensitive adhesive composition according to the present embodiment, the isocyanate-based crosslinking agent that is the component (C) is not particularly limited as long as it is a crosslinking agent that can be crosslinked with the component (A) at room temperature or under heating. For example, isocyanate monomers such as xylylene diisocyanate, tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, and divalent or higher divalents such as trimethylolpropane An isocyanate compound or an isocyanurate obtained by addition reaction with an alcohol compound or the like is exemplified. Examples of commercially available component (C) include Coronate L (Nippon Polyurethane Industry Co., Ltd.), Duranate 24A-100 (Asahi Kasei Co., Ltd.), Takenate D-120N (Mitsui Chemicals Co., Ltd.), Mytec NY260A (Mitsubishi Chemical Corporation). ) And the like.
　また、公知のポリエーテルポリオールやポリエステルポリオール、アクリルポリオール、ポリブタジエンポリオール、ポリイソプレンポリオールなどにイソシアネート化合物を付加反応させたウレタンプレポリマー型のイソシアネート等も挙げられる。これらのうち、キシリレンジイソシアネートおよびその誘導体などが好ましく用いられる。 Also, urethane prepolymer type isocyanates obtained by addition reaction of isocyanate compounds with known polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, and the like can be mentioned. Of these, xylylene diisocyanate and its derivatives are preferably used.
　本実施形態に係る粘着剤組成物における（Ｃ）成分の含有量は、所定のゲル分率（例えば２０％以上９５％以下）を達成できる観点から、（Ａ）成分１００質量部に対して０．１質量部以上５質量部以下であることができ、０．１質量部以上３質量部以下であることが好ましい。 The content of the component (C) in the pressure-sensitive adhesive composition according to this embodiment is 0 with respect to 100 parts by mass of the component (A) from the viewpoint of achieving a predetermined gel fraction (for example, 20% to 95%). It can be 1 part by mass or more and 5 parts by mass or less, and preferably 0.1 part by mass or more and 3 parts by mass or less.
　１．４．（Ｄ）成分
　（Ｄ）成分である光開始剤は、後述する（Ａ２）成分および（Ｂ）成分を含む粘着剤組成物に含有され、該粘着剤組成物を用いた粘着シートの形成の際の反応開始剤としての機能を有する。本実施形態に係る光学用粘着剤組成物中における（Ｄ）成分の含有量は、（Ａ２）成分１００質量部に対して０．０５質量部以上５質量部以下であることが好ましく、０．１質量部以上３質量部以下であることがより好ましい。（Ｄ）成分としては、例えば、紫外線によって重合が開始される紫外線重合開始剤であることが好ましい。 1.4. Component (D) (D) a photoinitiator as component, described later (A 2) contained in the component and (B) PSA composition comprising the component, the formation of the pressure-sensitive adhesive sheet using the PSA composition It functions as a reaction initiator. The content of the component (D) in the optical pressure-sensitive adhesive composition according to this embodiment is preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the component (A 2 ). More preferably, it is 1 part by mass or more and 3 parts by mass or less. The component (D) is preferably, for example, an ultraviolet polymerization initiator that initiates polymerization by ultraviolet rays.
　（Ｄ）成分としては、例えば、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、１－ヒドロキシ－シクロヘキシル－フェニルケトン、２-ヒロドキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル-プロピオニル）－ベンジル］フェニル}－２－メチル－プロパン－１－オン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、２－メチル－１［４－（メチルチオ）フェニル］－２－モリフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、６－トリメチルベンゾイルジフェニルホスフィンオキサイド、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインプロピルエーテル、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、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、アニソールメチルエーテル、２，２－ジエトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、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、２－ナフタレンスルホニルクロライドば、１－フェニル－１，１－プロパンジオン－２－（ｏ－エトキシカルボニル）－オキシム、ベンゾイン、ベンジル、ベンゾフェノン、ベンゾイル安息香酸、３，３´－ジメチル－４－メトキシベンゾフェノン、ポリビニルベンゾフェノン、α－ヒドロキシシクロヘキシルフェニルケトン、ベンジルジメチルケタール、チオキサントン、２－クロロチオキサントン、２－メチルチオキサントン、２，４－ジメチルチオキサントン、イソプロピルチオキサントン、２，４－ジクロロチオキサントン、２，４－ジエチルチオキサントン、２，４－ジイソプロピルチオキサントン、ドデシルチオキサントンなどを挙げることができる。このような光重合開始剤は単独であるいは組み合わせて使用することができる。 Examples of the component (D) include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenylketone, 2-hydroxy-1- {4- [4- (2- Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2- Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,6-trimethylbenzoyldiphenylphosphine oxide, benzoin methyl ether , Benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, anisole methyl ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 2-naphthalenesulfonyl chloride, 1-phenyl-1,1-propanedione-2- (O-ethoxycarbonyl) -oxime, benzoin, benzyl, benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydro Cycyclohexyl phenyl ketone, benzyldimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Examples thereof include thioxanthone and dodecyl thioxanthone. Such photopolymerization initiators can be used alone or in combination.
　１．５．（Ｅ）成分
　（Ｅ）成分は、（メタ）アクリロイル基を２個以上有する単量体である。（Ｅ）成分である多官能性単量体は、（Ａ２）成分および（Ｂ）成分を含む粘着剤組成物に含有させることができる。（Ｅ）成分が前記粘着剤組成物に含有されることにより、該粘着剤組成物から形成される粘着剤層に（Ｅ）成分と（Ａ２）成分中の単量体とが反応して架橋構造を形成することにより、耐久性により優れた粘着シートを得ることができる。本実施形態に係る光学用粘着剤組成物中における（Ｅ）成分の含有量は、（Ａ２）成分１００質量部に対して０．０１質量部以上１０質量部以下であることが好ましく、０．０１質量部以上５質量部以下であることがより好ましい。 1.5. (E) component (E) A component is a monomer which has 2 or more of (meth) acryloyl groups. The polyfunctional monomer as the component (E) can be contained in the pressure-sensitive adhesive composition containing the component (A 2 ) and the component (B). When the component (E) is contained in the pressure-sensitive adhesive composition, the component (E) and the monomer in the component (A 2 ) react with the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition. By forming a cross-linked structure, a pressure-sensitive adhesive sheet with superior durability can be obtained. The content of the component (E) in the optical pressure-sensitive adhesive composition according to this embodiment is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the component (A 2 ). It is more preferable that the amount be 0.01 parts by mass or more and 5 parts by mass or less.
　（Ｅ）成分としては、例えば、ペンタエリスリトールジ（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ヘキサ（メタ）アクリレート、１，２－エチレングリコールジ（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、１，１２－ドデカンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、ジビニルベンゼン、ウレタンアクリレート、ブチルジ（メタ）アクリレート、ヘキシルジ（メタ）アクリレート、ウレタンアクリレート等を挙げることができる。これらは単独であるいは組み合わせて使用することができる。 Examples of the component (E) include pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2-ethylene glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, divinylbenzene, urethane Examples include acrylate, butyl di (meth) acrylate, hexyl di (meth) acrylate, and urethane acrylate. These can be used alone or in combination.
　１．６．その他の成分
　本実施形態に係る光学用粘着剤組成物は、必要に応じて、（Ａ）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分および（Ｅ）成分以外の成分をさらに含むことができる。例えば、本実施形態に係る粘着剤組成物には、本発明の効果を損なわない範囲で、（Ｆ）シランカップリング剤（以下、単に「（Ｆ）成分」と記載することもある。）、（Ｇ）イオン性化合物（以下、単に「（Ｇ）成分」と記載する場合もある。）、（Ｈ）溶媒（以下、単に「（Ｈ）成分」と記載することもある。）、酸化防止剤、紫外線吸収剤、粘着付与剤、可塑剤等が配合されていても良い。 1.6. Other Components The optical pressure-sensitive adhesive composition according to this embodiment further includes components other than the (A) component, the (B) component, the (C) component, the (D) component, and the (E) component as necessary. Can be included. For example, the pressure-sensitive adhesive composition according to the present embodiment includes (F) a silane coupling agent (hereinafter sometimes simply referred to as “component (F)”), as long as the effects of the present invention are not impaired. (G) an ionic compound (hereinafter sometimes simply referred to as “(G) component”), (H) a solvent (hereinafter sometimes simply referred to as “(H) component”), and antioxidant. An agent, an ultraviolet absorber, a tackifier, a plasticizer, and the like may be blended.
　１．６．１．（Ｆ）シランカップリング剤
　本実施形態に係る光学フィルム用粘着剤組成物が（Ｆ）成分を含むことにより、本実施形態に係る光学用粘着剤組成物を用いて形成された粘着剤層と被着体との接着を良好に保つことができる。（Ｆ）成分は例えば、ビニルトリメトキシシラン，ビニルトリエトキシシランおよびメタクリロキシプロピルトリメトキシシラン等の重合性不飽和基含有ケイ素化合物；３－グリシドキシプロピルトリメトキシシラン，３－グリシドキシプロピルメチルジメトキシシランおよび２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン等のエポキシ構造を有するケイ素化合物；３－アミノプロピルトリメトキシシラン，Ｎ－（２－アミノエチル）３－アミノプロピルトリメトキシシランおよびＮ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン等のアミノ基含有ケイ素化合物；並びに３－クロロプロピルトリメトキシシラン；オリゴマー型シランカップリング剤等であってもよく、中でも、（Ａ）成分中に含まれる官能基および（Ｂ）成分に含まれるグリシジル基と反応する官能基を有するシランカップリング剤が湿熱環境下でハガレを生じさせにくいという点で好ましい。 1.6.1. (F) Silane coupling agent The pressure-sensitive adhesive layer formed using the optical pressure-sensitive adhesive composition according to the present embodiment by including the component (F) in the pressure-sensitive adhesive composition for optical films according to the present embodiment. Good adhesion to the adherend can be maintained. Component (F) is, for example, a polymerizable unsaturated group-containing silicon compound such as vinyltrimethoxysilane, vinyltriethoxysilane, or methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Silicon compounds having an epoxy structure such as methyldimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane And amino group-containing silicon compounds such as N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane; and 3-chloropropyltrimethoxysilane; oligomer-type silane coupling agents, etc. A) Contained in ingredients The silane coupling agent having a functional group reactive with the glycidyl group contained in the functional group and the component (B) is preferable because hardly cause peeling in wet heat environment.
　本実施形態に係る光学フィルム用粘着剤組成物における（Ｆ）成分の含有量は、被着体との接着を良好に保つことができる観点から、（Ａ）成分１００質量部に対して０．０１質量部以上１質量部以下であることができ、０．０５質量部以上１質量部以下であることが好ましい。 The content of the component (F) in the optical film pressure-sensitive adhesive composition according to the present embodiment is 0.000 parts by weight with respect to 100 parts by weight of the component (A) from the viewpoint of maintaining good adhesion to the adherend. It can be from 01 parts by weight to 1 part by weight, and is preferably from 0.05 parts by weight to 1 part by weight.
