WO2022185715A1 - Adhesive agent composition, adhesive sheet, and optical member - Google Patents

Adhesive agent composition, adhesive sheet, and optical member Download PDF

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Publication number
WO2022185715A1
WO2022185715A1 PCT/JP2022/000694 JP2022000694W WO2022185715A1 WO 2022185715 A1 WO2022185715 A1 WO 2022185715A1 JP 2022000694 W JP2022000694 W JP 2022000694W WO 2022185715 A1 WO2022185715 A1 WO 2022185715A1
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Prior art keywords
mass
monomer
polymer
meth
sensitive adhesive
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PCT/JP2022/000694
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French (fr)
Japanese (ja)
Inventor
恵子 近藤
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綜研化学株式会社
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Priority to CN202280017383.6A priority Critical patent/CN116997628A/en
Priority to JP2023503600A priority patent/JPWO2022185715A1/ja
Publication of WO2022185715A1 publication Critical patent/WO2022185715A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

  • One embodiment of the present invention relates to a pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet or optical member.
  • Optical members such as polarizing plates and retardation plates are used in display devices such as liquid crystal displays. It is used by attaching it to other members such as steel. Since the display devices and the like are used in various environments, the pressure-sensitive adhesive layer used as the lamination layer can exhibit desired properties such as heat resistance, cohesiveness, and adhesiveness in various environments. It has been demanded. Among various environments, for example, the inside of a vehicle such as an automobile is exemplified as a harsh environment that can become hot and humid.
  • Patent Documents 1 and 2 disclose pressure-sensitive adhesive compositions using acrylic polymers having carboxy groups as pressure-sensitive adhesive compositions that exhibit desired properties under high temperature and high humidity conditions.
  • the pressure-sensitive adhesive layers obtained from conventional pressure-sensitive adhesive compositions such as the pressure-sensitive adhesive compositions disclosed in Patent Document 1 and Patent Document 2 have a balance between cohesion and stress relaxation in a temperature range of 115 ° C. This causes foaming due to reduced cohesion, and problems such as peeling from the adherend and light leakage due to reduced stress relaxation. Therefore, it was found that the conventional PSA compositions have room for improvement in terms of high-temperature durability.
  • the adhesive layer when used by sticking it to the adherend, it does not peel off or float from the adherend, and when it is desired to be peeled off from the adherend, it adheres without leaving any adhesive residue. In some cases, it is required to have an appropriate adhesive strength that allows it to be peeled off from the body (excellent in reworkability).
  • the pressure-sensitive adhesive layer may be used in contact with a corrodible adherend such as a metal used for electrodes or a metal oxide such as ITO (indium tin oxide). It is also required not to corrode possible adherends.
  • One embodiment of the present invention is capable of suppressing corrosion of a corrodible adherend even when it is in contact with the adherend, has an appropriate adhesive strength, and foams even under high temperature and high humidity.
  • a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer that is less likely to be peeled off from an adherend.
  • a configuration example of the present invention is as follows.
  • the total content of the structural units derived from the hydroxyl group-containing monomer (b1) and the structural units derived from the amino group-containing monomer (b2) is 0.05% by mass or less, and the acid value is 1.0 mgKOH/g or less, weight average an acrylic polymer (B) having a molecular weight (Mw) of more than 250,000 and smaller than the Mw of the acrylic polymer (A); and an isocyanate curing agent (C),
  • the acrylic polymer (B) is contained in an amount of 10 parts by mass or more with respect to 100 parts by mass of the acrylic polymer
  • the acrylic polymer (A) contains 25 to 99.99% by mass of structural units derived from at least one monomer (a3) selected from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates, [ 1].
  • the acrylic polymer (B) contains 25 to 100% by mass of constitutional units derived from at least one monomer (b3) selected from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates [1] Or the pressure-sensitive adhesive composition according to [2].
  • the acrylic polymer (A) contains 25 to 98% by mass of structural units derived from at least one monomer (a3) selected from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates, and has an alicyclic [1] to [4] containing 1 to 50% by mass of structural units derived from at least one monomer (a4) selected from hydrocarbon group-containing (meth)acrylates and aromatic hydrocarbon group-containing (meth)acrylates.
  • the pressure-sensitive adhesive composition according to any one of the above.
  • the acrylic polymer (B) contains 25 to 98% by mass of structural units derived from at least one monomer (b3) selected from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates, and has an alicyclic [1] to [5] containing 1 to 50% by mass of structural units derived from at least one monomer (b4) selected from hydrocarbon group-containing (meth)acrylates and aromatic hydrocarbon group-containing (meth)acrylates.
  • the pressure-sensitive adhesive composition according to any one of the above.
  • the present invention even when in contact with a corrodible adherend, it is possible to suppress corrosion of the adherend, have an appropriate adhesive strength, and have a high temperature and high humidity.
  • the pressure-sensitive adhesive composition according to one embodiment of the present invention (hereinafter also referred to as "this composition") is a total of the structural units derived from the hydroxyl group-containing monomer (a1) and the structural units derived from the amino group-containing monomer (a2).
  • the total content of the structural units derived from the hydroxyl group-containing monomer (b1) and the structural units derived from the amino group-containing monomer (b2) is 0.05% by mass or less, and the acid value is 1.0 mgKOH/g or less, weight average an acrylic polymer (B) having a molecular weight (Mw) of more than 250,000 and smaller than the Mw of the acrylic polymer (A);
  • a pressure-sensitive adhesive composition containing an isocyanate curing agent (C) The acrylic polymer (B) is contained in an amount of 10 parts by mass or more with respect to 100 parts by mass of the acrylic polymer (A),
  • the isocyanate curing agent (C) is contained in an amount of more than 6 parts by mass and less than 30 parts by mass
  • the "acrylic polymer” refers to a structural unit derived from acrylic acid, a structural unit derived from acrylate, a structural unit derived from acrylic acid ester, a structural unit derived from methacrylic acid, a structural unit derived from methacrylate, and A polymer in which the total amount of structural units derived from methacrylic acid ester is 50% by mass or more with respect to 100% by mass of all structural units of the acrylic polymer.
  • (meth)acrylic is used as a generic term for acrylic and methacrylic, and may be acrylic or methacrylic.
  • (Meth)acrylate is used as a generic term for acrylate and methacrylate, and may be either acrylate or methacrylate.
  • (meth)acryloyl is used as a generic term for acryloyl and methacryloyl, and may be acryloyl or methacryloyl.
  • the acrylic polymer (A) (hereinafter also referred to as “polymer (A)”) is a structural unit derived from a hydroxyl group-containing monomer (a1) (hereinafter also referred to as “monomer (a1)”) and an amino group-containing monomer (a2) (hereinafter also referred to as “monomer (a2)”) containing structural units derived in an amount exceeding 0% by mass and 0.4% by mass or less, and having an acid value of 1.0 mgKOH/g or less, and , Mw is 600,000 or more.
  • the obtained pressure-sensitive adhesive layer has a low cross-linking density, which makes it possible to easily form a pressure-sensitive adhesive layer which is excellent in stress relaxation properties and which hardly causes peeling of the adherend.
  • the stress applied to the pressure-sensitive adhesive layer can be relaxed when using the pressure-sensitive adhesive layer obtained in contact with an adherend (e.g., polarizing plate) that can shrink significantly. Furthermore, shrinkage of the adherend can be suppressed.
  • the content of structural units derived from the monomer (a1) and the monomer (a2) can be calculated from the amounts of the monomer (a1) and the monomer (a2) in the monomer component used when synthesizing the polymer (A).
  • the polymer (A) can be synthesized by polymerizing a monomer component containing at least one selected from the monomer (a1) and the monomer (a2), and the monomer component preferably contains the monomer (a1).
  • the monomer (a1) may be used alone or in combination of two or more.
  • Examples of the monomer (a1) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate.
  • Polymer (A) can be synthesized by polymerizing a monomer component containing at least one selected from monomer (a1) and monomer (a2), but the monomer component preferably does not contain monomer (a2).
  • the monomer (a2) may be used alone or in combination of two or more.
  • Monomer (a2) is a monomer other than monomer (a1).
  • a monomer having an amide group or an imide group and having no amino group other than the amide group or the imide group is a monomer (a2 )is not.
  • Examples of the monomer (a2) include dialkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.
  • Polymer (A) further contains structural units derived from at least one monomer (a3) selected from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates (hereinafter also referred to as "monomer (a3)"). is preferred, and it is particularly preferred to contain structural units derived from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates.
  • Monomer (a3) is a monomer other than monomer (a1), monomer (a2) and monomer (a4) below.
  • the adhesive strength and reworkability (reattachability) of the obtained pressure-sensitive adhesive layer can be easily adjusted.
  • the polymer (A) contains a structural unit derived from an alkoxyalkyl (meth)acrylate, the time until the physical properties (eg, gel fraction) of the resulting pressure-sensitive adhesive layer do not change is shortened (hereinafter referred to as "aging Therefore, it is possible to form a pressure-sensitive adhesive layer with excellent quality stability with good productivity.
  • the gel fraction can be measured by the method described in Examples below.
  • the content of the structural unit derived from the monomer (a3) is the total content of the polymer (A) from the viewpoint that the above effects are exhibited more. It is preferably 25 to 99.99% by mass, more preferably 50 to 99.99% by mass, based on 100% by mass of the structural units.
  • the polymer (A) contains structural units other than those derived from the monomer (a1), the monomer (a2) and the monomer (a3), particularly the monomer (a1), the monomer (a2) and the monomer (a3)
  • the upper limit of the content of the structural unit derived from the monomer (a3) is preferably 98% by mass or less, more preferably 97% by mass or less, and the lower limit is It is preferably 25% by mass or more, more preferably 50% by mass or more.
  • the content of structural units derived from the monomer (a3) can be calculated from the amount of the monomer (a3) in the monomer component used when synthesizing the polymer (A).
  • alkyl (meth)acrylates examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, iso-octyl (meth) acrylate, nonyl (meth) acrylate, iso-nonyl (meth) acrylate, decyl (meth) acrylate, iso-decyl (meth) acrylate, undeca (meth) acrylate, lauryl (meth) acrylate
  • alkoxyalkyl (meth)acrylates examples include methoxymethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (Meth)acrylate, 4-methoxybutyl (meth)acrylate, 4-ethoxybutyl (meth)acrylate.
  • One type of alkoxyalkyl (meth)acrylate may be used alone, or two or more types may be used.
  • the polymer (A) further contains at least one monomer (a4) selected from alicyclic hydrocarbon group-containing (meth)acrylates and aromatic hydrocarbon group-containing (meth)acrylates (hereinafter also referred to as "monomer (a4)" It may contain structural units derived from Monomer (a4) is a monomer other than monomer (a1) and monomer (a2).
  • monomer (a4) is a monomer other than monomer (a1) and monomer (a2).
  • the polymer (A) contains a structural unit derived from an aromatic hydrocarbon group-containing (meth)acrylate, it is possible to easily form a pressure-sensitive adhesive layer that has excellent adhesion to an adherend and can suppress light leakage. can be done.
  • the content of the structural unit derived from the monomer (a4) is the total content of the polymer (A) from the viewpoint that the above effects are exhibited more. It is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, based on 100% by mass of the structural units.
  • the content of structural units derived from the monomer (a4) can be calculated from the amount of the monomer (a4) in the monomer component used when synthesizing the polymer (A).
  • Examples of the alicyclic hydrocarbon group-containing (meth)acrylates include cyclohexyl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate.
  • the alicyclic hydrocarbon group-containing (meth)acrylates may be used alone or in combination of two or more.
  • aromatic hydrocarbon group-containing (meth)acrylates examples include benzyl (meth)acrylate, phenyl (meth)acrylate, and phenoxyethyl (meth)acrylate.
  • the aromatic hydrocarbon group-containing (meth)acrylates may be used singly or in combination of two or more.
  • the polymer (A) may further contain constituent units derived from monomers other than the monomer (a1), the monomer (a2), the monomer (a3) and the monomer (a4) as long as the object of the present invention is not impaired. good.
  • the content of the structural unit derived from the other monomer is preferably 30% by mass or less, preferably 20% by mass, based on 100% by mass of the total structural units of the polymer (A), from the viewpoint that the above effect is more exhibited. % or less.
  • the content of structural units derived from other monomers can be calculated from the amount of other monomers in the monomer component used when synthesizing the polymer (A).
  • Examples of the other monomers include (meth)acrylamide; N-alkyl (meth)acrylamide such as N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-hexyl (meth)acrylamide; N,N- N,N-dialkyl(meth)acrylamides such as dimethyl(meth)acrylamide and N,N-diethyl(meth)acrylamide; cyclic amide group-containing monomers such as N-vinylpyrrolidone, N-vinylcaprolactam and (meth)acryloylmorpholine;
  • amide group-containing monomers and nitrogen-based heterocyclic ring-containing monomers are preferable, and by using the polymer (A) containing structural units derived from these monomers, excellent aging resistance and excellent quality stability can be obtained.
  • a pressure-sensitive adhesive layer can be formed with good productivity.
  • Polymer (A) can be synthesized by polymerizing the aforementioned monomer components, and may be, for example, a random polymer, a block polymer or a graft polymer, and can be synthesized by various polymerization methods.
  • the polymerization method is not particularly limited, and examples thereof include solution polymerization, emulsion polymerization, and suspension polymerization. Among these, in producing the present composition using a mixture of copolymers obtained by polymerization, solution polymerization is preferred from the viewpoint that the processing steps are relatively simple and can be carried out in a short time. is preferred.
  • a reaction vessel is charged with other components such as a monomer component, a polymerization initiator and, if necessary, a chain transfer agent and a polymerization solvent, and the reaction initiation temperature is usually 40° C. or higher, preferably 50° C. C. or higher, usually 100.degree. C. or lower, preferably 80.degree. .
  • the reaction is performed, for example, under an inert gas atmosphere such as nitrogen gas.
  • at least one selected from monomer components, polymerization initiators, chain transfer agents and polymerization solvents may be additionally added during the polymerization reaction.
  • polymerization initiators include azo initiators and peroxide polymerization initiators.
  • azo initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2- cyclopropylpropionitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane-1-carbo nitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis(2-amidinopropane) dihydrochloride, 2,2′- azobis(N,N'-dimethyleneisobutylamidine), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide],
  • peroxide polymerization initiators examples include t-butyl hydroperoxide, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-i-propyl peroxide, Carbonate, di-2-ethylhexylperoxydicarbonate, t-butyl peroxypivalate, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 2,2-bis(4,4 -di-t-amylperoxycyclohexyl)propane, 2,2-bis(4,4-di-t-octylperoxycyclohexyl)propane, 2,2-bis(4,4-di- ⁇ -cumylperoxy cyclohexyl)propane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)butane, and 2,2-bis(4,
  • a polymerization initiator may be used individually by 1 type, and may use 2 or more types. Also, the polymerization initiator may be added multiple times during the polymerization.