　１．６．２．（Ｇ）イオン性化合物
　また、本実施形態に係る粘着剤組成物は、イオン性化合物（Ｇ）を含んでいてもよい。本実施形態に係る粘着剤組成物が（Ｇ）成分を含むことにより、被着体の帯電を効果的に防止することができる。（Ｇ）成分としては、例えば、アニオンとカチオンとからなる、２５℃で液体状、または固体状のイオン性化合物が挙げられ、具体的には、アルカリ金属塩、イオン性液体（２５℃で液体状）、界面活性剤等が挙げられる。 1.6.2. (G) Ionic compound Moreover, the adhesive composition which concerns on this embodiment may contain the ionic compound (G). When the pressure-sensitive adhesive composition according to this embodiment contains the component (G), charging of the adherend can be effectively prevented. Examples of the component (G) include ionic compounds that are liquid or solid at 25 ° C., which are composed of an anion and a cation. Specific examples include alkali metal salts, ionic liquids (liquid at 25 ° C. Shape), surfactants and the like.
　上記アルカリ金属塩としては、リチウム、ナトリウム、カリウム等のアルカリ金属カチオンと、アニオンとからなる化合物が挙げられ、具体的には、塩化ナトリウム、塩化カリウム、塩化リチウム、過塩素酸リチウム、塩素酸カリウム、硝酸カリウム、硝酸ナトリウム、炭酸ナトリウム、チオシアン酸ナトリウム、ＬｉＢｒ、ＬｉＩ、ＬｉＢＦ４、ＬｉＰＦ６、ＬｉＳＣＮ、酢酸ナトリウム、アルギン酸ナトリウム、リグニンスルホン酸ナトリウム、トルエンスルホン酸ナトリウム、ＬｉＣＦ３ＳＯ３、Ｌｉ（ＣＦ３ＳＯ２）２Ｎ、Ｌｉ（ＣＦ３ＳＯ２）ＩＮ、Ｌｉ（Ｃ２Ｆ５ＳＯ２）２Ｎ、Ｌｉ（Ｃ２Ｆ５ＳＯ２）ＩＮ、Ｌｉ（ＣＦ３ＳＯ２）３Ｃ等が挙げられる。 Examples of the alkali metal salt include compounds comprising an alkali metal cation such as lithium, sodium and potassium and an anion. Specifically, sodium chloride, potassium chloride, lithium chloride, lithium perchlorate, potassium chlorate , Potassium nitrate, sodium nitrate, sodium carbonate, sodium thiocyanate, LiBr, LiI, LiBF 4 , LiPF 6 , LiSCN, sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluene sulfonate, LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, Li (CF 3 SO 2 ) IN, Li (C 2 F 5 SO 2 ) 2 N, Li (C 2 F 5 SO 2 ) IN, Li (CF 3 SO 2 ) 3 C, and the like. It is done.
　上記イオン性液体を構成するカチオンとしては、ピペリジニウムカチオン、ピロリジニウムカチオン、ピロリン骨格を有するカチオン、ピロール骨格を有するカチオン、イミダゾリウムカチオン、テトラヒドロピリミジニウムカチオン、ジヒドロピリミジニウムカチオン、ピラゾリウムカチオン、ピラゾリニウムカチオン、テトラアルキルアンモニウムカチオン、トリアルキルスルホニウムカチオン、テトラアルキルホスホニウムカチオン等が挙げられ、上記イオン性液体を構成するアニオンとしては、Ｃｌ－、Ｂｒ－、Ｉ－、ＡｌＣｌ４ －、Ａｌ２Ｃｌ７ －、ＢＦ４ －、ＰＦ６ －、ＣｌＯ４ －、ＮＯ３ －、ＣＨ３ＣＯＯ－、ＣＦ３ＣＯＯ－、ＣＨ３ＳＯ３ －、ＣＦ３ＳＯ３ －、（ＣＦ３ＳＯ２）２Ｎ－、（ＣＦ３ＳＯ２）３Ｃ－、ＡｓＦ６ －、ＳｂＦ６ －、ＮｂＦ６ －、ＴａＦ６ －、Ｆ（ＨＦ）ｎ－（ｎ＝２～３）、（ＣＮ）２Ｎ－、Ｃ４Ｆ９ＳＯ３ －、（Ｃ２Ｆ５ＳＯ２）２Ｎ－、Ｃ３Ｆ７ＣＯＯ－、（ＣＦ３ＳＯ２）（ＣＦ３ＣＯ）Ｎ－等があげられる。 As the cation constituting the ionic liquid, piperidinium cation, pyrrolidinium cation, cation having pyrroline skeleton, cation having pyrrole skeleton, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, pyra Zolium cation, pyrazolinium cation, tetraalkylammonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation and the like. Examples of anions constituting the ionic liquid include Cl − , Br − , I − , AlCl 4. − , Al 2 Cl 7 − , BF 4 − , PF 6 − , ClO 4 − , NO 3 − , CH 3 COO − , CF 3 COO − , CH 3 SO 3 − , CF 3 SO 3 − , (CF 3 SO 2 ) 2 N − , (CF 3 SO 2 ) 3 C − , AsF 6 − , SbF 6 − , NbF 6 − , TaF 6 − , F (HF) n − (n = 2 to 3), (CN) 2 N − , C 4 F 9 SO 3 − , (C 2 F 5 SO 2 ) 2 N − , C 3 F 7 COO − , (CF 3 SO 2 ) (CF 3 CO) N − and the like.
　そして、上記イオン性化合物としては、これらのカチオンとアニオンとから構成され、２５℃で液状のイオン性化合物が挙げられる。このようなイオン性化合物としては、具体的には、２－メチル－１－ピロリンテトラフルオロボレート、１－エチル－２－フェニルインドールテトラフルオロボレート、１，２－ジメチルインドールテトラフルオロボレート、１－エチルカルバゾールテトラフルオロボレート、１－エチル－３－メチルイミダゾリウムテトラフルオロボレート、１－エチル－３－メチルイミダゾリウムアセテート、１－エチル－３－メチルイミダゾリウムトリフルオロアセテート、１－エチル－３－メチルイミダゾリウムヘプタフルオロブチレート、１－エチル－３－メチルイミダゾリウムトリフルオロメタンスルホネート、１－エチル－３－メチルイミダゾリウムペルフルオロブタンスルホネート、１－エチル－３－メチルイミダゾリウムジシアナミド、１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド、１－エチル－３－メチルイミダゾリウムビス（ペンタフルオロエタンスルホニル）イミド、１－エチル－３－メチルイミダゾリウムトリス（トリフルオロメタンスルホニル）メチド、１－ブチル－３－メチルイミダゾリウムテトラフルオロボレート、１－ブチル－３－メチルイミダゾリウムヘキサフルオロホスフェート、１－ブチル－３－メチルイミダゾリウムトリフルオロアセテート、１－ブチル－３－メチルイミダゾリウムヘプタフルオロブチレート、１－ブチル－３－メチルイミダゾリウムトリフルオロメタンスルホネート、１－ブチル－３－メチルイミダゾリウムペルフルオロブタンスルホネート、１－ブチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド、１－へキシル－３－メチルイミダゾリウムブロミド、１－へキシル－３－メチルイミダゾリウムクロライド、１－へキシル－３－メチルイミダゾリウムテトラフルオロボレート、１－へキシル－３－メチルイミダゾリウムヘキサフルオロホスフェート、１－へキシル－３－メチルイミダゾリウムトリフルオロメタンスルホネート、１－オクチル－３－メチルイミダゾリウムテトラフルオロボレート、１－オクチル－３－メチルイミダゾリウムヘキサフルオロホスフェート、１－へキシル－２，３－ジメチルイミダゾリウムテトラフルオロボレート、１，２－ジメチル－３－プロピルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド、１－メチルピラゾリウムテトラフルオロボレート、３－メチルピラゾリウムテトラフルオロボレート、テトラヘキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、ジアリルジメチルアンモニウムテトラフルオロボレート、ジアリルジメチルアンモニウムトリフルオロメタンスルホネート、ジアリルジメチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、ジアリルジメチルアンモニウムビス（ペンタフルオロエタンスルホニル）イミド、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－（２－メトキシエチル）アンモニウムテトラフルオロボレート、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－（２－メトキシエチル）アンモニウムトリフルオロメタンスルホネート、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－（２－メトキシエチル）アンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－（２－メトキシエチル）アンモニウムビス（ペンタフルオロエタンスルホニル）イミド、グリシジルトリメチルアンモニウムトリフルオロメタンスルホネート、グリシジルトリメチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、グリシジルトリメチルアンモニウムビス（ペンタフルオロエタンスルホニル）イミド、１－ブチルピリジニウム（トリフルオロメタンスルホニル）トリフルオロアセトアミド、１－ブチル－３－メチルピリジニウム（トリフルオロメタンスルホニル）トリフルオロアセトアミド、１－エチル－３－メチルイミダゾリウム（トリフルオロメタンスルホニル）トリフルオロアセトアミド、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－（２－メトキシエチル）アンモニウム（トリフルオロメタンスルホニル）トリフルオロアセトアミド、ジアリルジメチルアンモニウム（トリフルオロメタンスルホニル）トリフルオロアセトアミド、グリシジルトリメチルアンモニウム（トリフルオロメタンスルホニル）トリフルオロアセトアミド、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－プロピルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－ブチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－ペンチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－へキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－ヘプチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－ノニルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ，Ｎ－ジプロピルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－プロピル－Ｎ－ブチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－プロピル－Ｎ－ペンチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－プロピル－Ｎ－ヘキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－プロピル－Ｎ－ヘプチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－ブチル－Ｎ－ヘキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－ブチル－Ｎ－ヘプチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ－ペンチル－Ｎ－ヘキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジメチル－Ｎ，Ｎ－ジヘキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、トリメチルヘプチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－プロピルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－ペンチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－ヘプチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジエチル－Ｎ－プロピル－Ｎ－ペンチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、トリエチルプロピルアンモニウムビス（トリフルオロメタンスルホニル）イミド、トリエチルペンチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、トリエチルヘプチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジプロピル－Ｎ－メチル－Ｎ－エチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジプロピル－Ｎ－メチル－Ｎ－ペンチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジプロピル－Ｎ－ブチル－Ｎ－へキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジプロピル－Ｎ，Ｎ－ジヘキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジブチル－Ｎ－メチル－Ｎ－ペンチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ，Ｎ－ジブチル－Ｎ－メチル－Ｎ－ヘキシルアンモニウムビス（トリフルオロメタンスルホニル）イミド、トリオクチルメチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、Ｎ－メチル－Ｎ－エチル－Ｎ－プロピル－Ｎ－ペンチルアンモニウムビス（トリフルオロメタンスルホニル）イミド等が挙げられる。 And as said ionic compound, it is comprised from these cations and anions, and a liquid ionic compound is mentioned at 25 degreeC. Specific examples of such ionic compounds include 2-methyl-1-pyrroline tetrafluoroborate, 1-ethyl-2-phenylindole tetrafluoroborate, 1,2-dimethylindole tetrafluoroborate, and 1-ethyl. Carbazole tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazole Lithium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium perfluorobutanesulfonate, 1-ethyl-3-methylimidazolium dicyanamide, 1 Ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluoro 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis ( Trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl- 3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1 -Hexyl-2,3-dimethylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-methylpyrazolium tetrafluoroborate, 3- Methyl pyrazolium tetrafluoroborate, tetrahexylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium tetrafluoroborate, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (penta Fluoroethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium tetrafluoroborate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethane Sulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammonium bis (trifluoromethanesulfonyl) imide, glycidyltrimethyl Ammonium bis (pentafluoroethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium ( Trifluoromethanesulfonyl) trifluoroacetamide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) an Ni (trifluoromethanesulfonyl) trifluoroacetamide, diallyldimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, glycidyltrimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N, N-dimethyl-N-ethyl-N-propylammonium bis ( Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-he Ptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-nonylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) ) Imide, N, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N -Dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- -Butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-pentyl-N-hexyl Ammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl- N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl -N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (Trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-ethylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl- N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (trifluorome Tansulfonyl) imide, N, N-dipropyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N -Dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoro) Romethanesulfonyl) imide and the like.