  • the amount of the polymerization initiator used is usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, and usually 5 parts by mass or less, preferably 3 parts by mass or less, relative to 100 parts by mass of the monomer component.
  • polymerization solvent used for solution polymerization examples include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; cyclopentane, cyclohexane, cycloheptane, alicyclic hydrocarbons such as cyclooctane; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, Halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane, chlorobenzene; Esters such as ethyl acetate, propyl acetate, butyl acetate
  • ketones such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; and sulfoxides such as dimethylsulfoxide and sulfolane.
  • One type of polymerization solvent may be used alone, or two or more types may be used.
  • the weight average molecular weight (Mw) of the polymer (A) measured by gel permeation chromatography (GPC) is 600,000 or more, preferably 800,000 or more, more preferably 1,000,000 or more, preferably 300. 10,000 or less, more preferably 2,500,000 or less.
  • Mw is within the above range, a pressure-sensitive adhesive layer having excellent durability and cohesion can be easily formed.
  • the Mw can be measured by the method described in Examples below.
  • the acid value of polymer (A) is 1.0 mgKOH/g or less, preferably 0.8 mgKOH/g or less, more preferably 0 mgKOH/g.
  • the acid value of the polymer (A) is within the above range, corrosion of adherends in contact with the pressure-sensitive adhesive layer formed from the obtained pressure-sensitive adhesive composition can be suppressed.
  • the acid value can be measured by the method described in Examples below.
  • the amount of the acidic group-containing monomer used is 0.12% by mass or less with respect to 100% by mass of the monomer component, or , preferably without substantially using an acidic group-containing monomer.
  • acidic group-containing monomers examples include acrylic acid, methacrylic acid, ⁇ -carboxyethyl(meth)acrylate, 5-carboxypentyl(meth)acrylate, succinic acid mono(meth)acryloyloxyethyl ester, ⁇ -carboxy Examples include carboxyl group-containing monomers such as polycaprolactone mono(meth)acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid.
  • the composition can contain one or more polymers (A).
  • the content of the polymer (A) in the composition is preferably 20% by mass or more, more preferably 25% by mass or more, preferably 70% by mass or less, and more Preferably, it is 65% by mass or less.
  • the polymer (A) has an appropriate adhesive strength, is excellent in well-balanced cohesive strength and stress relaxation even under high temperature and high humidity, and is resistant to foaming and peeling from the adherend.
  • a pressure-sensitive adhesive layer that is difficult to form can be easily formed.
  • the acrylic polymer (B) (hereinafter also referred to as “polymer (B)”) is a structural unit derived from a hydroxyl group-containing monomer (b1) (hereinafter also referred to as “monomer (b1)”) and an amino group-containing monomer (b2). (hereinafter also referred to as “monomer (b2)”), the total content of structural units derived from it is 0.05% by mass or less, the acid value is 1.0 mgKOH/g or less, and the Mw is more than 250,000; Moreover, it is a polymer smaller than the Mw of the acrylic polymer (A).
  • the present composition contains the polymer (B), even when the pressure-sensitive adhesive layer obtained from the present composition is used in contact with an adherend (e.g., polarizing plate) that shrinks significantly due to temperature changes, the It is possible to easily form a pressure-sensitive adhesive layer that exhibits sufficient shear stress against contraction of an adherend and can be relaxed without residual internal stress.
  • adherend e.g., polarizing plate
  • the total content of structural units derived from the monomer (b1) and structural units derived from the monomer (b2) in the polymer (B) is 0.05% by mass or less with respect to 100% by mass of all structural units of the polymer (B). , preferably 0.02% by mass or less, more preferably 0.01% by mass or less.
  • the lower limit of the total content is preferably 0% by mass.
  • the stress applied to the pressure-sensitive adhesive layer can be relaxed when using the pressure-sensitive adhesive layer obtained in contact with an adherend (e.g., polarizing plate) that can shrink significantly. Furthermore, shrinkage of the adherend can be suppressed.
  • the content of structural units derived from the monomer (b1) and the monomer (b2) can be calculated from the amounts of the monomer (b1) and the monomer (b2) in the monomer component used when synthesizing the polymer (B).
  • Examples of the monomer (b1) and the monomer (b2) include the same monomers as the monomer (a1) and the monomer (a2), respectively.
  • the monomer (b1) may be used alone or in combination of two or more.
  • the monomer (b2) may also be used singly or in combination of two or more.
  • Monomer (b2) is a monomer other than monomer (b1).
  • the polymer (B) preferably contains structural units derived from at least one monomer (b3) selected from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates (hereinafter also referred to as "monomer (b3)"). , alkyl (meth)acrylate and alkoxyalkyl (meth)acrylate-derived structural units are particularly preferred.
  • alkyl (meth)acrylate and alkoxyalkyl (meth)acrylate-derived structural units are particularly preferred.
  • the adhesive strength and reworkability of the obtained pressure-sensitive adhesive layer can be easily adjusted.
  • the polymer (B) contains structural units derived from alkoxyalkyl (meth)acrylate, it is possible to form a pressure-sensitive adhesive layer excellent in aging resistance and quality stability with good productivity.
  • the content of the structural unit derived from the monomer (b3) is the total content of the polymer (B) from the viewpoint that the above effects are exhibited more. It is preferably 25 to 100% by mass, more preferably 50 to 100% by mass, based on 100% by mass of the structural units.
  • the polymer (B) contains structural units other than the structural units derived from the monomer (b1), the monomer (b2) and the monomer (b3), particularly the monomer (b1), the monomer (b2) and the monomer (b3 ) and a structural unit derived from the following monomer (b4)
  • the upper limit of the content of the structural unit derived from the monomer (b3) is preferably 98% by mass or less, more preferably 97% by mass or less, and the lower limit is , preferably 25% by mass or more, more preferably 50% by mass or more.
  • the content of structural units derived from the monomer (b3) can be calculated from the amount of the monomer (b3) in the monomer component used when synthesizing the polymer (B).
  • Examples of the monomer (b3) include monomers similar to the monomer (a3).
  • the monomer (b3) may be used alone or in combination of two or more.
  • Monomer (b3) is a monomer other than monomer (b1), monomer (b2) and monomer (b4) below.
  • Polymer (B) further contains at least one monomer (b4) selected from alicyclic hydrocarbon group-containing (meth)acrylates and aromatic hydrocarbon group-containing (meth)acrylates (hereinafter also referred to as "monomer (b4)" It may contain structural units derived from When the polymer (B) contains structural units derived from an alicyclic hydrocarbon group-containing (meth)acrylate, it is possible to easily adjust the cohesive strength and stress relaxation properties of the resulting pressure-sensitive adhesive layer.
  • the polymer (B) contains a structural unit derived from an aromatic hydrocarbon group-containing (meth)acrylate, it is possible to easily form a pressure-sensitive adhesive layer that has excellent adhesion to an adherend and can suppress light leakage. can be done.
  • the content of the structural unit derived from the monomer (b4) is the total content of the polymer (B) from the viewpoint that the above effects are exhibited more. It is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, based on 100% by mass of the structural units.
  • the content of structural units derived from the monomer (b4) can be calculated from the amount of the monomer (b4) in the monomer component used when synthesizing the polymer (B).
  • Examples of the monomer (b4) include monomers similar to the monomer (a4).
  • the monomer (b4) may be used alone or in combination of two or more.
  • Monomer (b4) is a monomer other than monomer (b1) and monomer (b2).
  • the polymer (B) may further contain constituent units derived from monomers other than the monomer (b1), the monomer (b2), the monomer (b3) and the monomer (b4), as long as the object of the present invention is not impaired. good.
  • the content of the structural unit derived from the other monomer is preferably 30% by mass or less, preferably 20% by mass, based on 100% by mass of the total structural units of the polymer (B), from the viewpoint that the above effect is more exhibited. % or less.
  • the content of structural units derived from other monomers can be calculated from the amount of other monomers in the monomer component used when synthesizing the polymer (B).
  • Examples of the other monomers include monomers similar to the other monomers listed in the column for polymer (A). Another monomer may be used individually by 1 type, and 2 or more types may be used.
  • Polymer (B) can be synthesized by polymerizing the aforementioned monomer components, and may be, for example, a random polymer, a block polymer or a graft polymer, and can be synthesized by various polymerization methods.
  • the polymerization method is not particularly limited, and examples thereof include solution polymerization, emulsion polymerization, and suspension polymerization. Among these, in producing the present composition using a mixture of polymers obtained by polymerization, solution polymerization is preferred from the viewpoint that the processing steps are relatively simple and can be carried out in a short period of time. preferable.
  • a reaction vessel is charged with other components such as a monomer component, a polymerization initiator and, if necessary, a chain transfer agent and a polymerization solvent, and the reaction initiation temperature is usually 40° C. or higher, preferably 50° C. C. or higher, usually 100.degree. C. or lower, preferably 80.degree. .
  • the reaction is performed, for example, under an inert gas atmosphere such as nitrogen gas.
  • at least one selected from monomer components, polymerization initiators, chain transfer agents, and polymerization solvents may be additionally added during the polymerization reaction.
  • the same polymerization initiator and polymerization solvent as those described in the section for the method for synthesizing the polymer (A) can be used. are mentioned.
  • Mw of polymer (B) measured by GPC method is greater than 250,000 and smaller than Mw of polymer (A).
  • the lower limit of Mw of the polymer (B) is preferably 300,000 or more, more preferably 500,000 or more.
  • the upper limit of the Mw of the polymer (B) is not particularly limited as long as it is smaller than the Mw of the polymer (A), preferably 1,000,000 or less.
  • the shrinkage of the adherend It is possible to easily form a pressure-sensitive adhesive layer that can be relieved without residual internal stress while exhibiting a sufficient shear stress against.
  • the Mw can be measured by the method described in Examples below.
  • the Mw of polymer (B) is smaller than the Mw of polymer (A), and the ratio of Mw of polymer (B) to Mw of polymer (A) (Mw of polymer (B)/Mw of polymer (A)) is preferably is 0.8 or less, more preferably 0.6 or less.
  • the acid value of polymer (B) is 1.0 mgKOH/g or less, preferably 0.8 mgKOH/g or less, more preferably 0 mgKOH/g.
  • the acid value of the polymer (B) is within the above range, corrosion of adherends in contact with the pressure-sensitive adhesive layer formed from the obtained pressure-sensitive adhesive composition can be suppressed.
  • the acid value can be measured by the method described in Examples below.
  • the amount of the acidic group-containing monomer used is 0.12% by mass or less with respect to 100% by mass of the monomer component, or , preferably without substantially using an acidic group-containing monomer.
  • the acidic group-containing monomer include monomers similar to the acidic group-containing monomers described in the column of polymer (A).
  • the composition can contain one or more polymers (B).
  • the content of the polymer (B) in the present composition is 10 parts by mass or more, preferably 25 parts by mass or more, more preferably 40 parts by mass or more, preferably 300 parts by mass with respect to 100 parts by mass of the polymer (A). It is not more than 200 parts by mass, more preferably not more than 200 parts by mass.
  • the content of the polymer (B) is within the above range, even when the pressure-sensitive adhesive layer obtained from the present composition is used in contact with an adherend (e.g., polarizing plate) that undergoes large shrinkage due to temperature changes, Therefore, it is possible to easily form a pressure-sensitive adhesive layer that can be relieved without residual internal stress while exhibiting sufficient shear stress against shrinkage of the adherend.
  • adherend e.g., polarizing plate
  • the composition contains an isocyanate-based curing agent (C) (hereinafter also referred to as “curing agent (C)”).
  • curing agent (C) examples include isocyanate compounds having two or more isocyanate groups in one molecule.
  • curing agent (C) examples include isocyanate monomers such as xylylene diisocyanate, tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenylmethane diisocyanate; Isocyanate compounds obtained by addition reaction with divalent or higher alcohol compounds such as trimethylolpropane; buret-type isocyanate compounds; polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, etc. added to isocyanate monomers. and urethane prepolymer type isocyanates; isocyanurate compounds.
  • isocyanate monomers such as xylylene diisocyanate, tolylene diisocyanate, chloropheny
  • the composition may contain one or more curing agents (C).
  • the content of the curing agent (C) in the present composition is more than 6 parts by mass and less than 30 parts by mass, preferably 7 parts by mass, with respect to a total of 100 parts by mass of the polymer (A) and the polymer (B). Above, more preferably 8 parts by mass or more, preferably 25 parts by mass or less, more preferably 20 parts by mass or less.
  • the fact that the content of the curing agent (C) is within the above range means that the amount of the curing agent (C) is such that the amount of isocyanate groups is excessive with respect to the number of crosslinkable functional groups possessed by the polymer (A). means to use in quantity.
  • the present composition may contain other components other than the polymer (A), the polymer (B) and the curing agent (C), such as a curing agent (D ), silane coupling agent (E), antistatic agent (F), tackifying resin, antioxidant, light stabilizer, metal corrosion inhibitor, plasticizer, cross-linking accelerator, surfactant, reworking agent, organic solvent may contain.
  • a curing agent (D ) silane coupling agent (E), antistatic agent (F), tackifying resin, antioxidant, light stabilizer, metal corrosion inhibitor, plasticizer, cross-linking accelerator, surfactant, reworking agent, organic solvent may contain.
  • a curing agent (D ), silane coupling agent (E), antistatic agent (F), tackifying resin, antioxidant, light stabilizer, metal corrosion inhibitor, plasticizer, cross-linking accelerator, surfactant, reworking agent, organic solvent may contain.
  • Each of these other components may be used singly or in combination of two or more.
  • the present composition may contain a curing agent (D) (hereinafter also referred to as "curing agent (D)”) other than the curing agent (C).
  • a curing agent (D) (hereinafter also referred to as "curing agent (D)") other than the curing agent (C).
  • curing agent (D) include epoxy curing agents and metal chelate curing agents.
  • epoxy-based curing agents include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N, N,N',N'-tetraglydyl-m-xylylenediamine, N,N,N',N'-tetraglydylaminophenylmethane, triglycidyl isocyanurate, mN,N-diglycidylaminophenylglycidyl ether , N,N-diglycidyltoluidine, N,N-diglycidylaniline, pentaerythritol polyglycidyl ether, 1,6-hexanediol diglycidyl ether.