　上記界面活性剤としては、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤および両性界面活性剤の何れも使用することができる。 As the surfactant, any of nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants can be used.
　上記ノニオン系界面活性剤としては、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル等のポリオキシエチレンアルキルエーテル類、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニエルフェニルエーテル等のポリオキシエチレンアルキルフェニルエーテル類、ソルビタンモノラウレート、ソルビタンモノステアレート、ソルビタントリオレエート等のソルビタン高級脂肪酸エステル類、ポリオキシエチレンソルビタンモノラウレート等のポリオキシエチレンソルビタン高級脂肪酸エステル類、ポリオキシエチレンモノラウレート、ポリオキシエチレンモノステアレート等のポリオキシエチレン高級脂肪酸エステル類；例えば、オレイン酸モノグリセライド、ステアリン酸モノグリセライド等のグリセリン高級脂肪酸エステル類、ポリオキシエチレン、ポリオキシプロピレン、ポリオキシブチレン等のポリオキシアルキレン類およびそれらのブロックコポリマーが挙げられる。 Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene alkylphenyls such as polyoxyethylene octylphenyl ether and polyoxyethylene nonielphenyl ether. Sorbitan higher fatty acid esters such as ethers, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene monolaurate, poly Polyoxyethylene higher fatty acid esters such as oxyethylene monostearate; for example, oleic acid monoglyceride, stearic acid monoglyceride Glycerine higher fatty acid esters such as id, polyoxyethylene, polyoxypropylene, polyoxyalkylenes and their block copolymers of polyoxybutylene and the like.
　上記カチオン系界面活性剤としては、塩化アルキルトリメチルアンモニウム、塩化ジアルキルジメチルアンモニウム、塩化ベンザルコニウム塩、アルキルジメチルアンモニウムエトサルフェート等が挙げられる。 Examples of the cationic surfactant include alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, benzalkonium chloride, alkyldimethylammonium ethosulphate and the like.
　上記アニオン系界面活性剤としては、ラウリン酸ナトリウム、オレイン酸ナトリウム、Ｎ－アシル－Ｎ－メチルグリシンナトリウム塩、ポリオキシエチレンラウリルエーテルカルボン酸ナトリウム等のカルボン酸塩、ドデシルベンゼンスルフォン酸ナトリウム、ジアルキルスルホコハク酸エステル塩、ジメチル－５－スルホイソフタレートナトリウム等のスルホン酸塩、ラウリル硫酸ナトリウム、ポリオキシエチレンラウリルエーテル硫酸ナトリウム、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム等の硫酸エステル塩、ポリオキシエチレンラウリル燐酸ナトリウム、ポリオキシエチレンノニルフェニルエーテルリン酸ナトリウム等の燐酸エステル塩等が挙げられる。 Examples of the anionic surfactant include sodium laurate, sodium oleate, N-acyl-N-methylglycine sodium salt, sodium carboxylate such as sodium polyoxyethylene lauryl ether carboxylate, sodium dodecylbenzenesulfonate, dialkylsulfosuccinate. Acid ester salts, sulfonates such as sodium dimethyl-5-sulfoisophthalate, sulfate salts such as sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, sodium polyoxyethylene lauryl phosphate And phosphoric acid ester salts such as sodium polyoxyethylene nonylphenyl ether phosphate.
　上記両性界面活性剤としては、カルボキシベタイン型界面活性剤、アミノカルボン酸塩、イミダゾリニウムペタイン、レシチン、アルキルアミンオキサイドが挙げられる。また、その他に、伝導性ポリマー、伝導性カーボン、塩化アンモニウム、塩化アルミニウム、塩化銅、塩化鉄、硫酸アンモニウム等を使用することができる。 Examples of the amphoteric surfactant include carboxybetaine surfactants, aminocarboxylates, imidazolinium petines, lecithins, and alkylamine oxides. In addition, conductive polymers, conductive carbon, ammonium chloride, aluminum chloride, copper chloride, iron chloride, ammonium sulfate, and the like can be used.
　１．６．３．（Ｈ）成分
　（Ｈ）成分である溶媒としては有機溶媒が挙げられる。有機溶媒としては、上述の「１．１．８．（Ａ１）成分の重合方法」欄で例示されたものをそれぞれ単独で、または２種以上混合して用いることができる。 1.6.3. (H) Component An organic solvent is mentioned as a solvent which is (H) component. As the organic solvent, can be mixed in the above "1.1.8. (A 1) component of the polymerization process" those exemplified in the section alone respectively, or two or more.
　１．７．ゲル分率
　本実施形態に係る光学用粘着剤組成物は、接着性および耐久性により優れた粘着シートを形成できる観点から、ゲル分率が２０％以上９５％以下であることが好ましく、５０％以上９５％以下であることがより好ましい。 1.7. Gel fraction The optical pressure-sensitive adhesive composition according to this embodiment preferably has a gel fraction of 20% or more and 95% or less, from the viewpoint of being able to form a pressure-sensitive adhesive sheet that is more excellent in adhesion and durability. More preferably, it is 95% or less.
　本実施形態に係る光学用粘着剤組成物において、上記ゲル分率は例えば、粘着剤組成物を調製する際に使用する単量体混合物中の（ａ２）成分の種類や使用量、ならびに（Ｃ）成分の種類や使用量によって調整することができる。なお、上記ゲル分率は、架橋された粘着剤を乾燥重量で０．１ｇ（乾燥重量（１））をサンプル瓶に採取し、更に、サンプル瓶に、酢酸エチル３０ｃｃを加えて２４時間振とうした後、該サンプル瓶の内容物を２００メッシュのステンレス製金網でろ別し、金網上の残留物を１００℃で２時間乾燥して乾燥重量（乾燥重量（２））を測定し、下記式（２）により求められる。
ゲル分率（％）＝（乾燥重量（２）／乾燥重量（１））×１００　・・・（２） In the optical pressure-sensitive adhesive composition according to this embodiment, the gel fraction is, for example, the type and amount of component (a2) in the monomer mixture used when preparing the pressure-sensitive adhesive composition, and (C ) It can be adjusted according to the type of component and the amount used. As for the gel fraction, 0.1 g (dry weight (1)) of the crosslinked adhesive was collected in a sample bottle, and 30 cc of ethyl acetate was further added to the sample bottle and shaken for 24 hours. After that, the contents of the sample bottle were filtered with a 200 mesh stainless steel wire mesh, the residue on the wire mesh was dried at 100 ° C. for 2 hours, and the dry weight (dry weight (2)) was measured. 2).
Gel fraction (%) = (dry weight (2) / dry weight (1)) × 100 (2)
　１．８．第１の粘着剤組成物を用いた粘着シートの製造方法（第１製造方法）
　本発明の一実施形態に係る第１製造方法は、第１の粘着剤組成物を用いた粘着シートの製造方法であって、第１の粘着剤組成物をセパレータの表面に塗布し、乾燥して得られる。より具体的には、第１製造方法は、第１の粘着剤組成物をセパレータの表面に塗布して、塗工液層を得る工程と、前記塗工液層から溶剤を除去し、熟成して、光学用粘着シートを得る工程と、を含む。すなわち、第１製造方法は第２製造方法と異なり、（Ｈ）溶媒を含む粘着剤組成物を用いて粘着シートを製造する。すなわち、第１の粘着剤組成物は例えば、（Ａ１）成分１００質量部と、（Ｂ）成分０．３質量部以上２０質量部以下と、（Ｃ）成分０．１質量部以上５質量部以下と、（Ｈ）溶媒５０質量部以上３００質量部以下とを含む。この場合、第１粘着剤組成物の（Ａ１）成分が水酸基を含有する場合、（Ｂ）成分中のグリシジル基同士の反応に加えて、（Ａ２）成分中の水酸基と（Ｃ）成分中のイソシアネート基との反応によって、架橋構造を形成することができるため、耐久性により優れた粘着剤層を得ることができる。 1.8. Method for producing pressure-sensitive adhesive sheet using first pressure-sensitive adhesive composition (first production method)
The 1st manufacturing method concerning one embodiment of the present invention is a manufacturing method of an adhesive sheet using the 1st adhesive composition, and applies the 1st adhesive composition on the surface of a separator, and dries. Obtained. More specifically, the first production method includes a step of applying the first pressure-sensitive adhesive composition to the surface of the separator to obtain a coating liquid layer, removing the solvent from the coating liquid layer, and aging. And obtaining an optical pressure-sensitive adhesive sheet. That is, the 1st manufacturing method differs from the 2nd manufacturing method, and manufactures an adhesive sheet using the adhesive composition containing (H) solvent. That is, the first pressure-sensitive adhesive composition includes, for example, 100 parts by mass of (A 1 ) component, 0.3 part by mass to 20 parts by mass of (B) component, and 0.1 part by mass to 5 parts by mass of (C) component. Part or less and (H) 50 parts by mass or more and 300 parts by mass or less of the solvent. In this case, when the component (A 1 ) of the first pressure-sensitive adhesive composition contains a hydroxyl group, in addition to the reaction between the glycidyl groups in the component (B), the hydroxyl group in the component (A 2 ) and the component (C) Since a cross-linked structure can be formed by reaction with the isocyanate group therein, a pressure-sensitive adhesive layer having superior durability can be obtained.