  • metal chelate curing agents include polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium combined with alkoxides, acetylacetone, ethyl acetoacetate, and the like.
  • a compound with a Specific examples include aluminum isopropylate, aluminum secondary butyrate, aluminum ethylacetoacetate/diisopropylate, aluminum trisethylacetoacetate, and aluminum trisacetylacetonate.
  • the content of the curing agent (D) in the present composition should be the same as the polymer (A) and the polymer (B) in terms of exhibiting the above effects more. It is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, preferably 6 parts by mass or less, and more preferably 3 parts by mass or less, relative to the total 100 parts by mass of .
  • the composition may contain a silane coupling agent (E).
  • a silane coupling agent (E) By including the silane coupling agent (E) in the present composition, it is possible to easily form a pressure-sensitive adhesive layer having high adhesion to an adherend.
  • Silane coupling agents (E) include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, silane coupling agents containing polymerizable unsaturated groups such as methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane; , 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and other epoxy groups Containing silane coupling agent; amino such as 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane Group-containing silane coupling agents; Hal
  • the content of the silane coupling agent (E) in the composition is It is usually 1 part by mass or less, preferably 0.01 mass part or more, more preferably 0.05 mass part or more, and preferably 1 mass part or less, more preferably 0.5 mass part or less.
  • the content of the silane coupling agent (E) is within the above range, peeling of the pressure-sensitive adhesive layer from the adherend can be easily suppressed even in a high-humidity and heat environment, and even in a high-temperature environment, the silane coupling It tends to be possible to easily form a pressure-sensitive adhesive layer in which bleeding of the agent (E) is difficult to occur.
  • the composition may contain an antistatic agent (F).
  • Antistatic agents (F) include, for example, surfactants, ionic compounds, and conductive polymers.
  • Surfactants include, for example, quaternary ammonium salts, quaternary amide quaternary ammonium salts, pyridium salts, cationic surfactants having cationic groups such as primary to tertiary amino groups; sulfonate groups, sulfate esters Anionic surfactants having anionic groups such as bases and phosphate ester bases; Amphoteric surfactants such as alkylbetaines, alkylimidazolinium betaines, alkylamine oxides, amino acid sulfate esters; , sorbitan fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, N-hydroxyethyl-N-2-hydroxyalkylamines, alkyldiethanolamides and other nonionic surfactants. be done.
  • the surfactant also includes a reactive emulsifier having a polymerizable group, and a polymer-based surfactant obtained by increasing the molecular weight of the monomer component containing the surfactant or reactive emulsifier can also be used.
  • the ionic compound is a compound composed of a cation portion and an anion portion, and may be a solid or liquid compound at room temperature (23°C) and 50% RH.
  • the cation moiety constituting the ionic compound may be either one or both of inorganic cations and organic cations.
  • inorganic cations alkali metal ions and alkaline earth metal ions are preferable, and Li + , Na + and K + which are excellent in antistatic properties are more preferable.
  • organic cations include pyridinium cations, piperidinium cations, pyrrolidinium cations, pyrroline cations, pyrrole cations, imidazolium cations, tetrahydropyrimidinium cations, dihydropyrimidinium cations, pyrazolium cations, and pyrazolium cations.
  • the anion portion constituting the ionic compound is not particularly limited as long as it can ionically bond with the cation portion to form an ionic compound.
  • Ionic compounds include lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium tris(trifluoromethanesulfonyl)methane, potassium bis(trifluoromethanesulfonyl)imide, potassium bis(fluorosulfonyl)imide, 1 - ethylpyridinium hexafluorophosphate, 1-butylpyridinium hexafluorophosphate, 1-hexyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium bis(fluoro sulfonyl)imide, 1-octyl-4-methylpyridinium bis(fluoro sulfonyl)imide, 1-octyl-4-methylpyridinium bis(trifluo
  • Examples of conductive polymers include polythiophene, polyaniline, polypyrrole, and derivatives thereof.
  • the content of the antistatic agent (F) in the present composition is usually 3 parts per 100 parts by mass of the total of the polymer (A) and the polymer (B). parts by mass or less, preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2.5 parts by mass.
  • the composition may contain an organic solvent as long as the effects of the present invention are not impaired.
  • the organic solvent includes, for example, the polymerization solvents described in the section of the method for synthesizing the polymer (A).
  • the composition may be prepared, for example, by mixing a polymer solution containing the polymer (A) and the polymerization solvent, a polymer solution containing the polymer (B) and the polymerization solvent, and the curing agent (C).
  • the content of the organic solvent in the present composition is, for example, 0% by mass or more, preferably 10% by mass or more, and is, for example, 90% by mass or less, preferably 80% by mass or less.
  • the present composition can be prepared, for example, by mixing the polymer (A), the polymer (B), the curing agent (C), and, if necessary, the other components by a known method using a stirring device or the like. can be manufactured by When mixing and stirring each component, each component may be mixed and stirred all at once, or may be mixed and stirred sequentially.
  • the stirring conditions are not particularly limited, but from the standpoint of workability and productivity, the stirring may be performed at room temperature for about 10 to 120 minutes.
  • the application of the present composition is not particularly limited, and it can be used without limitation in the applications in which the pressure-sensitive adhesive layer has been used. It is preferably used for bonding members, and more preferably used for bonding members constituting a display device such as a touch panel type input/output device.
  • Members (adherends) to be bonded using the present composition include, for example, polarizing films (including elliptical polarizing films), retardation films, antireflection films, brightness enhancement films, light diffusion films, and hard coats.
  • Optical films such as films, metal or metal oxide layers such as ITO layers, and substrates made of glass or resin can be used.
  • a pressure-sensitive adhesive sheet according to an embodiment of the present invention (hereinafter also referred to as “the present pressure-sensitive adhesive sheet") has a pressure-sensitive adhesive layer (hereinafter also referred to as “the present pressure-sensitive adhesive layer”) obtained from the present composition.
  • the present pressure-sensitive adhesive sheet may be a sheet consisting only of the present pressure-sensitive adhesive layer, and includes at least one adherend selected from the optical film, the metal or metal oxide layer, the substrate, etc., and the pressure-sensitive adhesive layer. It may be a laminate containing.
  • the pressure-sensitive adhesive layer contained in the laminate may be one layer or two or more layers. When there are two or more layers, these may be the same layer or different layers. The same applies to adherends (other layers such as optical films) included in the laminate.
  • the thickness of the adhesive sheet is not particularly limited.
  • the thickness is approximately the same as the thickness of the pressure-sensitive adhesive layer described below.
  • the pressure-sensitive adhesive sheet is the laminate, it varies depending on the type of the adherend and may be appropriately selected according to the application. 200 ⁇ m or less.
  • the present pressure-sensitive adhesive layer is formed from the present composition, and specifically, can be formed by subjecting the present composition to a cross-linking reaction.
  • Examples of preferred aspects of the present pressure-sensitive adhesive layer obtained by subjecting the present composition to a cross-linking reaction include an aspect including a cross-linked product of the polymer (A) with the curing agent (C). Excess self-condensate of curing agent (C) that did not contribute to the cross-linking reaction is entangled with at least one selected from polymer (A), cross-linked polymer (A) and polymer (B).
  • the gel fraction of the present pressure-sensitive adhesive layer is not particularly limited. It is preferably 50% or more, more preferably 60% or more, and preferably 90% or less, more preferably 85% or less. Specifically, the gel fraction can be measured by the method described in Examples below.
  • the thickness of the pressure-sensitive adhesive layer may be appropriately set according to the application of the pressure-sensitive adhesive sheet, and is not particularly limited, but is usually 5 ⁇ m or more, preferably 10 ⁇ m or more, and usually 125 ⁇ m or less, preferably 100 ⁇ m or less. .
  • the adhesive strength of the present pressure-sensitive adhesive layer is preferably 1.0 N/25 mm or more in terms of sufficient adhesion to the adherend, etc., and when used by adhering to the adherend, It is more preferably 2.0 to 20.0 to 2.0 to 20.0, since it does not peel off or float from the adherend, and when it is desired to be peeled off from the adherend, it has an appropriate adhesive strength that allows it to be peeled off from the adherend without leaving an adhesive residue. 0 N/25 mm. Specifically, the adhesive strength can be measured by the method described in Examples below.
  • the pressure-sensitive adhesive layer is formed on the adherend or support by, for example, applying the present composition to the adherend or support and causing a cross-linking reaction of the applied composition. can be formed. After coating the present composition on the adherend or support, if necessary, further arrange the adherend or support on the coated surface to allow the composition to undergo a cross-linking reaction. good.
  • the pressure-sensitive adhesive layer may be peeled off from the support.
  • the pressure-sensitive adhesive sheet consisting of only the pressure-sensitive adhesive layer is stored, transferred, etc. together with the support during storage, transfer, etc., and is peeled off from the support during use. Just do it.
  • the support includes a release-treated substrate.
  • the composition is applied onto the adherend, and a support is placed on the coated surface to obtain the adherend and the pressure-sensitive adhesive.
  • a laminate in which a layer and a support are laminated in this order can be obtained.
  • the laminate can be used as a pressure-sensitive adhesive sheet consisting of an adherend and the present pressure-sensitive adhesive layer after peeling off the support.
  • the substrate used as the adherend and the substrate used as the support are not particularly limited, and examples thereof include resin plates, glass plates, woven fabrics, non-woven fabrics, and paper.
  • the resin is preferably a transparent resin, and examples of the transparent resin include polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polypropylene (PP), acrylonitrile-butadiene-styrene copolymer ( ABS), polyamide (nylon), and the like.
  • the coating method of the composition a known method such as a spin coating method, a knife coating method, a roll coating method, a bar coating method, a blade coating method, a die coating method, or a gravure coating method can be used to obtain a predetermined pressure-sensitive adhesive layer. and a method of coating so as to have a thickness of .
  • the composition instead of coating, can be placed on the adherend or support by immersing the adherend or support in the composition.
  • the applied (arranging) composition may be dried, if necessary.
  • the drying conditions vary depending on the type of solvent, but are generally 50° C. or higher, preferably 60° C. or higher, generally 150° C. or lower, preferably 100° C. or lower, and generally 1 minute or longer, preferably 2 minutes or longer. Conditions for drying for 10 minutes or less, preferably 7 minutes or less are included.
  • the curing conditions are usually 5° C. or higher, preferably 15° C. or higher, usually 60° C. or lower, preferably 40° C. or lower, usually 5 to 70% RH, preferably 5 to 50% RH.
  • An optical member according to one embodiment of the present invention has the pressure-sensitive adhesive layer.
  • a specific example of the optical member is the laminate.
  • a liquid crystal display device including a laminate in which a polarizing plate, the present pressure-sensitive adhesive layer, a liquid crystal panel, the present pressure-sensitive adhesive layer, and a polarizing plate are laminated in this order
  • a touch panel includes a laminate in which a shatterproof film, the present pressure-sensitive adhesive layer, an ITO layer, and a glass panel are laminated in this order.
  • GPC gel permeation chromatography
  • the acid value (mgKOH/g) of each polymer refers to the amount (mg) of potassium hydroxide required to neutralize 1 g of polymer.
  • the measurement method is as follows. First, a measurement sample was prepared by adding 50 mL of a toluene/ethanol (volume ratio: 2/1) mixed solution to a sample of about 1 g of polymer and dissolving it. Next, the measurement sample is subjected to potentiometric titration with a 0.1 N potassium hydroxide ethanol solution using an automatic titrator (AUT-501, manufactured by Toa DKK Co., Ltd.). Necessary for neutralizing the measurement sample amount of potassium hydroxide ethanol solution was measured.
  • the acid value was calculated by the following formula (I).
  • Formula (I): Acid value (mgKOH/g) (B x f x 5.611)/S B: Amount (mL) of 0.1N potassium hydroxide ethanol solution used for titration f: factor of 0.1N potassium hydroxide ethanol solution S: mass (g) of solid content of measurement sample
  • Example 1 The polymer solution of the polymer (A-1) obtained in Production Example A-1 was mixed with the polymer solution of the polymer (B-1) obtained in Production Example B-1 to obtain a polymer mixture.
  • the blending amount of the polymer (B-1) is 60 parts by mass of the polymer (B-1) with respect to 100 parts by mass of the polymer (A-1) in the polymer solution obtained in Production Example A-1. is the amount.
  • an isocyanate curing agent L-45 manufactured by Soken Chemical Co., Ltd.
  • the amount of L-45 is such that the solid content of L-45 is 12 parts by mass with respect to the total of 100 parts by mass of polymer (A-1) and polymer (B-1).
  • Examples 2 to 36 and Comparative Examples 1 to 11 A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1, except that the formulation composition was changed as shown in Tables 1 to 3.
  • the added amount [parts by mass] in Tables 1 to 3 is the added amount of the polymer (B) or the polymer for comparison of the polymer (B) with respect to 100 parts by mass of the polymer (A) or the polymer for comparison of the polymer (A). is.
  • the numerical values in the columns of each curing agent, silane coupling agent, and antistatic agent are polymer (A) (or polymer for comparison of polymer (A)) and polymer (B) (or polymer (B) for comparison).
  • the amount (parts by mass) of the solid content of each of these components added to a total of 100 parts by mass with the polymer) is shown.
  • the pressure-sensitive adhesive layer-attached polarizing plate thus prepared was cut into a size of 150 mm ⁇ 250 mm, the PET film was peeled off, and the plate was adhered to a glass plate having a thickness of 1.1 mm and pressure-bonded.
  • the glass plate to which the pressure-sensitive adhesive layer-attached polarizing plate was attached was autoclaved under conditions of 50° C. and 5 atm for 20 minutes, and then left in an environment of 23° C./50% RH for 24 hours.
  • ⁇ Light leakage test> The pressure-sensitive adhesive layer-attached polarizing plate having the PET film produced as described above was cut into 150 mm ⁇ 250 mm, the PET film was peeled off, and the polarizing axes were perpendicular to each other.
  • a laminated body for a light leakage test was produced by crimping. The produced laminate for light leakage test was autoclaved under conditions of 50° C. and 5 atm for 20 minutes, and then left in an environment of 80° C. for 500 hours. The obtained laminate for light leakage test was irradiated with light from a backlight of a liquid crystal monitor, and the state of light leakage at that time was visually evaluated according to the following criteria. (Evaluation criteria) A: No light leakage is observed. ⁇ : Light leakage is slightly observed, but it is practically no problem. ⁇ : Light leakage is observed, and there is a possibility that a practical problem will occur. x: Significant light leakage is observed.
  • ⁇ Adhesion test> The pressure-sensitive adhesive layer-attached polarizing plate having the PET film produced as described above was cut to a width of 25 mm, the release-treated PET film was peeled off, and the plate was laminated to a glass plate in an environment of 23°C/50% RH, Autoclave treatment was performed for 20 minutes under conditions of 50° C. and 5 atm. After that, it was taken out in an environment of 23° C./50% RH and allowed to stand still for 1 hour, and the adhesive force was measured when the polarizing plate with an adhesive layer was peeled off from the glass plate at a peeling angle of 180° and a tensile speed of 300 mm/min. did.
  • the PET film of the adhesive layer-attached polarizing plate having the PET film prepared as described above was peeled off, and an ITO vapor deposition film cut to 10 mm ⁇ 60 mm was pasted on the adhesive layer, and the pressure was applied at 50°C and 5 atm for 20 minutes. It was autoclaved. Then, it was left under an environment of 23° C./50% RH for 1 hour, and then left under an environment of 60° C./90% RH for 500 hours. Then, after being left for 1 hour in an environment of 23° C./50% RH, the resistance value of the ITO deposited film (resistance value after the test) was measured.
  • the rate of change in the resistance value after the test with respect to the resistance value before the test was obtained. was evaluated according to the criteria of Here, since the change in the resistance value is considered to be caused by corrosion of ITO, it is determined that there is ITO corrosiveness when the rate of change exceeds 120%, and ITO corrosion when the rate of change is 120% or less. determined to be non-sexual. A tester (manufactured by Sanwa Electric Instrument Co., Ltd., digital multimeter PC510) was used to measure the resistance value.
  • the pressure-sensitive adhesive layer in each example had appropriate adhesive strength, and was excellent in durability and corrosion resistance under high-temperature and high-humidity environments.
  • Comparative Examples 1 and 2 using polymer (A) and polymer (B) with oxidation exceeding 1.0 mg KOH / g had insufficient high temperature durability, wet heat durability and corrosiveness. rice field.
  • Comparative Examples 3 and 4 using a polymer (B) containing more than 0.05% by mass of structural units derived from a hydroxyl group-containing monomer or an amino group-containing monomer as a constituent show high temperature durability and wet heat durability. was insufficient.
  • Comparative Examples 9 and 10 in which the content of the curing agent (C) is 6 parts by mass or less or 30 parts by mass or more with respect to a total of 100 parts by mass of the polymer (A) and the polymer (B), are excellent in high temperature durability and The wet heat durability was insufficient.
  • Comparative Example 11 using the polymer (A) in which the structural units derived from the hydroxyl group-containing monomer and the amino group-containing monomer are 0% by mass as the constituent components has poor high temperature durability, wet heat durability, reworkability, and light leakage prevention performance. was enough.

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Abstract

One embodiment of the present invention relates to an adhesive agent composition, an adhesive sheet or an optical member. The adhesive agent composition contains: an acrylic polymer (A) which contains more than 0% by mass but not more than 0.4% by mass of constituent units derived from a hydroxyl group-containing monomer and an amino group-containing monomer, while having an acid value of 1.0 mgKOH/g or less and an Mw of 600,000 or more; an acrylic polymer (B) which contains 0.05% by mass or less of constituent units derived from a hydroxyl group-containing monomer and an amino group-containing monomer, while having an acid value of 1.0 mgKOH/g or less and an Mw of more than 250,000 but less than the Mw of the component (A); and an isocyanate-based curing agent (C). With respect to this adhesive agent composition, 10 parts by mass or more of the component (B) is contained relative to 100 parts by mass of the component (A); and more than 6 parts by mass but less than 30 parts by mass of the component (C) is contained relative to a total of 100 parts by mass of the components (A) and (B).

Description

粘着剤組成物、粘着シートおよび光学部材Adhesive composition, adhesive sheet and optical member
　本発明の一実施形態は、粘着剤組成物、粘着シートまたは光学部材に関する。 One embodiment of the present invention relates to a pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet or optical member.
　液晶ディスプレイ等の表示装置などには、偏光板や位相差板などの光学部材が使用されており、該光学部材は、通常、粘着剤組成物から得られる粘着剤層を介してガラス製やプラスチック製等の他の部材に貼り付けて使用される。
　前記表示装置等は、様々な環境下で使用されるため、貼合層として用いられる粘着剤層にも、様々な環境下において耐熱性、凝集性、接着性等の所望の特性を示すことが求められている。様々な環境の中でも、例えば、高温高湿になり得る過酷な環境として、自動車などの車内が挙げられる。 Optical members such as polarizing plates and retardation plates are used in display devices such as liquid crystal displays. It is used by attaching it to other members such as steel.
Since the display devices and the like are used in various environments, the pressure-sensitive adhesive layer used as the lamination layer can exhibit desired properties such as heat resistance, cohesiveness, and adhesiveness in various environments. It has been demanded. Among various environments, for example, the inside of a vehicle such as an automobile is exemplified as a harsh environment that can become hot and humid.
　高温高湿下で所望の特性を示す粘着剤組成物として、例えば、特許文献１および２には、カルボキシ基を有するアクリル系重合体を用いる粘着剤組成物が開示されている。 For example, Patent Documents 1 and 2 disclose pressure-sensitive adhesive compositions using acrylic polymers having carboxy groups as pressure-sensitive adhesive compositions that exhibit desired properties under high temperature and high humidity conditions.
特開２０１４－１９６３７６号公報JP 2014-196376 A 特開２０１５－１１７３４４号公報JP 2015-117344 A
　前記自動車などの車内に搭載される表示装置等に用いられる粘着剤層には、例えば、１１５℃での耐久性が求められている。しかしながら、前記特許文献１および特許文献２に開示された粘着剤組成物などの従来の粘着剤組成物から得られる粘着剤層は、１１５℃の温度領域では、凝集力と応力緩和性とのバランスが悪く、凝集力が低下することなどにより発泡が生じたり、応力緩和性が低下することなどにより被着体からの剥がれや、さらには光漏れ等の不具合が生じたりする。したがって、従来の粘着剤組成物には、高温耐久性の点で改良の余地があることが分かった。 For example, durability at 115°C is required for the pressure-sensitive adhesive layer used in the display device and the like mounted inside the automobile. However, the pressure-sensitive adhesive layers obtained from conventional pressure-sensitive adhesive compositions such as the pressure-sensitive adhesive compositions disclosed in Patent Document 1 and Patent Document 2 have a balance between cohesion and stress relaxation in a temperature range of 115 ° C. This causes foaming due to reduced cohesion, and problems such as peeling from the adherend and light leakage due to reduced stress relaxation. Therefore, it was found that the conventional PSA compositions have room for improvement in terms of high-temperature durability.
　なお、粘着剤層には、被着体に粘着させて使用する際には、被着体から剥がれたり、浮いたりせず、被着体から剥離したい時には、糊残り等が起こらずに被着体から剥離できる（リワーク性に優れる）適度な粘着力を有することが求められることもある。
　また、粘着剤層は、電極に使用される金属やＩＴＯ（酸化インジウムスズ）などの金属酸化物等の腐食し得る被着体に接して用いられることがあり、このような場合に、該腐食し得る被着体を腐食させないことも求められている。 In addition, when the adhesive layer is used by sticking it to the adherend, it does not peel off or float from the adherend, and when it is desired to be peeled off from the adherend, it adheres without leaving any adhesive residue. In some cases, it is required to have an appropriate adhesive strength that allows it to be peeled off from the body (excellent in reworkability).
In addition, the pressure-sensitive adhesive layer may be used in contact with a corrodible adherend such as a metal used for electrodes or a metal oxide such as ITO (indium tin oxide). It is also required not to corrode possible adherends.
　本発明の一実施形態は、腐食し得る被着体に接した場合であっても該被着体の腐食を抑制することができ、適度な粘着力を有し、高温や高湿下でも発泡や被着体からの剥がれ等が生じ難い粘着剤層を形成することができる粘着剤組成物を提供する。 One embodiment of the present invention is capable of suppressing corrosion of a corrodible adherend even when it is in contact with the adherend, has an appropriate adhesive strength, and foams even under high temperature and high humidity. Provided is a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer that is less likely to be peeled off from an adherend.
　本発明者らは、前記課題を解決すべく鋭意検討を行った。その結果、下記構成例によれば、前記課題を解決できることを見出した。
　本発明の構成例は以下のとおりである。 The present inventors have made extensive studies to solve the above problems. As a result, the inventors have found that the problem can be solved by the following configuration example.
A configuration example of the present invention is as follows.
　［１］　水酸基含有モノマー（ａ１）由来の構成単位およびアミノ基含有モノマー（ａ２）由来の構成単位を合計して０質量％を超えて０．４質量％以下の量で含み、酸価が１．０ｍｇＫＯＨ／ｇ以下である、重量平均分子量（Ｍｗ）が６０万以上のアクリル系ポリマー（Ａ）と、
　水酸基含有モノマー（ｂ１）由来の構成単位およびアミノ基含有モノマー（ｂ２）由来の構成単位の合計含有量が０．０５質量％以下であり、酸価が１．０ｍｇＫＯＨ／ｇ以下である、重量平均分子量（Ｍｗ）が２５万超であり、かつ、前記アクリル系ポリマー（Ａ）のＭｗよりも小さいアクリル系ポリマー（Ｂ）と、
　イソシアネート系硬化剤（Ｃ）と
を含み、
　前記アクリル系ポリマー（Ａ）１００質量部に対し、前記アクリル系ポリマー（Ｂ）を１０質量部以上の量で含み、
　前記アクリル系ポリマー（Ａ）とアクリル系ポリマー（Ｂ）との合計１００質量部に対し、前記イソシアネート系硬化剤（Ｃ）を６質量部を超えて３０質量部未満の量で含む、
粘着剤組成物。 [1] Containing the structural unit derived from the hydroxyl group-containing monomer (a1) and the structural unit derived from the amino group-containing monomer (a2) in an amount exceeding 0% by mass and 0.4% by mass or less in total, and having an acid value of 1 an acrylic polymer (A) having a weight average molecular weight (Mw) of 600,000 or more, which is 0 mgKOH/g or less;
The total content of the structural units derived from the hydroxyl group-containing monomer (b1) and the structural units derived from the amino group-containing monomer (b2) is 0.05% by mass or less, and the acid value is 1.0 mgKOH/g or less, weight average an acrylic polymer (B) having a molecular weight (Mw) of more than 250,000 and smaller than the Mw of the acrylic polymer (A);
and an isocyanate curing agent (C),
The acrylic polymer (B) is contained in an amount of 10 parts by mass or more with respect to 100 parts by mass of the acrylic polymer (A),
The isocyanate curing agent (C) is contained in an amount of more than 6 parts by mass and less than 30 parts by mass with respect to a total of 100 parts by mass of the acrylic polymer (A) and the acrylic polymer (B).
Adhesive composition.
　［２］　前記アクリル系ポリマー（Ａ）が、アルキル（メタ）アクリレートおよびアルコキシアルキル（メタ）アクリレートから選ばれる少なくとも１種のモノマー（ａ３）由来の構成単位を２５～９９．９９質量％含む、［１］に記載の粘着剤組成物。 [2] The acrylic polymer (A) contains 25 to 99.99% by mass of structural units derived from at least one monomer (a3) selected from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates, [ 1].
　［３］　前記アクリル系ポリマー（Ｂ）が、アルキル（メタ）アクリレートおよびアルコキシアルキル（メタ）アクリレートから選ばれる少なくとも１種のモノマー（ｂ３）由来の構成単位を２５～１００質量％含む、［１］または［２］に記載の粘着剤組成物。 [3] The acrylic polymer (B) contains 25 to 100% by mass of constitutional units derived from at least one monomer (b3) selected from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates [1] Or the pressure-sensitive adhesive composition according to [2].
　［４］　前記アクリル系ポリマー（Ａ）が、前記水酸基含有モノマー（ａ１）由来の構成単位を０質量％を超えて０．４質量％以下の量で含む、［１］～［３］のいずれかに記載の粘着剤組成物。 [4] Any of [1] to [3], wherein the acrylic polymer (A) contains the structural unit derived from the hydroxyl group-containing monomer (a1) in an amount of more than 0% by mass and 0.4% by mass or less The pressure-sensitive adhesive composition according to 1.
　［５］　前記アクリル系ポリマー（Ａ）が、アルキル（メタ）アクリレートおよびアルコキシアルキル（メタ）アクリレートから選ばれる少なくとも１種のモノマー（ａ３）由来の構成単位を２５～９８質量％含み、脂環式炭化水素基含有（メタ）アクリレートおよび芳香族炭化水素基含有（メタ）アクリレートから選ばれる少なくとも１種のモノマー（ａ４）由来の構成単位を１～５０質量％含む、［１］～［４］のいずれかに記載の粘着剤組成物。 [5] The acrylic polymer (A) contains 25 to 98% by mass of structural units derived from at least one monomer (a3) selected from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates, and has an alicyclic [1] to [4] containing 1 to 50% by mass of structural units derived from at least one monomer (a4) selected from hydrocarbon group-containing (meth)acrylates and aromatic hydrocarbon group-containing (meth)acrylates. The pressure-sensitive adhesive composition according to any one of the above.
　［６］　前記アクリル系ポリマー（Ｂ）が、アルキル（メタ）アクリレートおよびアルコキシアルキル（メタ）アクリレートから選ばれる少なくとも１種のモノマー（ｂ３）由来の構成単位を２５～９８質量％含み、脂環式炭化水素基含有（メタ）アクリレートおよび芳香族炭化水素基含有（メタ）アクリレートから選ばれる少なくとも１種のモノマー（ｂ４）由来の構成単位を１～５０質量％含む、［１］～［５］のいずれかに記載の粘着剤組成物。 [6] The acrylic polymer (B) contains 25 to 98% by mass of structural units derived from at least one monomer (b3) selected from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates, and has an alicyclic [1] to [5] containing 1 to 50% by mass of structural units derived from at least one monomer (b4) selected from hydrocarbon group-containing (meth)acrylates and aromatic hydrocarbon group-containing (meth)acrylates. The pressure-sensitive adhesive composition according to any one of the above.
　［７］　前記イソシアネート系硬化剤（Ｃ）以外の硬化剤（Ｄ）をさらに含む、［１］～［６］のいずれかに記載の粘着剤組成物。 [7] The pressure-sensitive adhesive composition according to any one of [1] to [6], further comprising a curing agent (D) other than the isocyanate-based curing agent (C).