　１．９．第２の粘着剤組成物を用いた粘着シートの製造方法（第２製造方法）
　本発明の一実施形態に係る第２製造方法は、第２の粘着剤組成物を用いた粘着シートの製造方法である。第２製造方法は第１製造方法と異なり、溶媒を実質的に含まない粘着剤組成物を用いて粘着シートを製造する。すなわち、第２の粘着剤組成物は例えば、（Ａ２）成分１００質量部と、（Ｂ）成分０．３質量部以上２０質量部以下とを含み、（Ｈ）溶媒を実質的に含まないものである。第２粘着剤組成物は、（Ａ２）成分１００質量部と、（Ｂ）成分０．３質量部以上２０質量部以下とを含み、（Ｈ）溶媒を実質的に含まないことにより、溶媒が実質的に存在しない状態にて粘着剤層を形成することができる。この場合、第１粘着剤組成物の（Ａ２）成分が水酸基を含有する場合、（Ｂ）成分中のグリシジル基同士の反応に加えて、（Ｃ）成分の添加により（Ａ２）成分中の水酸基と（Ｃ）成分中のイソシアネート基との架橋構造を形成することができるため、耐久性により優れた粘着剤層を得ることができる。 1.9. Method for producing pressure-sensitive adhesive sheet using second pressure-sensitive adhesive composition (second production method)
The 2nd manufacturing method which concerns on one Embodiment of this invention is a manufacturing method of the adhesive sheet using the 2nd adhesive composition. Unlike a 1st manufacturing method, a 2nd manufacturing method manufactures an adhesive sheet using the adhesive composition which does not contain a solvent substantially. That is, the second pressure-sensitive adhesive composition contains, for example, 100 parts by mass of the (A 2 ) component and 0.3 parts by mass or more and 20 parts by mass or less of the (B) component, and does not substantially contain (H) the solvent. Is. The second pressure-sensitive adhesive composition contains 100 parts by mass of the (A 2 ) component, 0.3 parts by mass or more and 20 parts by mass or less of the (B) component, and does not substantially contain (H) a solvent. The pressure-sensitive adhesive layer can be formed in a state where substantially no is present. In this case, when the (A 2 ) component of the first pressure-sensitive adhesive composition contains a hydroxyl group, in addition to the reaction between the glycidyl groups in the (B) component, the addition of the (C) component in the (A 2 ) component Since the crosslinked structure of the hydroxyl group of this and the isocyanate group in (C) component can be formed, the adhesive layer excellent in durability can be obtained.
　より具体的には、第２製造方法は、（ａ１）（メタ）アクリル酸アルキルエステル単量体６０質量％以上８５質量％以下および（ａ２）水酸基含有単量体１５質量％以上４０質量％以下を含む単量体混合物（ここで、前記（ａ１）（メタ）アクリル酸アルキルエステル単量体および前記（ａ２）水酸基含有単量体の合計量は、前記（Ａ）アクリル系ポリマー１００質量％に対して７５質量％以上１００質量％以下である。）の部分共重合物（Ａ２）１００質量部と、（Ｂ）成分０．３質量部以上２０質量部以下と、（Ｄ）成分と、を含む塗工液をセパレータの表面に塗布して、塗工液層を得る工程と、前記塗工液層に光（例えば紫外線）を照射して、光学用粘着シートを得る工程と、を含む。 More specifically, the second production method comprises (a1) (meth) acrylic acid alkyl ester monomer 60% by mass to 85% by mass and (a2) hydroxyl group-containing monomer 15% by mass to 40% by mass. The total amount of the (a1) (meth) acrylic acid alkyl ester monomer and the (a2) hydroxyl group-containing monomer is 100% by mass of the (A) acrylic polymer. 100 parts by mass of a partial copolymer (A 2 ) of 75% by mass or more and 100% by mass or less), (B) component 0.3 part by mass or more and 20 parts by mass or less, (D) component, A step of applying a coating liquid containing a liquid to the surface of the separator to obtain a coating liquid layer, and a step of irradiating the coating liquid layer with light (for example, ultraviolet rays) to obtain an optical pressure-sensitive adhesive sheet. .
　前記塗工液は、第２の粘着剤組成物に（Ｄ）成分を添加して調製されたものであってもよい。また、前記塗工液は、溶媒を実質的に含有しないものであってもよい。ここで、「塗工液が溶媒を実質的に含有しない」とは、塗工液に含まれる溶媒の含有量が１質量％以下であることをいい、具体的には、塗工液に溶媒が配合されないことをいう。上記第２製造方法によれば、前記塗工液は、（Ａ２）成分、（Ｂ）成分および（Ｄ）成分を含み、かつ、溶媒を実質的に含有しないものであることにより、前記該組成物を含む塗工液を用いて粘着シートを製造する場合、該塗工液を用いて形成された塗工液層に対する光照射工程の前後で膜厚がほぼ変化しないため、得られる粘着シートの膜厚を予め予測することができるうえ、溶媒を除去する工程を省くことができるため、製造工程の簡素化を図ることができる。 The coating liquid may be prepared by adding the component (D) to the second pressure-sensitive adhesive composition. The coating solution may be substantially free of a solvent. Here, “the coating solution contains substantially no solvent” means that the content of the solvent contained in the coating solution is 1% by mass or less. Specifically, the coating solution contains a solvent. Means not blended. According to the second production method, the coating liquid contains the component (A 2 ), the component (B), and the component (D) and does not substantially contain a solvent. When a pressure-sensitive adhesive sheet is produced using a coating liquid containing the composition, the thickness of the pressure-sensitive adhesive sheet obtained before and after the light irradiation step on the coating liquid layer formed using the coating liquid is not substantially changed. The film thickness can be predicted in advance, and the process of removing the solvent can be omitted, so that the manufacturing process can be simplified.
　さらに、第２製造方法において、前記塗工液は、（Ｅ）成分および（Ｃ）成分またはいずれか一方をさらに含むことができる。すなわち、この場合、第２の粘着剤組成物に（Ｅ）成分および（Ｃ）成分またはいずれか一方を添加して調製されたものである。 Furthermore, in the second manufacturing method, the coating solution may further include (E) component and / or (C) component. That is, in this case, the second pressure-sensitive adhesive composition is prepared by adding (E) component and (C) component or any one of them.
　また、塗工液をセパレータの表面に塗布して得られた塗工液層に紫外線などの光を照射して、該塗工液層中の重合性成分を重合させる。すなわち、（Ａ２）成分中に含有される単量体を（（Ｅ）成分および（Ｃ）成分またはいずれか一方が含まれる場合は、（Ｅ）成分および（Ｃ）成分またはいずれか一方と）を反応させる。この場合、紫外線などの光の照射時間は通常は１秒以上３００秒以下、好ましくは１秒以上１８０秒以下である。 Further, the coating liquid layer obtained by applying the coating liquid to the surface of the separator is irradiated with light such as ultraviolet rays to polymerize the polymerizable component in the coating liquid layer. That is, when (A) component and (C) component or any one of the monomers contained in (A 2 ) component are included, (E) component and (C) component or any one and ). In this case, the irradiation time of light such as ultraviolet rays is usually from 1 second to 300 seconds, preferably from 1 second to 180 seconds.
　このように光照射することにより、（Ａ２）成分中の単量体が重合するとともに、（Ｂ）成分中のグリシジル基同士が反応して（さらには（Ａ２）成分が水酸基を含み、（Ｃ）成分をさらに含む場合、該水酸基と該（Ｃ）成分のイソシアネート基が反応し、（Ｅ）成分を含む場合には、（Ａ２）成分中のモノマーと（Ｅ）成分との反応により）架橋構造が形成されるため、耐久性に優れた粘着シートが得られる。また、上記第２の粘着剤組成物は溶媒を実質的に含まないため、該組成物を用いて粘着シートを製造する際、該組成物を用いて形成された塗工液層に対する光照射工程の前後で膜厚がほぼ変化しないため、得られる粘着シートの膜厚を予め予測することができる。 By irradiating in this way, the monomer in the component (A 2 ) is polymerized, and the glycidyl groups in the component (B) react with each other (further, the component (A 2 ) contains a hydroxyl group, When the component (C) is further included, the hydroxyl group reacts with the isocyanate group of the component (C). When the component (E) is included, the reaction between the monomer in the component (A 2 ) and the component (E) ), A cross-linked structure is formed, and thus a pressure-sensitive adhesive sheet having excellent durability can be obtained. Moreover, since the said 2nd adhesive composition does not contain a solvent substantially, when manufacturing an adhesive sheet using this composition, the light irradiation process with respect to the coating liquid layer formed using this composition Therefore, the film thickness of the obtained pressure-sensitive adhesive sheet can be predicted in advance.
　１．１０．用途
　本実施形態に係る光学用粘着剤組成物は、タッチパネル式入出力装置を構成する部材の貼り合わせに用いられることができる。本実施形態に係る光学用粘着剤組成物を用いた貼り合わせの対象となる部材は、光学部材（例えば、偏光フィルム、位相差フィルム、楕円偏光フィルム、反射防止フィルム、輝度向上フィルム、光拡散フィルムおよびハードコートフィルムからなる群から選択される光学フィルム）、ＩＴＯ層等の金属層、または、ガラスまたはプラスチックからなる基材であってもよい。より具体的には、本実施形態に係る光学用粘着剤組成物は、タッチパネル式入出力装置を構成する部材の貼り合わせに好適に用いることができる。 1.10. Applications The optical pressure-sensitive adhesive composition according to this embodiment can be used for bonding members constituting a touch panel type input / output device. The member to be bonded using the optical pressure-sensitive adhesive composition according to this embodiment is an optical member (for example, a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a brightness enhancement film, a light diffusion film). And an optical film selected from the group consisting of hard coat films), a metal layer such as an ITO layer, or a substrate made of glass or plastic. More specifically, the optical pressure-sensitive adhesive composition according to this embodiment can be suitably used for bonding members constituting a touch panel type input / output device.
　本実施形態に係る光学用粘着剤組成物を、タッチパネル式出入力装置を構成する部材の貼り合わせに使用した例を、図１を参照して説明する。図１は、本発明の一実施形態に係る出入力装置（タッチパネル式入出力装置１００）の構成を模式的に示す断面図である。本実施形態に係るタッチパネル式出入力装置１００は、液晶表示装置（ＬＣＤ）１０と、タッチパネル部２０と、ＬＣＤ１０とタッチパネル部２０との間に設けられた粘着剤層３０とを含む。粘着剤層３０はＬＣＤ１０とタッチパネル部２０とを接着する。 An example in which the optical pressure-sensitive adhesive composition according to this embodiment is used for bonding members constituting a touch panel type input / output device will be described with reference to FIG. FIG. 1 is a cross-sectional view schematically showing a configuration of an input / output device (touch panel type input / output device 100) according to an embodiment of the present invention. The touch panel type input / output device 100 according to the present embodiment includes a liquid crystal display device (LCD) 10, a touch panel unit 20, and an adhesive layer 30 provided between the LCD 10 and the touch panel unit 20. The pressure-sensitive adhesive layer 30 bonds the LCD 10 and the touch panel unit 20 together.
　粘着剤層３０は、例えば、本実施形態に係る第１製造方法にしたがって、本実施形態に係る第１光学用粘着剤組成物をセパレータ（図示せず）の表面に塗布し、乾燥して得られた粘着シートをセパレータから剥離して、ＬＣＤ１０とタッチパネル２０との間に設置したものである。 The pressure-sensitive adhesive layer 30 is obtained, for example, by applying the first optical pressure-sensitive adhesive composition according to this embodiment on the surface of a separator (not shown) and drying according to the first manufacturing method according to this embodiment. The obtained pressure-sensitive adhesive sheet is peeled off from the separator and installed between the LCD 10 and the touch panel 20.
　あるいは、粘着剤層３０は、例えば、本実施形態に係る第２製造方法にしたがって、本実施形態に係る第２光学用粘着剤組成物に（Ｄ）成分（さらに、必要に応じて（Ｅ）成分および（Ｃ）成分またはいずれか一方）を添加した塗工液をセパレータ（図示せず）の表面に塗布して塗工液層を形成し、該塗工液層に光（例えば紫外線）を照射することにより、粘着シートを形成し、この粘着シートをセパレータから剥離して、ＬＣＤ１０とタッチパネル２０との間に設置したものである。 Alternatively, the pressure-sensitive adhesive layer 30 is prepared by adding the component (D) (and, if necessary, (E) to the second optical pressure-sensitive adhesive composition according to the present embodiment, for example, according to the second production method according to the present embodiment. The coating liquid to which the component and the component (C) or any one of them is added is applied to the surface of a separator (not shown) to form a coating liquid layer, and light (for example, ultraviolet rays) is applied to the coating liquid layer. By irradiating, a pressure-sensitive adhesive sheet is formed, this pressure-sensitive adhesive sheet is peeled off from the separator, and installed between the LCD 10 and the touch panel 20.
　また、図１に示すように、ＬＣＤ１０は、偏光板１１と、粘着剤層１２と、液晶パネル１３と、粘着剤層１４と、偏光板１５とがこの順で積層されて構成されている。粘着剤層１２は偏光板１１と液晶パネル１３とを接着し、粘着剤層１４は液晶パネル１３と偏光板１５とを接着する。 Further, as shown in FIG. 1, the LCD 10 is configured by laminating a polarizing plate 11, an adhesive layer 12, a liquid crystal panel 13, an adhesive layer 14, and a polarizing plate 15 in this order. The pressure-sensitive adhesive layer 12 bonds the polarizing plate 11 and the liquid crystal panel 13, and the pressure-sensitive adhesive layer 14 bonds the liquid crystal panel 13 and the polarizing plate 15.
　また、図１に示すように、タッチパネル部２０は、飛散防止フィルム１６と、粘着剤層１７と、ＩＴＯ層１８と、ガラスパネル１９とがこの順で積層されて構成されている。粘着剤層１７は、飛散防止フィルム１６とＩＴＯ層１８とを接着する。 Further, as shown in FIG. 1, the touch panel unit 20 is configured by a scattering prevention film 16, an adhesive layer 17, an ITO layer 18, and a glass panel 19 laminated in this order. The pressure-sensitive adhesive layer 17 bonds the scattering prevention film 16 and the ITO layer 18.
　粘着剤層１２，１４，１７は、粘着剤層３０と同じく、本実施形態に係る光学用粘着剤組成物を用いて、上記第１製造方法または第２製造方法によって製造されたものである。 The pressure-sensitive adhesive layers 12, 14, and 17 are manufactured by the first manufacturing method or the second manufacturing method using the optical pressure-sensitive adhesive composition according to this embodiment, like the pressure-sensitive adhesive layer 30.
　１．１１．作用効果
　本実施形態に係る光学用粘着剤組成物は、（Ａ）成分１００質量部と、（Ｂ）成分０．３質量部以上２０質量部以下と、を含むことにより、該光学用粘着剤組成物を用いて粘着シートを製造する際に、（Ｂ）成分中のグリシジル基同士が反応して（さらには（Ａ）成分が水酸基を含む場合、（Ｃ）成分の添加により該水酸基と（Ｃ）成分のイソシアネート基が反応して）架橋構造が形成されるため、該粘着シートは高湿度条件下において浮きや剥がれが生じにくく、耐久性に優れている。特に、本実施形態に係る光学用粘着剤組成物は、（Ａ）成分がカルボキシル基を実質的に含まないので、金属を腐食する性質を有さないため、ＩＴＯ等の金属を含むタッチパネル式入出力装置を構成する部材の貼り合わせに好適に使用することができる。 1.11. Effect The optical pressure-sensitive adhesive composition according to this embodiment includes (A) component 100 parts by mass and (B) component 0.3 parts by mass or more and 20 parts by mass or less. When the pressure-sensitive adhesive sheet is produced using the composition, the glycidyl groups in the component (B) react with each other (in addition, when the component (A) includes a hydroxyl group, Since the isocyanate group of component C) reacts to form a crosslinked structure, the pressure-sensitive adhesive sheet is less likely to float or peel off under high humidity conditions and is excellent in durability. In particular, since the optical pressure-sensitive adhesive composition according to this embodiment does not have a property of corroding a metal because the component (A) does not substantially contain a carboxyl group, a touch panel type input containing a metal such as ITO is used. It can be suitably used for bonding members constituting the output device.
　２．粘着シート
　本実施形態に係る粘着シート（光学用粘着シート）は、例えば、第１粘着剤組成物または第２粘着剤組成物を用いて、上記第１製造方法または第２製造方法によって得ることができる。粘着シートの厚みは、通常は１０μｍ以上５００μｍ以下、好ましくは２０μｍ以上３００μｍ以下程度である。 2. Pressure-sensitive adhesive sheet The pressure-sensitive adhesive sheet (optical pressure-sensitive adhesive sheet) according to this embodiment can be obtained, for example, by using the first pressure-sensitive adhesive composition or the second pressure-sensitive adhesive composition by the first manufacturing method or the second manufacturing method. it can. The thickness of the pressure-sensitive adhesive sheet is usually from 10 μm to 500 μm, preferably from about 20 μm to 300 μm.
　より具体的には、基材上に、上記第１粘着剤組成物をグラビアコーター、メイヤーバーコーター、エアナイフコーター、ロールコーター等により塗布し、必要に応じて常温または加熱により乾燥させて、本実施形態に係る粘着シートを作製することができる。 More specifically, the first pressure-sensitive adhesive composition is applied on a substrate with a gravure coater, Mayer bar coater, air knife coater, roll coater, etc., and dried by normal temperature or heating as necessary. The adhesive sheet which concerns on a form can be produced.
　あるいは、上記第２粘着剤組成物を含む塗工液をグラビアコーター、メイヤーバーコーター、エアナイフコーター、ロールコーター等により塗布し、該塗工液層に光を照射することにより、本実施形態に係る粘着シートを作製することができる。 Alternatively, a coating liquid containing the second pressure-sensitive adhesive composition is applied by a gravure coater, a Mayer bar coater, an air knife coater, a roll coater, etc., and the coating liquid layer is irradiated with light, thereby relating to the present embodiment. An adhesive sheet can be produced.
　本実施形態に係る粘着シートによれば、上記実施形態に係る粘着剤組成物（第１粘着剤組成物または第２粘着剤組成物）を用いて形成されることにより、密着性および耐久性に優れているため、高湿度条件下における浮きや剥がれの発生が低減されており、かつ、金属を腐食する性質を有さない。よって、本実施形態に係る粘着シートは、光学部材の貼り合わせに好適に用いることができ、より具体的には、タッチパネル式入出力装置を構成する部材の貼り合わせに好適に用いることができる。 According to the pressure-sensitive adhesive sheet according to the present embodiment, it is formed using the pressure-sensitive adhesive composition (the first pressure-sensitive adhesive composition or the second pressure-sensitive adhesive composition) according to the above-described embodiment, thereby improving adhesion and durability. Since it is excellent, the occurrence of floating and peeling under high humidity conditions is reduced, and it does not have the property of corroding metals. Therefore, the pressure-sensitive adhesive sheet according to this embodiment can be suitably used for bonding optical members, and more specifically, can be suitably used for bonding members constituting the touch panel type input / output device.
　３．画像表示装置および入出力装置
　本発明の別の実施形態に係る画像表示装置は、上記実施形態に係る光学用粘着シートを含む。本実施形態に係る画像表示装置としては、例えば、液晶表示装置が挙げられる。 3. Image Display Device and Input / Output Device An image display device according to another embodiment of the present invention includes the optical pressure-sensitive adhesive sheet according to the above-described embodiment. An example of the image display device according to the present embodiment is a liquid crystal display device.
　また、本発明の他の実施形態に係る入出力装置は、上記実施形態に係る光学用粘着シートを含む。この場合、入出力装置としては、例えば、静電容量方式のタッチパネル式出入力装置が挙げられる。 Also, an input / output device according to another embodiment of the present invention includes the optical pressure-sensitive adhesive sheet according to the above-described embodiment. In this case, examples of the input / output device include a capacitive touch panel type input / output device.
　４．実施例
　以下、本発明を下記実施例に基づいて説明するが、本発明は実施例に限定されない。 4). EXAMPLES Hereinafter, the present invention will be described based on the following examples, but the present invention is not limited to the examples.