　［８］　シランカップリング剤（Ｅ）をさらに含む、［１］～［７］のいずれかに記載の粘着剤組成物。 [8] The adhesive composition according to any one of [1] to [7], further comprising a silane coupling agent (E).
　［９］　帯電防止剤（Ｆ）をさらに含む、［１］～［８］のいずれかに記載の粘着剤組成物。 [9] The adhesive composition according to any one of [1] to [8], further comprising an antistatic agent (F).
　［１０］　光学部材に用いられる、［１］～［９］のいずれかに記載の粘着剤組成物。 [10] The adhesive composition according to any one of [1] to [9], which is used for optical members.
　［１１］　［１］～［１０］のいずれかに記載の粘着剤組成物から得られた粘着剤層を有する粘着シート。
　［１２］　［１］～［１０］のいずれかに記載の粘着剤組成物から得られた粘着剤層を有する光学部材。 [11] A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition according to any one of [1] to [10].
[12] An optical member having a pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition according to any one of [1] to [10].
　本発明の一実施形態によれば、腐食し得る被着体に接した場合であっても該被着体の腐食を抑制することができ、適度な粘着力を有し、高温や高湿下でも、凝集力および応力緩和性にバランスよく優れ、発泡や被着体からの剥がれ等が生じ難い粘着剤層を形成することができる。また、本発明の一実施形態によれば、リワーク性に優れる粘着剤層を形成することができ、得られる粘着剤層を偏光板などの光学部材に用いた場合、該光学部材からの光漏れを十分に抑制することができる。 According to one embodiment of the present invention, even when in contact with a corrodible adherend, it is possible to suppress corrosion of the adherend, have an appropriate adhesive strength, and have a high temperature and high humidity. However, it is possible to form a pressure-sensitive adhesive layer that is excellent in well-balanced cohesive force and stress relaxation properties, and that hardly causes foaming or peeling from the adherend. Further, according to one embodiment of the present invention, it is possible to form a pressure-sensitive adhesive layer having excellent reworkability, and when the obtained pressure-sensitive adhesive layer is used for an optical member such as a polarizing plate, light leakage from the optical member can be prevented. can be sufficiently suppressed.
≪粘着剤組成物≫
　本発明の一実施形態に係る粘着剤組成物（以下「本組成物」ともいう。）は、水酸基含有モノマー（ａ１）由来の構成単位およびアミノ基含有モノマー（ａ２）由来の構成単位を合計して０質量％を超えて０．４質量％以下の量で含み、酸価が１．０ｍｇＫＯＨ／ｇ以下である、重量平均分子量（Ｍｗ）が６０万以上のアクリル系ポリマー（Ａ）と、
　水酸基含有モノマー（ｂ１）由来の構成単位およびアミノ基含有モノマー（ｂ２）由来の構成単位の合計含有量が０．０５質量％以下であり、酸価が１．０ｍｇＫＯＨ／ｇ以下である、重量平均分子量（Ｍｗ）が２５万超であり、かつ、前記アクリル系ポリマー（Ａ）のＭｗよりも小さいアクリル系ポリマー（Ｂ）と、
　イソシアネート系硬化剤（Ｃ）と
を含む粘着剤組成物であり、
　前記アクリル系ポリマー（Ａ）１００質量部に対し、前記アクリル系ポリマー（Ｂ）を１０質量部以上の量で含み、
　前記アクリル系ポリマー（Ａ）とアクリル系ポリマー（Ｂ）との合計１００質量部に対し、前記イソシアネート系硬化剤（Ｃ）を６質量部を超えて３０質量部未満の量で含む。 <<Adhesive composition>>
The pressure-sensitive adhesive composition according to one embodiment of the present invention (hereinafter also referred to as "this composition") is a total of the structural units derived from the hydroxyl group-containing monomer (a1) and the structural units derived from the amino group-containing monomer (a2). an acrylic polymer (A) having a weight average molecular weight (Mw) of 600,000 or more, which is contained in an amount of more than 0% by mass and 0.4% by mass or less, and has an acid value of 1.0 mgKOH/g or less;
The total content of the structural units derived from the hydroxyl group-containing monomer (b1) and the structural units derived from the amino group-containing monomer (b2) is 0.05% by mass or less, and the acid value is 1.0 mgKOH/g or less, weight average an acrylic polymer (B) having a molecular weight (Mw) of more than 250,000 and smaller than the Mw of the acrylic polymer (A);
A pressure-sensitive adhesive composition containing an isocyanate curing agent (C),
The acrylic polymer (B) is contained in an amount of 10 parts by mass or more with respect to 100 parts by mass of the acrylic polymer (A),
The isocyanate curing agent (C) is contained in an amount of more than 6 parts by mass and less than 30 parts by mass with respect to a total of 100 parts by mass of the acrylic polymer (A) and the acrylic polymer (B).
　本発明において、「アクリル系ポリマー」とは、アクリル酸由来の構成単位、アクリル酸塩由来の構成単位、アクリル酸エステル由来の構成単位、メタクリル酸由来の構成単位、メタクリル酸塩由来の構成単位およびメタクリル酸エステル由来の構成単位の合計が、アクリル系ポリマーの全構成単位１００質量％に対し、５０質量％以上であるポリマーのことをいう。 In the present invention, the "acrylic polymer" refers to a structural unit derived from acrylic acid, a structural unit derived from acrylate, a structural unit derived from acrylic acid ester, a structural unit derived from methacrylic acid, a structural unit derived from methacrylate, and A polymer in which the total amount of structural units derived from methacrylic acid ester is 50% by mass or more with respect to 100% by mass of all structural units of the acrylic polymer.
　本明細書において（メタ）アクリルは、アクリルおよびメタクリルの総称で用い、アクリルでもメタクリルでもよい。また、（メタ）アクリレートは、アクリレートおよびメタクリレートの総称で用い、アクリレートでもメタクリレートでもよい。さらに、（メタ）アクリロイルは、アクリロイルおよびメタクリロイルの総称で用い、アクリロイルでもメタクリロイルでもよい。 In this specification, (meth)acrylic is used as a generic term for acrylic and methacrylic, and may be acrylic or methacrylic. (Meth)acrylate is used as a generic term for acrylate and methacrylate, and may be either acrylate or methacrylate. Furthermore, (meth)acryloyl is used as a generic term for acryloyl and methacryloyl, and may be acryloyl or methacryloyl.
＜アクリル系ポリマー（Ａ）＞
　アクリル系ポリマー（Ａ）（以下「ポリマー（Ａ）」ともいう。）は、水酸基含有モノマー（ａ１）（以下「モノマー（ａ１）」ともいう。）由来の構成単位およびアミノ基含有モノマー（ａ２）（以下「モノマー（ａ２）」ともいう。）由来の構成単位を合計して０質量％を超えて０．４質量％以下の量で含み、酸価が１．０ｍｇＫＯＨ／ｇ以下であり、かつ、Ｍｗが６０万以上である。
　このようなポリマー（Ａ）を用いることで、腐食し得る被着体に接した場合であっても該被着体の腐食を抑制することができ、得られる粘着剤層の架橋密度を低くすることができるため、応力緩和性に優れ、被着体からの剥がれ等が生じ難い粘着剤層を容易に形成することができる。 <Acrylic polymer (A)>
The acrylic polymer (A) (hereinafter also referred to as "polymer (A)") is a structural unit derived from a hydroxyl group-containing monomer (a1) (hereinafter also referred to as "monomer (a1)") and an amino group-containing monomer (a2) (hereinafter also referred to as "monomer (a2)") containing structural units derived in an amount exceeding 0% by mass and 0.4% by mass or less, and having an acid value of 1.0 mgKOH/g or less, and , Mw is 600,000 or more.
By using such a polymer (A), it is possible to suppress corrosion of a corrodible adherend even when it is in contact with the adherend, thereby lowering the crosslink density of the obtained pressure-sensitive adhesive layer. Therefore, it is possible to easily form a pressure-sensitive adhesive layer that has excellent stress relaxation properties and is less likely to be peeled off from an adherend.
　ポリマー（Ａ）におけるモノマー（ａ１）由来の構成単位およびモノマー（ａ２）由来の構成単位の合計含有量、好ましくはポリマー（Ａ）におけるモノマー（ａ１）由来の構成単位の含有量は、ポリマー（Ａ）の全構成単位１００質量％に対し、０質量％を超えて０．４質量％以下であり、好ましくは０．２質量％以下、より好ましくは０．１５質量％以下、好ましくは０．００１質量％以上、より好ましくは０．００２質量％以上である。
　該含有量が前記範囲にあると、得られる粘着剤層の架橋密度が低くなり、応力緩和性に優れ、被着体の剥がれが生じ難い粘着剤層を容易に形成することができる。特に、該含有量が前記範囲にあると、大きく収縮し得る被着体（例：偏光板）に接して得られる粘着剤層を使用する場合、粘着剤層にかかる応力を緩和することができ、さらに該被着体の収縮を抑えることができる。
　モノマー（ａ１）およびモノマー（ａ２）由来の構成単位の含有量は、ポリマー（Ａ）を合成する際に用いるモノマー成分中のモノマー（ａ１）およびモノマー（ａ２）の量から算出することができる。 The total content of the structural units derived from the monomer (a1) and the structural units derived from the monomer (a2) in the polymer (A), preferably the content of the structural units derived from the monomer (a1) in the polymer (A) is the polymer (A ) is more than 0% by mass and 0.4% by mass or less, preferably 0.2% by mass or less, more preferably 0.15% by mass or less, preferably 0.001% by mass, based on 100% by mass of all structural units of It is at least 0.002% by mass, more preferably at least 0.002% by mass.
When the content is within the above range, the obtained pressure-sensitive adhesive layer has a low cross-linking density, which makes it possible to easily form a pressure-sensitive adhesive layer which is excellent in stress relaxation properties and which hardly causes peeling of the adherend. In particular, when the content is within the above range, the stress applied to the pressure-sensitive adhesive layer can be relaxed when using the pressure-sensitive adhesive layer obtained in contact with an adherend (e.g., polarizing plate) that can shrink significantly. Furthermore, shrinkage of the adherend can be suppressed.
The content of structural units derived from the monomer (a1) and the monomer (a2) can be calculated from the amounts of the monomer (a1) and the monomer (a2) in the monomer component used when synthesizing the polymer (A).
［水酸基含有モノマー（ａ１）］
　ポリマー（Ａ）は、モノマー（ａ１）およびモノマー（ａ２）から選ばれる少なくとも１種を含むモノマー成分を重合することで合成できるが、該モノマー成分は、モノマー（ａ１）を含むことが好ましい。モノマー（ａ１）は、１種単独で用いてもよく、２種以上を用いてもよい。 [Hydroxyl group-containing monomer (a1)]
The polymer (A) can be synthesized by polymerizing a monomer component containing at least one selected from the monomer (a1) and the monomer (a2), and the monomer component preferably contains the monomer (a1). The monomer (a1) may be used alone or in combination of two or more.
　モノマー（ａ１）としては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロシキブチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、８－ヒドロキシオクチル（メタ）アクリレート、１０－ヒドロキシデシル（メタ）アクリレート、１２－ヒドロキシラウリル（メタ）アクリレート、（４－ヒドロキシメチルシクロヘキシル）メチル（メタ）アクリレートが挙げられる。 Examples of the monomer (a1) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate.
［アミノ基含有モノマー（ａ２）］
　ポリマー（Ａ）は、モノマー（ａ１）およびモノマー（ａ２）から選ばれる少なくとも１種を含むモノマー成分を重合することで合成できるが、該モノマー成分は、モノマー（ａ２）を含まないことが好ましい。モノマー（ａ２）は、１種単独で用いてもよく、２種以上を用いてもよい。モノマー（ａ２）は、モノマー（ａ１）以外のモノマーである。
　なお、アミド基やイミド基は通常アミノ基には包含されないため、本発明において、アミド基やイミド基を有し、該アミド基やイミド基以外にアミノ基を有さないモノマーは、モノマー（ａ２）ではない。 [Amino group-containing monomer (a2)]
Polymer (A) can be synthesized by polymerizing a monomer component containing at least one selected from monomer (a1) and monomer (a2), but the monomer component preferably does not contain monomer (a2). The monomer (a2) may be used alone or in combination of two or more. Monomer (a2) is a monomer other than monomer (a1).
In addition, since an amide group or an imide group is not usually included in an amino group, in the present invention, a monomer having an amide group or an imide group and having no amino group other than the amide group or the imide group is a monomer (a2 )is not.
　モノマー（ａ２）としては、例えば、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート等のジアルキルアミノアルキル（メタ）アクリレートが挙げられる。 Examples of the monomer (a2) include dialkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.
［アルキル（メタ）アクリレートおよびアルコキシアルキル（メタ）アクリレート］
　ポリマー（Ａ）は、さらに、アルキル（メタ）アクリレートおよびアルコキシアルキル（メタ）アクリレートから選ばれる少なくとも１種のモノマー（ａ３）（以下「モノマー（ａ３）」ともいう。）由来の構成単位を含むことが好ましく、アルキル（メタ）アクリレートおよびアルコキシアルキル（メタ）アクリレート由来の構成単位を含むことが特に好ましい。モノマー（ａ３）は、モノマー（ａ１）、モノマー（ａ２）および下記モノマー（ａ４）以外のモノマーである。
　ポリマー（Ａ）がアルキル（メタ）アクリレート由来の構成単位を含むことにより、得られる粘着剤層の粘着力やリワーク性（貼り直し性）を容易に調整することができる。
　また、ポリマー（Ａ）がアルコキシアルキル（メタ）アクリレート由来の構成単位を含むことにより、得られる粘着剤層の物性（例：ゲル分率）が変化しなくなるまでの時間が短くなる（以下「エージング性に優れる」ともいう。）ため、品質安定性に優れる粘着剤層を生産性よく形成することができる。
　該ゲル分率は、具体的には下記実施例に記載の方法で測定できる。 [Alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates]
Polymer (A) further contains structural units derived from at least one monomer (a3) selected from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates (hereinafter also referred to as "monomer (a3)"). is preferred, and it is particularly preferred to contain structural units derived from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates. Monomer (a3) is a monomer other than monomer (a1), monomer (a2) and monomer (a4) below.
By including structural units derived from alkyl (meth)acrylate in the polymer (A), the adhesive strength and reworkability (reattachability) of the obtained pressure-sensitive adhesive layer can be easily adjusted.
In addition, when the polymer (A) contains a structural unit derived from an alkoxyalkyl (meth)acrylate, the time until the physical properties (eg, gel fraction) of the resulting pressure-sensitive adhesive layer do not change is shortened (hereinafter referred to as "aging Therefore, it is possible to form a pressure-sensitive adhesive layer with excellent quality stability with good productivity.