　４．１．実施例１（（Ａ１）成分を含む粘着剤組成物を用いた、第１製造方法による粘着シートの製造）
　４．１．１．調製例１（アクリル系ポリマーの調製）
　攪拌機、還流冷却器、温度計および窒素導入管を備えた反応装置に、下記表２に示す配合比率を有する単量体混合物を仕込み、次に、等質量の酢酸エチルおよびトルエンを、単量体混合物の濃度が３０質量％になる配合量にて仕込んだ。次に、アゾビスイソブチロニトリル０．１質量部を加え、反応容器内の空気を窒素ガスで置換しながら撹拌を行い７０℃に昇温した後、６時間反応させた。反応終了後、酢酸エチルで希釈して、アクリル系ポリマー１ないし５を得た。 4.1. Example 1 (Production of pressure-sensitive adhesive sheet by the first production method using a pressure-sensitive adhesive composition containing the component (A 1 ))
4.1.1. Preparation Example 1 (Preparation of acrylic polymer)
Into a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, a monomer mixture having the blending ratio shown in Table 2 below was charged, and then an equal amount of ethyl acetate and toluene were added to the monomer. The blending amount was 30% by mass of the mixture. Next, 0.1 part by mass of azobisisobutyronitrile was added, the mixture was stirred while the air in the reaction vessel was replaced with nitrogen gas, and the temperature was raised to 70 ° C., followed by reaction for 6 hours. After completion of the reaction, the reaction mixture was diluted with ethyl acetate to obtain acrylic polymers 1 to 5.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　４．１．２．製造例１（粘着シートの作製）
　上記４．１．１．で得られたアクリル系ポリマー１ないし５を用いて、下記表３の配合（固形分配合）にて各成分を添加して、実施例１ないし１０および比較例１ないし４の粘着剤組成物の溶液を得た。この粘着剤組成物の溶液を剥離処理したポリエステルフィルムの表面に塗布して乾燥させることにより、粘着剤層の厚さ５０μｍの粘着シートを得た。得られた粘着シートの粘着剤層側に、厚さ１００μｍのポリエチレンテレフタレートフィルムを貼り合わせて評価用粘着シートを得た。 4.1.2. Production Example 1 (Preparation of adhesive sheet)
4.1.1. Using the acrylic polymers 1 to 5 obtained in 1 above, each component was added in the composition (solid content composition) shown in Table 3 below, and the adhesive compositions of Examples 1 to 10 and Comparative Examples 1 to 4 were added. A solution was obtained. The pressure-sensitive adhesive composition solution was applied to the surface of a peeled polyester film and dried to obtain a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer thickness of 50 μm. A 100 μm-thick polyethylene terephthalate film was bonded to the pressure-sensitive adhesive layer side of the obtained pressure-sensitive adhesive sheet to obtain a pressure-sensitive adhesive sheet for evaluation.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　４．２．実施例２（（Ａ２）成分を含む粘着剤組成物を用いた、第２製造方法による粘着シートの製造）
　４．２．１．調製例２（アクリル系ポリマーの調製）
　攪拌機、還流冷却器、温度計および窒素導入管を備えた反応装置に、下記表４に示す配合比率を有する単量体混合物、および連鎖移動剤であるノルマルドデシルメルカプタンをポリマー６、７、９については０．０５質量部、ポリマー８については１質量部をさらに仕込み、空気を窒素ガスで置換しながら撹拌を行い５０℃に昇温した。次いで、２，２’－アゾビス(４－メトキシ－２，４－ジメチルバレロニトリルを反応液が１２０℃以上１４０℃以下にまで発熱するよう適量加え重合をおこない、アクリル系ポリマー６ないし９（ポリマー分２５％以上６０％以下の部分重合物）を得た。なお、アクリル系ポリマーのポリマー分とは、アクリル系ポリマー（部分重合物）を１５０℃で１時間加熱した場合に残存する固形分の割合（質量％）をいう。なお、表４に示す各ポリマーの「Ｔｇ」は、使用した単量体混合物がすべて重合したと仮定した場合のＴｇの値を示す。 4.2. Example 2 (Production of pressure-sensitive adhesive sheet by the second production method using a pressure-sensitive adhesive composition containing the component (A 2 ))
4.2.1. Preparation Example 2 (Preparation of acrylic polymer)
In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, a monomer mixture having a blending ratio shown in Table 4 below, and normal dodecyl mercaptan, which is a chain transfer agent, are used for polymers 6, 7, and 9. Was added in an amount of 0.05 part by mass and 1 part by mass of polymer 8 was further added, and the temperature was raised to 50 ° C. while stirring while replacing the air with nitrogen gas. Subsequently, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile was added in an appropriate amount so that the reaction solution generated heat to 120 ° C. or more and 140 ° C. or less, and polymerization was performed. The polymer content of the acrylic polymer is the ratio of the solid content remaining when the acrylic polymer (partial polymer) is heated at 150 ° C. for 1 hour. In addition, “Tg” of each polymer shown in Table 4 indicates a value of Tg when it is assumed that the monomer mixture used is completely polymerized.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　４．２．２．製造例２（粘着シートの作製）
　上記４．２．１．で得られたアクリル系ポリマー６ないし９を用いて、下記表５の配合（固形分配合）にて各成分を添加して、実施例１１ないし１９および比較例５ないし８の粘着剤組成物を含む塗工液を得た。この塗工液を剥離処理したポリエステルフィルムの表面に塗布した後、剥離処理したポリエステルフィルムを被せて塗工液層をサンドし、ブラックライトを強度３０ｍＷ／ｃｍ２で塗工液層の上下両方から１８０秒間照射することにより、粘着剤層の厚さ１５０μｍの粘着シートを得た。得られた粘着シートの片側のポリエステルフィルムを剥離し、厚さ１００μｍのポリエチレンテレフタレートフィルムを貼り合わせて評価用粘着シートを得た。 4.2.2. Production Example 2 (Preparation of adhesive sheet)
Above 4.2.1. Using the acrylic polymers 6 to 9 obtained in the above, the respective components were added according to the blending (solid blending) shown in Table 5 below, and the pressure-sensitive adhesive compositions of Examples 11 to 19 and Comparative Examples 5 to 8 were obtained. A coating liquid containing was obtained. After coating this coating liquid on the surface of the release-treated polyester film, the release-treated polyester film is applied to sand the coating liquid layer, and black light is applied at both the upper and lower sides of the coating liquid layer at an intensity of 30 mW / cm 2. By irradiating for 180 seconds, a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer thickness of 150 μm was obtained. The polyester film on one side of the obtained pressure-sensitive adhesive sheet was peeled off, and a polyethylene terephthalate film having a thickness of 100 μm was bonded to obtain a pressure-sensitive adhesive sheet for evaluation.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　各粘着シートについて、上記表３および表５に示す湿熱耐久性および金属腐食性については以下の方法にて評価した。また、各粘着剤組成物のゲル分率を測定した。また、実施例２の粘着シートについては、湿熱試験後のヘイズ変化について評価を行った。なお、アクリルポリマー１ないし４および６ないし８が水酸基を有することは、例えば、各アクリル系ポリマー１ないし４および６ないし８に関するＩＲスペクトルにおいて、３４００－３２００ｃｍ－１に吸収が現れることによって確認された。 About each adhesive sheet, the wet heat durability shown in the said Table 3 and Table 5 and metal corrosivity were evaluated with the following method. Moreover, the gel fraction of each adhesive composition was measured. Moreover, about the adhesive sheet of Example 2, it evaluated about the haze change after a wet heat test. The fact that acrylic polymers 1 to 4 and 6 to 8 have a hydroxyl group was confirmed by, for example, the appearance of absorption at 3400-3200 cm −1 in the IR spectrum for each of acrylic polymers 1 to 4 and 6 to 8. .
　４．３．評価方法
　４．３．１．ゲル分率
　各粘着剤組成物のゲル分率は、上記実施形態の欄に記載された方法で測定した。 4.3. Evaluation method 4.3.1. Gel fraction The gel fraction of each pressure-sensitive adhesive composition was measured by the method described in the above embodiment.
　４．３．２．湿熱サイクル試験（耐久性）
　上記４．２．２．で調製された評価用粘着シートを（５０ｍｍ×６０ｍｍ）裁断し、剥離処理したポリエステルフィルムを剥がして、厚さ２．０ｍｍのポリカーボネート板の片面に、粘着剤層が前記ポリカーボネート板に接するようにして、ラミネータロールを用いて貼り付けた。貼付後、オートクレーブ（栗原製作所製）にて０．５ＭＰａ、５０℃、２０分の条件で加圧処理して試験用プレートを得た。こうして得られた試験用プレートを６０℃／９５％ＲＨの条件下に２４時間、８５℃で乾燥環境下に２４時間放置するサイクル試験を１００回実施した。試験終了後、試験用プレートを試験環境より取り出し、２３℃／５０％ＲＨ雰囲気下で１時間静置した後、粘着剤層の湿熱サイクル試験（耐久性）を目視により下記評価基準にて評価した。 4.3.2. Wet heat cycle test (durability)
Above 4.2.2. The evaluation pressure-sensitive adhesive sheet prepared in (1) was cut (50 mm × 60 mm), the peeled polyester film was peeled off, and the pressure-sensitive adhesive layer was in contact with the polycarbonate plate on one side of a 2.0 mm-thick polycarbonate plate. Attached using a laminator roll. After pasting, a test plate was obtained by pressurizing in an autoclave (manufactured by Kurihara Seisakusho) under conditions of 0.5 MPa, 50 ° C., and 20 minutes. A cycle test in which the test plate thus obtained was allowed to stand in a dry environment at 85 ° C. for 24 hours under the condition of 60 ° C./95% RH was conducted 100 times. After completion of the test, the test plate was removed from the test environment and allowed to stand in a 23 ° C./50% RH atmosphere for 1 hour, and then the wet heat cycle test (durability) of the adhesive layer was visually evaluated according to the following evaluation criteria. .
　（評価）
　○：ウキ、ハガレ、発泡等がない
　×：ウキ、ハガレ、発泡等がある (Evaluation)
○: There is no uki, peeling, foaming, etc. ×: There are uki, peeling, foaming, etc.
　４．３．３．金属腐食性
　１０ｍｍ×１００ｍｍにカットしたＩＴＯ蒸着ＰＥＴフィルムに、製造例１で得られた、実施例１ないし１４および比較例１ないし５の組成物を用いて得られた粘着シートを１０ｍｍ×６０ｍｍにカットして貼り付け、５０℃×５ａｔｍで２０分間オートクレーブ処理を行った。次いで、１時間室温で静置した後、６０℃でかつ９０％ＲＨの環境下に５００時間置き、２３℃でかつ湿度６５％ＲＨの条件下に１時間静置した後、ＩＴＯ蒸着フィルムの抵抗値を測定し、あらかじめ測定しておいた試験前の抵抗値と比較し、試験前の抵抗値に対する抵抗値の変化率を求めた。 4.3.3. Metal corrosive pressure-sensitive adhesive sheets obtained by using the compositions of Examples 1 to 14 and Comparative Examples 1 to 5 obtained in Production Example 1 on an ITO vapor-deposited PET film cut to 10 mm x 100 mm, to 10 mm x 60 mm Cut and pasted and autoclaved at 50 ° C. × 5 atm for 20 minutes. Next, after standing at room temperature for 1 hour, placing it in an environment of 60 ° C. and 90% RH for 500 hours, standing at 23 ° C. and humidity of 65% RH for 1 hour, then the resistance of the ITO deposited film The value was measured and compared with the resistance value before the test measured in advance, and the rate of change of the resistance value with respect to the resistance value before the test was obtained.