Specifically, the gel fraction can be measured by the method described in Examples below.
　ポリマー（Ａ）が、モノマー（ａ３）由来の構成単位を含有する場合、モノマー（ａ３）由来の構成単位の含有量は、前記効果がより発揮される等の点から、ポリマー（Ａ）の全構成単位１００質量％に対し、好ましくは２５～９９．９９質量％、より好ましくは５０～９９．９９質量％である。なお、ポリマー（Ａ）がモノマー（ａ１）、モノマー（ａ２）およびモノマー（ａ３）由来の構成単位以外の構成単位を含有する場合、特に、モノマー（ａ１）、モノマー（ａ２）、モノマー（ａ３）および下記モノマー（ａ４）由来の構成単位を含有する場合、モノマー（ａ３）由来の構成単位の含有量の上限は、好ましくは９８質量％以下、より好ましくは９７質量％以下であり、下限は、好ましくは２５質量％以上、より好ましくは５０質量％以上である。
　モノマー（ａ３）由来の構成単位の含有量は、ポリマー（Ａ）を合成する際に用いるモノマー成分中のモノマー（ａ３）の量から算出することができる。 When the polymer (A) contains a structural unit derived from the monomer (a3), the content of the structural unit derived from the monomer (a3) is the total content of the polymer (A) from the viewpoint that the above effects are exhibited more. It is preferably 25 to 99.99% by mass, more preferably 50 to 99.99% by mass, based on 100% by mass of the structural units. When the polymer (A) contains structural units other than those derived from the monomer (a1), the monomer (a2) and the monomer (a3), particularly the monomer (a1), the monomer (a2) and the monomer (a3) And if it contains a structural unit derived from the following monomer (a4), the upper limit of the content of the structural unit derived from the monomer (a3) is preferably 98% by mass or less, more preferably 97% by mass or less, and the lower limit is It is preferably 25% by mass or more, more preferably 50% by mass or more.
The content of structural units derived from the monomer (a3) can be calculated from the amount of the monomer (a3) in the monomer component used when synthesizing the polymer (A).
　前記アルキル（メタ）アクリレートとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｉｓｏ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｉｓｏ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、ｉｓｏ－オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、ｉｓｏ－ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ｉｓｏ－デシル（メタ）アクリレート、ウンデカ（メタ）アクリレート、ラウリル（メタ）アクリレート、オレイル（メタ）アクリレート、ｎ－ステアリル（メタ）アクリレート、ｉｓｏ－ステアリル（メタ）アクリレート等の炭素数１～２０のアルキル（メタ）アクリレートが挙げられる。
　前記アルキル（メタ）アクリレートが有するアルキル基の炭素数は、好ましくは１～１２、より好ましくは１～８である。
　アルキル（メタ）アクリレートは、１種単独で用いてもよく、２種以上を用いてもよい。 Examples of the alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, iso-octyl (meth) acrylate, nonyl (meth) acrylate, iso-nonyl (meth) acrylate, decyl (meth) acrylate, iso-decyl (meth) acrylate, undeca (meth) acrylate, lauryl (meth) acrylate, oleyl (meth) acrylate , n-stearyl (meth)acrylate, iso-stearyl (meth)acrylate and other alkyl (meth)acrylates having 1 to 20 carbon atoms.
The number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is preferably 1-12, more preferably 1-8.
Alkyl (meth)acrylate may be used individually by 1 type, and may use 2 or more types.
　前記アルコキシアルキル（メタ）アクリレートとしては、例えば、メトキシメチル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、３－メトキシプロピル（メタ）アクリレート、３－エトキシプロピル（メタ）アクリレート、４－メトキシブチル（メタ）アクリレート、４－エトキシブチル（メタ）アクリレートが挙げられる。
　アルコキシアルキル（メタ）アクリレートは、１種単独で用いてもよく、２種以上を用いてもよい。 Examples of the alkoxyalkyl (meth)acrylates include methoxymethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (Meth)acrylate, 4-methoxybutyl (meth)acrylate, 4-ethoxybutyl (meth)acrylate.
One type of alkoxyalkyl (meth)acrylate may be used alone, or two or more types may be used.
［脂環式炭化水素基含有（メタ）アクリレートおよび芳香族炭化水素基含有（メタ）アクリレート］
　ポリマー（Ａ）は、さらに、脂環式炭化水素基含有（メタ）アクリレートおよび芳香族炭化水素基含有（メタ）アクリレートから選ばれる少なくとも１種のモノマー（ａ４）（以下「モノマー（ａ４）」ともいう。）由来の構成単位を含んでいてもよい。モノマー（ａ４）は、モノマー（ａ１）およびモノマー（ａ２）以外のモノマーである。
　ポリマー（Ａ）が脂環式炭化水素基含有（メタ）アクリレート由来の構成単位を含むことにより、得られる粘着剤層の凝集力と応力緩和性を容易に調整することができる。
　また、ポリマー（Ａ）が芳香族炭化水素基含有（メタ）アクリレート由来の構成単位を含むことにより、被着体との密着性により優れ、光漏れを抑制できる粘着剤層を容易に形成することができる。 [Alicyclic hydrocarbon group-containing (meth)acrylate and aromatic hydrocarbon group-containing (meth)acrylate]
The polymer (A) further contains at least one monomer (a4) selected from alicyclic hydrocarbon group-containing (meth)acrylates and aromatic hydrocarbon group-containing (meth)acrylates (hereinafter also referred to as "monomer (a4)" It may contain structural units derived from Monomer (a4) is a monomer other than monomer (a1) and monomer (a2).
When the polymer (A) contains structural units derived from an alicyclic hydrocarbon group-containing (meth)acrylate, it is possible to easily adjust the cohesive strength and stress relaxation properties of the resulting pressure-sensitive adhesive layer.
In addition, since the polymer (A) contains a structural unit derived from an aromatic hydrocarbon group-containing (meth)acrylate, it is possible to easily form a pressure-sensitive adhesive layer that has excellent adhesion to an adherend and can suppress light leakage. can be done.
　ポリマー（Ａ）が、モノマー（ａ４）由来の構成単位を含有する場合、モノマー（ａ４）由来の構成単位の含有量は、前記効果がより発揮される等の点から、ポリマー（Ａ）の全構成単位１００質量％に対し、好ましくは１～５０質量％、より好ましくは１～３０質量％である。
　モノマー（ａ４）由来の構成単位の含有量は、ポリマー（Ａ）を合成する際に用いるモノマー成分中のモノマー（ａ４）の量から算出することができる。 When the polymer (A) contains a structural unit derived from the monomer (a4), the content of the structural unit derived from the monomer (a4) is the total content of the polymer (A) from the viewpoint that the above effects are exhibited more. It is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, based on 100% by mass of the structural units.
The content of structural units derived from the monomer (a4) can be calculated from the amount of the monomer (a4) in the monomer component used when synthesizing the polymer (A).
　前記脂環式炭化水素基含有（メタ）アクリレートとしては、例えば、シクロヘキシル（メタ）アクリレート、４－ｔ－ブチルシクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレートが挙げられる。
　脂環式炭化水素基含有（メタ）アクリレートは、１種単独で用いてもよく、２種以上を用いてもよい。 Examples of the alicyclic hydrocarbon group-containing (meth)acrylates include cyclohexyl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate.
The alicyclic hydrocarbon group-containing (meth)acrylates may be used alone or in combination of two or more.
　前記芳香族炭化水素基含有（メタ）アクリレートとしては、例えば、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレートが挙げられる。
　芳香族炭化水素基含有（メタ）アクリレートは、１種単独で用いてもよく、２種以上を用いてもよい。 Examples of the aromatic hydrocarbon group-containing (meth)acrylates include benzyl (meth)acrylate, phenyl (meth)acrylate, and phenoxyethyl (meth)acrylate.
The aromatic hydrocarbon group-containing (meth)acrylates may be used singly or in combination of two or more.
［他のモノマー］
　ポリマー（Ａ）は、本発明の目的を損なわない範囲で、モノマー（ａ１）、モノマー（ａ２）、モノマー（ａ３）およびモノマー（ａ４）以外の他のモノマー由来の構成単位をさらに含有してもよい。
　前記他のモノマー由来の構成単位の含有量は、前記効果がより発揮される等の点から、ポリマー（Ａ）の全構成単位１００質量％に対し、好ましくは３０質量％以下、好ましくは２０質量％以下である。
　他のモノマー由来の構成単位の含有量は、ポリマー（Ａ）を合成する際に用いるモノマー成分中の他のモノマーの量から算出することができる。 [Other monomers]
The polymer (A) may further contain constituent units derived from monomers other than the monomer (a1), the monomer (a2), the monomer (a3) and the monomer (a4) as long as the object of the present invention is not impaired. good.
The content of the structural unit derived from the other monomer is preferably 30% by mass or less, preferably 20% by mass, based on 100% by mass of the total structural units of the polymer (A), from the viewpoint that the above effect is more exhibited. % or less.
The content of structural units derived from other monomers can be calculated from the amount of other monomers in the monomer component used when synthesizing the polymer (A).
　前記他のモノマーとしては、例えば、
　（メタ）アクリルアミド；Ｎ－メチル（メタ）アクリルアミド、Ｎ－エチル（メタ）アクリルアミド、Ｎ－プロピル（メタ）アクリルアミド、Ｎ－ヘキシル（メタ）アクリルアミド等のＮ－アルキル（メタ）アクリルアミド；Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド等のＮ，Ｎ－ジアルキル（メタ）アクリルアミド；Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム、（メタ）アクリロイルモルホリン等の環状アミド基含有モノマーなどのアミド基含有モノマー：
　Ｎ－シクロヘキシルマレイミド、Ｎ－フェニルマレイミド、Ｎ－ラウリルマレイミド、Ｎ－ベンジルマレイミド等の窒素系複素環含有モノマー：
　アクリロニトリル、メタクリロニトリル等のシアノ基含有モノマー：
　スチレン、α－メチルスチレン、ｐ－メチルスチレン、ｐ－クロロスチレン、ｐ－クロロメチルスチレン、ｐ－メトキシスチレン、ｐ－ｔｅｒｔ－ブトキシスチレン、ジビニルベンゼン、インデン等のスチレンおよびスチレン誘導体：
　酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプロン酸ビニル、安息香酸ビニル、珪皮酸ビニル等のビニルエステル化合物：
が挙げられる。
　他のモノマーは、１種単独で用いてもよく、２種以上を用いてもよい。 Examples of the other monomers include
(meth)acrylamide; N-alkyl (meth)acrylamide such as N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-hexyl (meth)acrylamide; N,N- N,N-dialkyl(meth)acrylamides such as dimethyl(meth)acrylamide and N,N-diethyl(meth)acrylamide; cyclic amide group-containing monomers such as N-vinylpyrrolidone, N-vinylcaprolactam and (meth)acryloylmorpholine; The amide group-containing monomer of:
Nitrogen-based heterocyclic ring-containing monomers such as N-cyclohexylmaleimide, N-phenylmaleimide, N-laurylmaleimide, and N-benzylmaleimide:
Cyano group-containing monomers such as acrylonitrile and methacrylonitrile:
Styrene and styrene derivatives such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, divinylbenzene, indene:
Vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, and vinyl cinnamate:
is mentioned.
Another monomer may be used individually by 1 type, and 2 or more types may be used.
　前記他のモノマーの中では、アミド基含有モノマー、窒素系複素環含有モノマーが好ましく、これらのモノマー由来の構成単位を含むポリマー（Ａ）を用いることで、エージング性に優れ、品質安定性に優れる粘着剤層を生産性よく形成することができる。 Among the other monomers, amide group-containing monomers and nitrogen-based heterocyclic ring-containing monomers are preferable, and by using the polymer (A) containing structural units derived from these monomers, excellent aging resistance and excellent quality stability can be obtained. A pressure-sensitive adhesive layer can be formed with good productivity.
［ポリマー（Ａ）の合成方法］
　ポリマー（Ａ）は、前述のモノマー成分を重合することにより合成することができ、例えば、ランダム重合体、ブロック重合体またはグラフト重合体のいずれでもよく、種々の重合法により合成することができる。その重合法は特に限定されないが、例えば、溶液重合、乳化重合、懸濁重合が挙げられる。これらの中でも、重合により得られた共重合体の混合物を用いて、本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うことができる観点から、溶液重合により重合することが好ましい。 [Method for synthesizing polymer (A)]
Polymer (A) can be synthesized by polymerizing the aforementioned monomer components, and may be, for example, a random polymer, a block polymer or a graft polymer, and can be synthesized by various polymerization methods. The polymerization method is not particularly limited, and examples thereof include solution polymerization, emulsion polymerization, and suspension polymerization. Among these, in producing the present composition using a mixture of copolymers obtained by polymerization, solution polymerization is preferred from the viewpoint that the processing steps are relatively simple and can be carried out in a short time. is preferred.
　溶液重合の具体例としては、反応容器内に、モノマー成分、重合開始剤および必要に応じて連鎖移動剤、重合溶媒等の他の成分を仕込み、反応開始温度を通常４０℃以上、好ましくは５０℃以上、通常１００℃以下、好ましくは８０℃以下に設定し、通常は５０～９０℃、好ましくは６０～９０℃の温度に反応系を維持して、２～２０時間反応させる方法が挙げられる。反応は、例えば、窒素ガス等の不活性ガス雰囲気下で行う。また、重合反応中に、モノマー成分、重合開始剤、連鎖移動剤および重合溶媒から選択される少なくとも１種等を追加添加してもよい。 As a specific example of solution polymerization, a reaction vessel is charged with other components such as a monomer component, a polymerization initiator and, if necessary, a chain transfer agent and a polymerization solvent, and the reaction initiation temperature is usually 40° C. or higher, preferably 50° C. C. or higher, usually 100.degree. C. or lower, preferably 80.degree. . The reaction is performed, for example, under an inert gas atmosphere such as nitrogen gas. Moreover, at least one selected from monomer components, polymerization initiators, chain transfer agents and polymerization solvents may be additionally added during the polymerization reaction.
　重合開始剤としては、例えば、アゾ系開始剤、過酸化物系重合開始剤が挙げられる。
　アゾ系開始剤としては、例えば、２，２'－アゾビスイソブチロニトリル、２，２'－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）、２，２'－アゾビス（２－シクロプロピルプロピオニトリル）、２，２'－アゾビス（２，４－ジメチルバレロニトリル）、２，２'－アゾビス（２－メチルブチロニトリル）、１，１'－アゾビス（シクロヘキサン－１－カルボニトリル）、２－（カルバモイルアゾ）イソブチロニトリル、２－フェニルアゾ－４－メトキシ－２，４－ジメチルバレロニトリル、２，２'－アゾビス（２－アミジノプロパン）ジヒドロクロリド、２，２'－アゾビス（Ｎ，Ｎ'－ジメチレンイソブチルアミジン）、２，２'－アゾビス〔２－メチル－Ｎ－（２－ヒドロキシエチル）－プロピオンアミド〕、２，２'－アゾビス（イソブチルアミド）ジヒドレート、４，４'－アゾビス（４－シアノペンタン酸）、２，２'－アゾビス（２－シアノプロパノール）、ジメチル－２，２'－アゾビス（２－メチルプロピオネート）、２，２'－アゾビス（２－メチル－Ｎ－（２－ヒドロキシエチル）プロピオンアミド）等のアゾ化合物が挙げられる。 Examples of polymerization initiators include azo initiators and peroxide polymerization initiators.
Examples of azo initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2- cyclopropylpropionitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane-1-carbo nitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis(2-amidinopropane) dihydrochloride, 2,2′- azobis(N,N'-dimethyleneisobutylamidine), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(isobutylamide) dihydrate, 4 , 4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (2-cyanopropanol), dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis ( 2-methyl-N-(2-hydroxyethyl)propionamide) and other azo compounds.
　過酸化物系重合開始剤としては、例えば、ｔ－ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ジクミルパーオキサイド、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、カプロイルパーオキサイド、ジ－ｉ－プロピルパーオキシジカーボネート、ジ－２－エチルヘキシルパーオキシジカーボネート、ｔ－ブチルパーオキシピバレート、２，２－ビス（４，４－ジ－ｔ－ブチルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジ－ｔ－アミルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジ－ｔ－オクチルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジ－α－クミルパーオキシシクロヘキシル）プロパン、２，２－ビス（４，４－ジ－ｔ－ブチルパーオキシシクロヘキシル）ブタン、２，２－ビス（４，４－ジ－ｔ－オクチルパーオキシシクロヘキシル）ブタンが挙げられる。 Examples of peroxide polymerization initiators include t-butyl hydroperoxide, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-i-propyl peroxide, Carbonate, di-2-ethylhexylperoxydicarbonate, t-butyl peroxypivalate, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 2,2-bis(4,4 -di-t-amylperoxycyclohexyl)propane, 2,2-bis(4,4-di-t-octylperoxycyclohexyl)propane, 2,2-bis(4,4-di-α-cumylperoxy cyclohexyl)propane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)butane, and 2,2-bis(4,4-di-t-octylperoxycyclohexyl)butane.
　重合開始剤は、１種単独で用いてもよく、２種以上を用いてもよい。また、重合中に、重合開始剤を複数回添加してもよい。
　重合開始剤の使用量は、モノマー成分１００質量部に対し、通常０．００１質量部以上、好ましくは０．００５質量部以上であり、通常５質量部以下、好ましくは３質量部以下である。 A polymerization initiator may be used individually by 1 type, and may use 2 or more types. Also, the polymerization initiator may be added multiple times during the polymerization.
The amount of the polymerization initiator used is usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, and usually 5 parts by mass or less, preferably 3 parts by mass or less, relative to 100 parts by mass of the monomer component.
　溶液重合に用いる重合溶媒としては、例えば、ベンゼン、トルエン、キシレン等の芳香族炭化水素類；ｎ－ペンタン、ｎ－ヘキサン、ｎ－ヘプタン、ｎ－オクタン等の脂肪族炭化水素類；シクロペンタン、シクロヘキサン、シクロヘプタン、シクロオクタン等の脂環式炭化水素類；ジエチルエーテル、ジイソプロピルエーテル、１，２－ジメトキシエタン、ジブチルエーテル、テトラヒドロフラン、ジオキサン、アニソール、フェニルエチルエーテル、ジフェニルエーテル等のエーテル類；クロロホルム、四塩化炭素、１，２－ジクロロエタン、クロロベンゼン等のハロゲン化炭化水素類；酢酸エチル、酢酸プロピル、酢酸ブチル、プロピオン酸メチル等のエステル類；アセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン等のアミド類；アセトニトリル、ベンゾニトリル等のニトリル類；ジメチルスルホキシド、スルホラン等のスルホキシド類が挙げられる。
　重合溶媒は、１種単独で用いてもよく、２種以上を用いてもよい。 Examples of the polymerization solvent used for solution polymerization include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; cyclopentane, cyclohexane, cycloheptane, alicyclic hydrocarbons such as cyclooctane; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, Halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane, chlorobenzene; Esters such as ethyl acetate, propyl acetate, butyl acetate, and methyl propionate; Acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. ketones; amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; and sulfoxides such as dimethylsulfoxide and sulfolane.
One type of polymerization solvent may be used alone, or two or more types may be used.
［ポリマー（Ａ）の物性］
　ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定されるポリマー（Ａ）の重量平均分子量（Ｍｗ）は、６０万以上であり、好ましくは８０万以上、より好ましくは１００万以上であり、好ましくは３００万以下、より好ましくは２５０万以下である。
　Ｍｗが前記範囲にあると、耐久性および凝集力に優れる粘着剤層を容易に形成することができる。
　該Ｍｗは、具体的には下記実施例に記載の方法で測定できる。 [Physical properties of polymer (A)]
The weight average molecular weight (Mw) of the polymer (A) measured by gel permeation chromatography (GPC) is 600,000 or more, preferably 800,000 or more, more preferably 1,000,000 or more, preferably 300. 10,000 or less, more preferably 2,500,000 or less.
When Mw is within the above range, a pressure-sensitive adhesive layer having excellent durability and cohesion can be easily formed.
Specifically, the Mw can be measured by the method described in Examples below.
　ポリマー（Ａ）の酸価は、１．０ｍｇＫＯＨ／ｇ以下であり、好ましくは０．８ｍｇＫＯＨ／ｇ以下、より好ましくは０ｍｇＫＯＨ／ｇである。
　ポリマー（Ａ）の酸価が前記範囲にあると、得られる粘着剤組成物から形成された粘着剤層に接した被着体の腐食を抑制することができる。
　該酸価は、具体的には下記実施例に記載の方法で測定できる。 The acid value of polymer (A) is 1.0 mgKOH/g or less, preferably 0.8 mgKOH/g or less, more preferably 0 mgKOH/g.
When the acid value of the polymer (A) is within the above range, corrosion of adherends in contact with the pressure-sensitive adhesive layer formed from the obtained pressure-sensitive adhesive composition can be suppressed.
Specifically, the acid value can be measured by the method described in Examples below.
　酸価が前記範囲にあるポリマー（Ａ）は、例えば、ポリマー（Ａ）を合成する際における、酸性基含有モノマーの使用量をモノマー成分１００質量％に対し０．１２質量％以下とする、または、好ましくは酸性基含有モノマーを実質的に用いないことで合成することができる。
　ここで、酸性基含有モノマーとしては、例えば、アクリル酸、メタクリル酸、β－カルボキシエチル（メタ）アクリレート、５－カルボキシペンチル（メタ）アクリレート、コハク酸モノ（メタ）アクリロイルオキシエチルエステル、ω－カルボキシポリカプロラクトンモノ（メタ）アクリレート、クロトン酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸等のカルボキシル基含有モノマーが挙げられる。 For the polymer (A) having an acid value within the above range, for example, when synthesizing the polymer (A), the amount of the acidic group-containing monomer used is 0.12% by mass or less with respect to 100% by mass of the monomer component, or , preferably without substantially using an acidic group-containing monomer.
Examples of acidic group-containing monomers include acrylic acid, methacrylic acid, β-carboxyethyl(meth)acrylate, 5-carboxypentyl(meth)acrylate, succinic acid mono(meth)acryloyloxyethyl ester, ω-carboxy Examples include carboxyl group-containing monomers such as polycaprolactone mono(meth)acrylate, crotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid.
［ポリマー（Ａ）の含有量］
　本組成物は、１種または２種以上のポリマー（Ａ）を含有することができる。
　本組成物におけるポリマー（Ａ）の含有量は、本組成物の不揮発分１００質量％に対し、好ましくは２０質量％以上、より好ましくは２５質量％以上であり、好ましくは７０質量％以下、より好ましくは６５質量％以下である。
　ポリマー（Ａ）の含有量が前記範囲にあると、適度な粘着力を有し、高温や高湿下でも、凝集力および応力緩和性にバランスよく優れ、発泡や被着体からの剥がれ等が生じ難い粘着剤層を容易に形成することができる。 [Content of polymer (A)]
The composition can contain one or more polymers (A).
The content of the polymer (A) in the composition is preferably 20% by mass or more, more preferably 25% by mass or more, preferably 70% by mass or less, and more Preferably, it is 65% by mass or less.
When the content of the polymer (A) is within the above range, the polymer (A) has an appropriate adhesive strength, is excellent in well-balanced cohesive strength and stress relaxation even under high temperature and high humidity, and is resistant to foaming and peeling from the adherend. A pressure-sensitive adhesive layer that is difficult to form can be easily formed.
＜アクリル系ポリマー（Ｂ）＞
　アクリル系ポリマー（Ｂ）（以下「ポリマー（Ｂ）」ともいう。）は、水酸基含有モノマー（ｂ１）（以下「モノマー（ｂ１）」ともいう。）由来の構成単位およびアミノ基含有モノマー（ｂ２）（以下「モノマー（ｂ２）」ともいう。）由来の構成単位の合計含有量が０．０５質量％以下であり、酸価が１．０ｍｇＫＯＨ／ｇ以下である、Ｍｗが２５万超であり、かつ、アクリル系ポリマー（Ａ）のＭｗより小さいポリマーである。
　本組成物はポリマー（Ｂ）を含むため、本組成物から得られる粘着剤層を、温度変化による収縮が大きい被着体（例：偏光板）に接して使用する場合であっても、該被着体の収縮に対し充分な剪断応力を発現しつつ、内部応力を残留させずに緩和することが可能な粘着剤層を容易に形成することができる。 <Acrylic polymer (B)>
The acrylic polymer (B) (hereinafter also referred to as "polymer (B)") is a structural unit derived from a hydroxyl group-containing monomer (b1) (hereinafter also referred to as "monomer (b1)") and an amino group-containing monomer (b2). (hereinafter also referred to as “monomer (b2)”), the total content of structural units derived from it is 0.05% by mass or less, the acid value is 1.0 mgKOH/g or less, and the Mw is more than 250,000; Moreover, it is a polymer smaller than the Mw of the acrylic polymer (A).
Since the present composition contains the polymer (B), even when the pressure-sensitive adhesive layer obtained from the present composition is used in contact with an adherend (e.g., polarizing plate) that shrinks significantly due to temperature changes, the It is possible to easily form a pressure-sensitive adhesive layer that exhibits sufficient shear stress against contraction of an adherend and can be relaxed without residual internal stress.
　ポリマー（Ｂ）におけるモノマー（ｂ１）由来の構成単位およびモノマー（ｂ２）由来の構成単位の合計含有量は、ポリマー（Ｂ）の全構成単位１００質量％に対し、０．０５質量％以下であり、好ましくは０．０２質量％以下、より好ましくは０．０１質量％以下である。該合計含有量の下限は、好ましくは０質量％である。
　該合計含有量が前記範囲にあると、得られる粘着剤層の架橋密度が低くなり、応力緩和性に優れ、被着体の剥がれが生じ難い粘着剤層を容易に形成することができる。特に、該含有量が前記範囲にあると、大きく収縮し得る被着体（例：偏光板）に接して得られる粘着剤層を使用する場合、粘着剤層にかかる応力を緩和することができ、さらに該被着体の収縮を抑えることができる。
　モノマー（ｂ１）およびモノマー（ｂ２）由来の構成単位の含有量は、ポリマー（Ｂ）を合成する際に用いるモノマー成分中のモノマー（ｂ１）およびモノマー（ｂ２）の量から算出することができる。 The total content of structural units derived from the monomer (b1) and structural units derived from the monomer (b2) in the polymer (B) is 0.05% by mass or less with respect to 100% by mass of all structural units of the polymer (B). , preferably 0.02% by mass or less, more preferably 0.01% by mass or less. The lower limit of the total content is preferably 0% by mass.
When the total content is within the above range, the resulting pressure-sensitive adhesive layer has a low cross-linking density, which makes it possible to easily form a pressure-sensitive adhesive layer which is excellent in stress relaxation properties and which hardly causes peeling of the adherend. In particular, when the content is within the above range, the stress applied to the pressure-sensitive adhesive layer can be relaxed when using the pressure-sensitive adhesive layer obtained in contact with an adherend (e.g., polarizing plate) that can shrink significantly. Furthermore, shrinkage of the adherend can be suppressed.
The content of structural units derived from the monomer (b1) and the monomer (b2) can be calculated from the amounts of the monomer (b1) and the monomer (b2) in the monomer component used when synthesizing the polymer (B).
　モノマー（ｂ１）およびモノマー（ｂ２）としてはそれぞれ、例えば、モノマー（ａ１）およびモノマー（ａ２）と同様のモノマーが挙げられる。モノマー（ｂ１）は、１種単独で用いてもよく、２種以上を用いてもよい。モノマー（ｂ２）も、１種単独で用いてもよく、２種以上を用いてもよい。モノマー（ｂ２）は、モノマー（ｂ１）以外のモノマーである。 Examples of the monomer (b1) and the monomer (b2) include the same monomers as the monomer (a1) and the monomer (a2), respectively. The monomer (b1) may be used alone or in combination of two or more. The monomer (b2) may also be used singly or in combination of two or more. Monomer (b2) is a monomer other than monomer (b1).
［モノマー（ｂ３）］
　ポリマー（Ｂ）は、アルキル（メタ）アクリレートおよびアルコキシアルキル（メタ）アクリレートから選ばれる少なくとも１種のモノマー（ｂ３）（以下「モノマー（ｂ３）」ともいう。）由来の構成単位を含むことが好ましく、アルキル（メタ）アクリレートおよびアルコキシアルキル（メタ）アクリレート由来の構成単位を含むことが特に好ましい。
　ポリマー（Ｂ）がアルキル（メタ）アクリレート由来の構成単位を含むことにより、得られる粘着剤層の粘着力やリワーク性を容易に調整することができる。
　また、ポリマー（Ｂ）がアルコキシアルキル（メタ）アクリレート由来の構成単位を含むことにより、エージング性に優れ、品質安定性に優れる粘着剤層を生産性よく形成することができる。 [Monomer (b3)]
The polymer (B) preferably contains structural units derived from at least one monomer (b3) selected from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates (hereinafter also referred to as "monomer (b3)"). , alkyl (meth)acrylate and alkoxyalkyl (meth)acrylate-derived structural units are particularly preferred.