　試験前の抵抗値に対する抵抗値の変化率が１１５％以上である場合を、ＩＴＯ腐食性が有る（×）と判定し、試験前の抵抗値に対する抵抗値の変化率が１１５％未満である場合を、ＩＴＯ腐食性がなし（○）と判定した。なお、抵抗値の測定には、テスター（三和電気計器（株）製、デジタルマルチメーターＰＣ５１０)を用いた。 When the change rate of the resistance value with respect to the resistance value before the test is 115% or more, it is determined that there is ITO corrosivity (x), and the change rate of the resistance value with respect to the resistance value before the test is less than 115% Was judged to have no ITO corrosiveness (O). Note that a tester (manufactured by Sanwa Denki Keiki Co., Ltd., Digital Multimeter PC510) was used for measuring the resistance value.
　４．３．４．湿熱試験後のヘイズ
　上記４．２．２．で調製された評価用粘着シートを、剥離処理したポリエステルフィルムを剥がし、粘着剤層がガラス基板に接するようにラミネータロールを用いて貼り付けて測定試料を作製し、ヘイズメーター（型名「ＨＭ－１５０」、村上色彩技術研究所社製）でヘイズを測定した（初期ヘイズ）。次に、６０℃－９５％ＲＨ条件下で該試料を５００時間投入した後、２３℃－５０％ＲＨ条件下に移してから１０分後にヘイズを測定した（湿熱試験後ヘイズ）。初期ヘイズ－湿熱試験後ヘイズの値（ヘイズの変化値）が０．５以下であることが望ましい。 4.3.4. Haze after wet heat test 4.2.2. The peel-off polyester film was peeled off from the evaluation pressure-sensitive adhesive sheet prepared in (1) above, and a measurement sample was prepared using a laminator roll so that the pressure-sensitive adhesive layer was in contact with the glass substrate, and a haze meter (model name “HM-” 150 ", manufactured by Murakami Color Research Laboratory Co., Ltd.), the haze was measured (initial haze). Next, after putting the sample under a condition of 60 ° C.-95% RH for 500 hours, haze was measured 10 minutes after the sample was transferred to a condition of 23 ° C.-50% RH (haze after wet heat test). Initial haze-Haze value after wet heat test (change value of haze) is preferably 0.5 or less.
　なお、表２ないし５における略語は以下の意味である。
　ＡＡ：アクリル酸
　ＡＭ：アクリルアミド
　ＢＡ：ｎ－ブチルアクリレート
　ｔ－ＢＡ：ｔｅｒｔ－（ターシャリー）ブチルアクリレート
　ＤＭＡＥＡ：ジメチルアミノエチルアクリレート
　２－ＥＨＡ：２－エチルヘキシルアクリレート
　２－ＨＥＡ：２－ヒドロキシエチルアクリレート
　ＭＡ：メチルアクリレート
　ＴＭＰＴＡ：トリメチロールプロパントリアクリレート
　テトラッドＣ：１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン（分子量３８５、１分子に含まれるグリシジル基の数４個、三菱瓦斯化学株式会社製）
　テトラッドＸ：Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミン（分子量３８０、１分子に含まれるグリシジル基の数４個、三菱瓦斯化学株式会社製）
　デナコールＥＸ２１２Ｌ：１，６－ヘキサンジオールグリシジルエーテル（分子量２６０、１分子に含まれるグリシジル基の数２個、ナガセケムテックス株式会社製）
　ｊＥＲ１００４：（分子量１，６５０、１分子に含まれるグリシジル基の数２個、三菱化学株式会社製）
　コロネートＬ：トリレンジイソシアネ－トのトリメチロールプロパン付加物（日本ポリウレタン工業株式会社製）
　デュラネート２４Ａ－１００：ビウレット型イソシアネート化合物（旭化成株式会社製）
　ダロキュア１１７３：２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン（ＢＡＳＦジャパン株式会社製） Abbreviations in Tables 2 to 5 have the following meanings.
AA: acrylic acid AM: acrylamide BA: n-butyl acrylate t-BA: tert- (tertiary) butyl acrylate DMAEA: dimethylaminoethyl acrylate 2-EHA: 2-ethylhexyl acrylate 2-HEA: 2-hydroxyethyl acrylate MA: Methyl acrylate TMPTA: Trimethylolpropane triacrylate Tetrad C: 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (molecular weight 385, number of glycidyl groups contained in one molecule, manufactured by Mitsubishi Gas Chemical Co., Ltd.) )
Tetrad X: N, N, N ′, N′-tetraglycidyl-m-xylenediamine (molecular weight 380, number of glycidyl groups contained in one molecule, 4 manufactured by Mitsubishi Gas Chemical Co., Ltd.)
Denacol EX212L: 1,6-hexanediol glycidyl ether (molecular weight 260, two glycidyl groups contained in one molecule, manufactured by Nagase ChemteX Corporation)
jER1004: (molecular weight 1,650, two glycidyl groups contained in one molecule, manufactured by Mitsubishi Chemical Corporation)
Coronate L: Trimethylolpropane adduct of tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.)
Duranate 24A-100: Biuret type isocyanate compound (Asahi Kasei Corporation)
Darocur 1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by BASF Japan Ltd.)
　表３の結果から、上記実施例１ないし１０の組成物は、（Ａ）成分１００質量部および（Ｂ）成分０．３質量部以上２０質量部以下を含むことにより、（Ｂ）成分に含まれるグリシジル基が分子内および／または分子間で反応するとともに、（Ａ）成分に含まれる水酸基と（Ｃ）成分に含まれるイソシアネート基との反応により、架橋構造が形成されるため、該組成物を用いて形成された粘着シートは高湿度条件下において浮きや剥がれを生じにくく、高い接着性および優れた耐久性を実現することができる。また、（Ａ）成分がカルボキシル基を実質的に有さないため、金属を腐食する性質を有さない。 From the results of Table 3, the compositions of Examples 1 to 10 above are included in the component (B) by including (A) component 100 parts by mass and (B) component 0.3 parts by mass to 20 parts by mass. The glycidyl group reacts within and / or between the molecules, and a cross-linked structure is formed by the reaction between the hydroxyl group contained in the component (A) and the isocyanate group contained in the component (C). The pressure-sensitive adhesive sheet formed using is less likely to float or peel off under high humidity conditions, and can achieve high adhesion and excellent durability. Moreover, since (A) component does not have a carboxyl group substantially, it does not have a property which corrodes a metal.
　これに対して、上記比較例１および２の組成物は、（Ｂ）成分の割合が（Ａ）成分１００質量部に対して０．３質量部以上２０質量部以下の範囲にないため、該組成物を用いて形成された粘着シートは高温高湿度条件下から急激に高温低湿度条件下に変化した際に浮きや剥がれが生じ、耐久性に劣る。 In contrast, in the compositions of Comparative Examples 1 and 2, the ratio of the component (B) is not in the range of 0.3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the component (A). The pressure-sensitive adhesive sheet formed using the composition is inferior in durability because it floats or peels off when it is rapidly changed from a high-temperature and high-humidity condition to a high-temperature and low-humidity condition.
　また、上記比較例３の組成物は、１分子中にグリシジル基を２個以上有するものの、分子量１，０００を超える化合物を使用したため、（Ｂ）成分中におけるグリシジル基の密度が小さいことに起因して、グリシジル基同士による架橋が起こりにくく、結果として、耐久性に劣ると推測される。 Moreover, although the composition of the said comparative example 3 has two or more glycidyl groups in 1 molecule, since the compound exceeding molecular weight 1,000 was used, it originates in the density of the glycidyl group in (B) component being small. Thus, crosslinking by glycidyl groups is unlikely to occur, and as a result, it is estimated that the durability is poor.
　さらに、上記比較例４の組成物は、（Ａ）成分の代わりに、水酸基を有さないがカルボキシル基を有するアクリル系ポリマーを使用したため、（Ｂ）成分の分子内および／または分子間での反応より優先して（Ｂ）成分中のグリシジル基と（Ａ）成分中のカルボキシル基が過剰に反応してしまうため、架橋が密になりすぎて、耐久性に劣るうえに、カルボキシル基の存在に起因して、金属の腐食性を有すると推測される。 Furthermore, since the composition of Comparative Example 4 used an acrylic polymer that does not have a hydroxyl group but has a carboxyl group in place of the component (A), the (B) component within and / or between the molecules. Since the glycidyl group in the component (B) and the carboxyl group in the component (A) react excessively in preference to the reaction, the cross-linking becomes too dense and inferior in durability, and the presence of the carboxyl group It is estimated that the metal has corrosive properties.
　表５の結果から、上記実施例１１ないし１９の組成物は、（Ａ）成分（（Ａ２）成分）１００質量部および（Ｂ）成分０．３質量部以上２０質量部以下を含むことにより、（Ｂ）成分に含まれるグリシジル基が分子内および／または分子間で反応するとともに、（Ｅ）成分を含有することで（Ａ２）成分中のモノマーと（Ｅ）成分とが反応し、架橋構造を形成するため、該組成物を用いて形成された粘着シートは高湿度条件下において浮きや剥がれを生じにくく、高い接着性および優れた耐久性を実現することができる。 The results in Table 5, the compositions of Examples 11 to 19, by including a component (A) ((A 2) component) 100 parts by mass of the component (B) 0.3 part by weight or more and 20 parts by weight In addition, the glycidyl group contained in the component (B) reacts within and / or between the molecules, and by containing the component (E), the monomer in the component (A 2 ) reacts with the component (E), Since the cross-linked structure is formed, the pressure-sensitive adhesive sheet formed using the composition is less likely to float or peel off under high humidity conditions, and can achieve high adhesiveness and excellent durability.
　また、（Ａ）成分がカルボキシル基を実質的に有さないため、金属を腐食する性質を有さない。さらに、上記実施例１１ないし１９の組成物は溶媒を実質的に含まないため、該組成物を含む塗工液を用いて粘着シートを製造する際、該塗工液を用いて形成された塗工液層に対する光照射工程の前後で膜厚がほぼ変化しないため、得られる粘着シートの膜厚を予め予測することができる。 Also, since the component (A) has substantially no carboxyl group, it does not have the property of corroding metals. Furthermore, since the compositions of Examples 11 to 19 are substantially free of a solvent, when a pressure-sensitive adhesive sheet is produced using a coating liquid containing the composition, a coating formed using the coating liquid is used. Since the film thickness does not substantially change before and after the light irradiation process for the working liquid layer, the film thickness of the obtained pressure-sensitive adhesive sheet can be predicted in advance.
　これに対して、上記比較例５および６の組成物は、（Ｂ）成分の割合が（Ａ）成分１００質量部に対して１質量部以上２０質量部以下の範囲にないため、該組成物を用いて形成された粘着シートは高湿度条件下において浮きや剥がれが生じ、耐久性に劣る。 On the other hand, the compositions of Comparative Examples 5 and 6 have a ratio of the component (B) that is not in the range of 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the component (A). The pressure-sensitive adhesive sheet formed using the material is floated or peeled off under high humidity conditions, and is inferior in durability.
　また、上記比較例７の組成物は、１分子中にグリシジル基を２個以上有するものの、分子量１，０００を超える化合物を使用したため、（Ｂ）成分中におけるグリシジル基の密度が小さいことに起因して、グリシジル基同士による架橋が起こりにくく、結果として、耐久性に劣ると推測される。 Moreover, although the composition of the said comparative example 7 has two or more glycidyl groups in 1 molecule, since the compound exceeding molecular weight 1,000 was used, it originates in the density of the glycidyl group in (B) component being small. Thus, crosslinking by glycidyl groups is unlikely to occur, and as a result, it is estimated that the durability is poor.
　さらに、上記比較例８の組成物は、（Ａ）成分の代わりに、水酸基を有さないがカルボキシル基を有するアクリル系ポリマーを使用したため、（Ｂ）成分の分子内および／または分子間での反応より優先して（Ｂ）成分中のグリシジル基と（Ａ）成分中のカルボキシル基が過剰に反応してしまうため、架橋が密になりすぎて、耐久性に劣るうえに、カルボキシル基の存在に起因して、金属の腐食性を有すると推測される。 Furthermore, since the composition of Comparative Example 8 used an acrylic polymer that does not have a hydroxyl group but has a carboxyl group in place of the component (A), the intramolecular and / or intermolecular components of the component (B) Since the glycidyl group in the component (B) and the carboxyl group in the component (A) react excessively in preference to the reaction, the cross-linking becomes too dense and inferior in durability, and the presence of the carboxyl group It is estimated that the metal has corrosive properties.
［符号の説明］
　１０　液晶表示装置（ＬＣＤ）
　１１，１５　偏光板
　１２，１４，１７　粘着剤層
　１３　液晶パネル
　１６　飛散防止フィルム
　１８　ＩＴＯ層
　１９　ガラスパネル
　２０　タッチパネル部
　３０　粘着剤層
　１００　タッチパネル式出入力装置 [Explanation of symbols]
10 Liquid crystal display (LCD)
DESCRIPTION OF SYMBOLS 11, 15 Polarizing plate 12, 14, 17 Adhesive layer 13 Liquid crystal panel 16 Anti-scattering film 18 ITO layer 19 Glass panel 20 Touch panel part 30 Adhesive layer 100 Touch panel type input / output device

Claims (13)

  1. 　（Ａ）カルボキシル基を実質的に含有しないアクリル系ポリマー１００質量部と、
    　（Ｂ）１分子中にグリシジル基を２個以上有する、分子量１，０００以下の化合物０．３質量部以上２０質量部以下と、を含む、光学用粘着剤組成物。     (A) 100 parts by mass of an acrylic polymer substantially free of carboxyl groups;
    (B) An optical pressure-sensitive adhesive composition comprising 0.3 to 20 parts by mass of a compound having a molecular weight of 1,000 or less and having two or more glycidyl groups in one molecule.
  2. 　前記（Ａ）アクリル系ポリマーは、（ａ１）（メタ）アクリル酸アルキルエステル単量体６０質量％以上８５質量％以下および（ａ２）水酸基含有単量体１５質量％以上４０質量％以下を含む単量体混合物の共重合体（Ａ１）である（ここで、前記（ａ１）（メタ）アクリル酸アルキルエステル単量体および前記（ａ２）水酸基含有単量体の合計量は、前記単量体混合物１００質量％とした場合、７５質量％以上１００質量％以下である。）、請求項１に記載の光学用粘着剤組成物。 The (A) acrylic polymer comprises (a1) a (meth) acrylic acid alkyl ester monomer of 60% by mass to 85% by mass and (a2) a hydroxyl group-containing monomer of 15% by mass to 40% by mass. It is a copolymer (A1) of a monomer mixture (here, the total amount of the (a1) (meth) acrylic acid alkyl ester monomer and the (a2) hydroxyl group-containing monomer is the monomer mixture The optical pressure-sensitive adhesive composition according to claim 1, wherein when it is 100% by mass, it is 75% by mass or more and 100% by mass or less.
  3. 　（Ｃ）イソシアネート系架橋剤をさらに含む、請求項１または２に記載の光学用粘着剤組成物。 The optical pressure-sensitive adhesive composition according to claim 1 or 2, further comprising (C) an isocyanate-based crosslinking agent.
  4. 　前記（Ａ）アクリル系ポリマーは、（ａ１）（メタ）アクリル酸アルキルエステル単量体６０質量％以上８５質量％以下および（ａ２）水酸基含有単量体１５質量％以上４０質量％以下を含む単量体混合物の部分重合物（Ａ２）を含む組成物より得られるものである（ここで、前記（ａ１）（メタ）アクリル酸アルキルエステル単量体および前記（ａ２）水酸基含有単量体の合計量は、前記単量体混合物１００質量％とした場合、７５質量％以上１００質量％以下である。）、請求項１に記載の光学用粘着剤組成物。 The (A) acrylic polymer comprises (a1) a (meth) acrylic acid alkyl ester monomer of 60% by mass to 85% by mass and (a2) a hydroxyl group-containing monomer of 15% by mass to 40% by mass. It is obtained from a composition containing a partial polymer (A 2 ) of a monomer mixture (wherein (a1) (meth) acrylic acid alkyl ester monomer and (a2) hydroxyl group-containing monomer The total amount is 75% by mass or more and 100% by mass or less when the monomer mixture is 100% by mass.), The optical pressure-sensitive adhesive composition according to claim 1.
  5. 　前記部分重合物（Ａ２）を含む前記組成物は、（Ｅ）多官能性単量体をさらに含み、
    　前記（Ａ）アクリル系ポリマーは、前記部分重合物（Ａ２）および前記（Ｅ）多官能性単量体を含む前記組成物より得られるものである、請求項４に記載の光学用粘着剤組成物。     The composition containing the partial polymer (A 2 ) further includes (E) a polyfunctional monomer,
    The optical pressure-sensitive adhesive according to claim 4, wherein the (A) acrylic polymer is obtained from the composition containing the partial polymer (A 2 ) and the (E) polyfunctional monomer. Composition.
  6. 　前記単量体混合物は、（ａ３）窒素原子含有単量体０．１質量％以上５質量％以下をさらに含む、請求項２ないし５のいずれか１項に記載の光学用粘着剤組成物。 6. The optical pressure-sensitive adhesive composition according to claim 2, wherein the monomer mixture further comprises (a3) a nitrogen atom-containing monomer of 0.1% by mass to 5% by mass.
  7. 　ゲル分率が２０％以上９５％以下である、請求項１ないし６のいずれか１項に記載の光学用粘着剤組成物。 The optical pressure-sensitive adhesive composition according to any one of claims 1 to 6, wherein the gel fraction is 20% to 95%.
  8. 　タッチパネル式入出力装置を構成する部材の貼り合わせに用いられる、請求項１ないし７のいずれか１項に記載の光学用粘着剤組成物。 The optical pressure-sensitive adhesive composition according to any one of claims 1 to 7, which is used for bonding members constituting a touch panel type input / output device.
  9. 　請求項１ないし７のいずれか１項に記載の光学用粘着剤組成物より得られる粘着剤層を有する、光学用粘着シート。 An optical pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer obtained from the optical pressure-sensitive adhesive composition according to any one of claims 1 to 7.
  10. 　（Ａ）カルボキシル基を実質的に含有しないアクリル系ポリマー１００質量部と、（Ｂ）１分子中にグリシジル基を２個以上有する、分子量１，０００以下の化合物０．３質量部以上２０質量部以下とを含む粘着剤組成物をセパレータの表面に塗布して、塗工液層を得る工程と、
    　前記塗工液層から溶剤を除去し、熟成して、光学用粘着シートを得る工程と、を含む、光学用粘着シートの製造方法。     (A) 100 parts by mass of an acrylic polymer substantially free of carboxyl groups, and (B) 0.3 to 20 parts by mass of a compound having a molecular weight of 1,000 or less and having two or more glycidyl groups in one molecule. Applying a pressure-sensitive adhesive composition containing the following to the surface of the separator to obtain a coating liquid layer;
    Removing the solvent from the coating liquid layer and aging to obtain an optical pressure-sensitive adhesive sheet.
  11. 　前記粘着剤組成物は、（Ｃ）イソシアネート系架橋剤をさらに含む、請求項１０に記載の光学用粘着シートの製造方法。 The method for producing an optical pressure-sensitive adhesive sheet according to claim 10, wherein the pressure-sensitive adhesive composition further comprises (C) an isocyanate-based crosslinking agent.
  12. 　（ａ１）（メタ）アクリル酸アルキルエステル単量体６０質量％以上８５質量％以下および（ａ２）水酸基含有単量体１５質量％以上４０質量％以下を含む単量体混合物の部分重合物（Ａ２）１００質量部（ここで、前記（ａ１）（メタ）アクリル酸アルキルエステル単量体および前記（ａ２）水酸基含有単量体の合計量は、前記単量体混合物１００質量％とした場合、７５質量％以上１００質量％以下である。）と、（Ｂ）１分子中にグリシジル基を２個以上有する、分子量１，０００以下の化合物０．３質量部以上２０質量部以下と、（Ｄ）光重合開始剤と、を含む塗工液をセパレータの表面に塗布して、塗工液層を得る工程と、
    　前記塗工液層に光を照射して、光学用粘着シートを得る工程と、を含む、光学用粘着シートの製造方法。     (A1) (meth) acrylic acid alkyl ester monomer 60% by mass to 85% by mass and (a2) hydroxyl group-containing monomer 15% by mass to 40% by mass partial polymer (A 2 ) 100 parts by mass (wherein the total amount of the (a1) (meth) acrylic acid alkyl ester monomer and the (a2) hydroxyl group-containing monomer is 100% by mass of the monomer mixture, 75% by mass or more and 100% by mass or less.) (B) 0.3 to 20 parts by mass of a compound having two or more glycidyl groups in one molecule and having a molecular weight of 1,000 or less, and (D ) Applying a coating liquid containing a photopolymerization initiator to the surface of the separator to obtain a coating liquid layer;
    Irradiating the coating liquid layer with light to obtain an optical pressure-sensitive adhesive sheet, and a method for producing an optical pressure-sensitive adhesive sheet.
  13. 　前記塗工液は、（Ｅ）多官能性単量体をさらに含む、請求項１２に記載の光学用粘着シートの製造方法。 The method for producing an optical pressure-sensitive adhesive sheet according to claim 12, wherein the coating liquid further comprises (E) a polyfunctional monomer.
PCT/JP2014/059138 2013-04-02 2014-03-28 Adhesive composition for optics, adhesive sheet for optics, and method for producing adhesive sheet for optics WO2014163003A1 (en)

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