By including structural units derived from alkyl (meth)acrylate in the polymer (B), the adhesive strength and reworkability of the obtained pressure-sensitive adhesive layer can be easily adjusted.
In addition, since the polymer (B) contains structural units derived from alkoxyalkyl (meth)acrylate, it is possible to form a pressure-sensitive adhesive layer excellent in aging resistance and quality stability with good productivity.
　ポリマー（Ｂ）が、モノマー（ｂ３）由来の構成単位を含有する場合、モノマー（ｂ３）由来の構成単位の含有量は、前記効果がより発揮される等の点から、ポリマー（Ｂ）の全構成単位１００質量％に対し、好ましくは２５～１００質量％、より好ましくは５０～１００質量％である。なお、ポリマー（Ｂ）が、モノマー（ｂ１）、モノマー（ｂ２）およびモノマー（ｂ３）由来の構成単位以外の構成単位を含有する場合、特に、モノマー（ｂ１）、モノマー（ｂ２）、モノマー（ｂ３）および下記モノマー（ｂ４）由来の構成単位を含有する場合、モノマー（ｂ３）由来の構成単位の含有量の上限は、好ましくは９８質量％以下、より好ましくは９７質量％以下であり、下限は、好ましくは２５質量％以上、より好ましくは５０質量％以上である。
　モノマー（ｂ３）由来の構成単位の含有量は、ポリマー（Ｂ）を合成する際に用いるモノマー成分中のモノマー（ｂ３）の量から算出することができる。 When the polymer (B) contains a structural unit derived from the monomer (b3), the content of the structural unit derived from the monomer (b3) is the total content of the polymer (B) from the viewpoint that the above effects are exhibited more. It is preferably 25 to 100% by mass, more preferably 50 to 100% by mass, based on 100% by mass of the structural units. When the polymer (B) contains structural units other than the structural units derived from the monomer (b1), the monomer (b2) and the monomer (b3), particularly the monomer (b1), the monomer (b2) and the monomer (b3 ) and a structural unit derived from the following monomer (b4), the upper limit of the content of the structural unit derived from the monomer (b3) is preferably 98% by mass or less, more preferably 97% by mass or less, and the lower limit is , preferably 25% by mass or more, more preferably 50% by mass or more.
The content of structural units derived from the monomer (b3) can be calculated from the amount of the monomer (b3) in the monomer component used when synthesizing the polymer (B).
　モノマー（ｂ３）としては、例えば、モノマー（ａ３）と同様のモノマーが挙げられる。モノマー（ｂ３）は、１種単独で用いてもよく、２種以上を用いてもよい。モノマー（ｂ３）は、モノマー（ｂ１）、モノマー（ｂ２）および下記モノマー（ｂ４）以外のモノマーである。 Examples of the monomer (b3) include monomers similar to the monomer (a3). The monomer (b3) may be used alone or in combination of two or more. Monomer (b3) is a monomer other than monomer (b1), monomer (b2) and monomer (b4) below.
［脂環式炭化水素基含有（メタ）アクリレートおよび芳香族炭化水素基含有（メタ）アクリレート］
　ポリマー（Ｂ）は、さらに、脂環式炭化水素基含有（メタ）アクリレートおよび芳香族炭化水素基含有（メタ）アクリレートから選ばれる少なくとも１種のモノマー（ｂ４）（以下「モノマー（ｂ４）」ともいう。）由来の構成単位を含んでいてもよい。
　ポリマー（Ｂ）が脂環式炭化水素基含有（メタ）アクリレート由来の構成単位を含むことにより、得られる粘着剤層の凝集力と応力緩和性を容易に調整することができる。
　また、ポリマー（Ｂ）が芳香族炭化水素基含有（メタ）アクリレート由来の構成単位を含むことにより、被着体との密着性により優れ、光漏れを抑制できる粘着剤層を容易に形成することができる。 [Alicyclic hydrocarbon group-containing (meth)acrylate and aromatic hydrocarbon group-containing (meth)acrylate]
Polymer (B) further contains at least one monomer (b4) selected from alicyclic hydrocarbon group-containing (meth)acrylates and aromatic hydrocarbon group-containing (meth)acrylates (hereinafter also referred to as "monomer (b4)" It may contain structural units derived from
When the polymer (B) contains structural units derived from an alicyclic hydrocarbon group-containing (meth)acrylate, it is possible to easily adjust the cohesive strength and stress relaxation properties of the resulting pressure-sensitive adhesive layer.
In addition, since the polymer (B) contains a structural unit derived from an aromatic hydrocarbon group-containing (meth)acrylate, it is possible to easily form a pressure-sensitive adhesive layer that has excellent adhesion to an adherend and can suppress light leakage. can be done.
　ポリマー（Ｂ）が、モノマー（ｂ４）由来の構成単位を含有する場合、モノマー（ｂ４）由来の構成単位の含有量は、前記効果がより発揮される等の点から、ポリマー（Ｂ）の全構成単位１００質量％に対し、好ましくは１～５０質量％、より好ましくは１～３０質量％である。
　モノマー（ｂ４）由来の構成単位の含有量は、ポリマー（Ｂ）を合成する際に用いるモノマー成分中のモノマー（ｂ４）の量から算出することができる。 When the polymer (B) contains a structural unit derived from the monomer (b4), the content of the structural unit derived from the monomer (b4) is the total content of the polymer (B) from the viewpoint that the above effects are exhibited more. It is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, based on 100% by mass of the structural units.
The content of structural units derived from the monomer (b4) can be calculated from the amount of the monomer (b4) in the monomer component used when synthesizing the polymer (B).
　モノマー（ｂ４）としては、例えば、モノマー（ａ４）と同様のモノマーが挙げられる。モノマー（ｂ４）は、１種単独で用いてもよく、２種以上を用いてもよい。モノマー（ｂ４）は、モノマー（ｂ１）およびモノマー（ｂ２）以外のモノマーである。 Examples of the monomer (b4) include monomers similar to the monomer (a4). The monomer (b4) may be used alone or in combination of two or more. Monomer (b4) is a monomer other than monomer (b1) and monomer (b2).
［他のモノマー］
　ポリマー（Ｂ）は、本発明の目的を損なわない範囲で、モノマー（ｂ１）、モノマー（ｂ２）、モノマー（ｂ３）およびモノマー（ｂ４）以外の他のモノマー由来の構成単位をさらに含有してもよい。
　前記他のモノマー由来の構成単位の含有量は、前記効果がより発揮される等の点から、ポリマー（Ｂ）の全構成単位１００質量％に対し、好ましくは３０質量％以下、好ましくは２０質量％以下である。
　他のモノマー由来の構成単位の含有量は、ポリマー（Ｂ）を合成する際に用いるモノマー成分中の他のモノマーの量から算出することができる。 [Other monomers]
The polymer (B) may further contain constituent units derived from monomers other than the monomer (b1), the monomer (b2), the monomer (b3) and the monomer (b4), as long as the object of the present invention is not impaired. good.
The content of the structural unit derived from the other monomer is preferably 30% by mass or less, preferably 20% by mass, based on 100% by mass of the total structural units of the polymer (B), from the viewpoint that the above effect is more exhibited. % or less.
The content of structural units derived from other monomers can be calculated from the amount of other monomers in the monomer component used when synthesizing the polymer (B).
　前記他のモノマーとしては、例えば、ポリマー（Ａ）の欄で挙げた他のモノマーと同様のモノマーが挙げられる。他のモノマーは、１種単独で用いてもよく、２種以上を用いてもよい。 Examples of the other monomers include monomers similar to the other monomers listed in the column for polymer (A). Another monomer may be used individually by 1 type, and 2 or more types may be used.
［ポリマー（Ｂ）の合成方法］
　ポリマー（Ｂ）は、前述のモノマー成分を重合することにより合成することができ、例えば、ランダム重合体、ブロック重合体またはグラフト重合体のいずれでもよく、種々の重合法により合成することができる。その重合法は特に限定されないが、例えば、溶液重合、乳化重合、懸濁重合が挙げられる。これらの中でも、重合により得られた重合体の混合物を用いて、本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うことができる観点から、溶液重合により重合することが好ましい。 [Method for synthesizing polymer (B)]
Polymer (B) can be synthesized by polymerizing the aforementioned monomer components, and may be, for example, a random polymer, a block polymer or a graft polymer, and can be synthesized by various polymerization methods. The polymerization method is not particularly limited, and examples thereof include solution polymerization, emulsion polymerization, and suspension polymerization. Among these, in producing the present composition using a mixture of polymers obtained by polymerization, solution polymerization is preferred from the viewpoint that the processing steps are relatively simple and can be carried out in a short period of time. preferable.
　溶液重合の具体例としては、反応容器内に、モノマー成分、重合開始剤および必要に応じて連鎖移動剤、重合溶媒等の他の成分を仕込み、反応開始温度を通常４０℃以上、好ましくは５０℃以上、通常１００℃以下、好ましくは８０℃以下に設定し、通常は５０～９０℃、好ましくは６０～９０℃の温度に反応系を維持して、２～２０時間反応させる方法が挙げられる。反応は、例えば、窒素ガス等の不活性ガス雰囲気下で行う。また、重合反応中に、モノマー成分、重合開始剤、連鎖移動剤および重合溶媒から選択される少なくとも１種等を追加添加してもよい。 As a specific example of solution polymerization, a reaction vessel is charged with other components such as a monomer component, a polymerization initiator and, if necessary, a chain transfer agent and a polymerization solvent, and the reaction initiation temperature is usually 40° C. or higher, preferably 50° C. C. or higher, usually 100.degree. C. or lower, preferably 80.degree. . The reaction is performed, for example, under an inert gas atmosphere such as nitrogen gas. Moreover, at least one selected from monomer components, polymerization initiators, chain transfer agents, and polymerization solvents may be additionally added during the polymerization reaction.
　ポリマー（Ｂ）の合成に用いてもよい、重合開始剤および重合溶媒としては、前記ポリマー（Ａ）の合成方法の欄で記載した重合開始剤および重合溶媒と同様の重合開始剤および重合溶媒等が挙げられる。 As the polymerization initiator and polymerization solvent that may be used for synthesizing the polymer (B), the same polymerization initiator and polymerization solvent as those described in the section for the method for synthesizing the polymer (A) can be used. are mentioned.
［ポリマー（Ｂ）の物性］
　ＧＰＣ法により測定されるポリマー（Ｂ）のＭｗは、２５万超であってポリマー（Ａ）のＭｗより小さい。ポリマー（Ｂ）のＭｗの下限値は、好ましくは３０万以上、より好ましくは５０万以上である。ポリマー（Ｂ）のＭｗの上限値は、ポリマー（Ａ）のＭｗより小さければ特に制限されないが、好ましくは１００万以下である。
　Ｍｗが前記範囲にあると、本組成物から得られる粘着剤層を、温度変化による収縮が大きい被着体（例：偏光板）に接して使用する場合であっても、被着体の収縮に対し充分な剪断応力を発現しつつ、内部応力を残留させずに緩和することが可能な粘着剤層を容易に形成することができる。
　該Ｍｗは、具体的には下記実施例に記載の方法で測定できる。 [Physical properties of polymer (B)]
Mw of polymer (B) measured by GPC method is greater than 250,000 and smaller than Mw of polymer (A). The lower limit of Mw of the polymer (B) is preferably 300,000 or more, more preferably 500,000 or more. The upper limit of the Mw of the polymer (B) is not particularly limited as long as it is smaller than the Mw of the polymer (A), preferably 1,000,000 or less.
When Mw is in the above range, even when the adhesive layer obtained from the present composition is used in contact with an adherend that undergoes large shrinkage due to temperature change (e.g., polarizing plate), the shrinkage of the adherend It is possible to easily form a pressure-sensitive adhesive layer that can be relieved without residual internal stress while exhibiting a sufficient shear stress against.
Specifically, the Mw can be measured by the method described in Examples below.
　ポリマー（Ｂ）のＭｗは、ポリマー（Ａ）のＭｗより小さく、ポリマー（Ａ）のＭｗに対するポリマー（Ｂ）のＭｗの比（ポリマー（Ｂ）のＭｗ／ポリマー（Ａ）のＭｗ）は、好ましくは０．８以下、より好ましくは０．６以下である。
　ポリマー（Ａ）と（Ｂ）のＭｗの関係が前記範囲にあることで、凝集力および応力緩和性にバランスよく優れる粘着剤層を容易に形成することができる。 The Mw of polymer (B) is smaller than the Mw of polymer (A), and the ratio of Mw of polymer (B) to Mw of polymer (A) (Mw of polymer (B)/Mw of polymer (A)) is preferably is 0.8 or less, more preferably 0.6 or less.
When the relationship between the Mws of the polymers (A) and (B) is within the above range, it is possible to easily form a pressure-sensitive adhesive layer that is excellent in well-balanced cohesion and stress relaxation.
　ポリマー（Ｂ）の酸価は、１．０ｍｇＫＯＨ／ｇ以下であり、好ましくは０．８ｍｇＫＯＨ／ｇ以下、より好ましくは０ｍｇＫＯＨ／ｇである。
　ポリマー（Ｂ）の酸価が前記範囲にあると、得られる粘着剤組成物から形成された粘着剤層に接した被着体の腐食を抑制することができる。
　該酸価は、具体的には下記実施例に記載の方法で測定できる。 The acid value of polymer (B) is 1.0 mgKOH/g or less, preferably 0.8 mgKOH/g or less, more preferably 0 mgKOH/g.
When the acid value of the polymer (B) is within the above range, corrosion of adherends in contact with the pressure-sensitive adhesive layer formed from the obtained pressure-sensitive adhesive composition can be suppressed.
Specifically, the acid value can be measured by the method described in Examples below.
　酸価が前記範囲にあるポリマー（Ｂ）は、例えば、ポリマー（Ｂ）を合成する際における、酸性基含有モノマーの使用量をモノマー成分１００質量％に対し０．１２質量％以下とする、または、好ましくは酸性基含有モノマーを実質的に用いないことで合成することができる。
　該酸性基含有モノマーとしては、ポリマー（Ａ）の欄に記載した酸性基含有モノマーと同様のモノマーが挙げられる。 For the polymer (B) having an acid value within the above range, for example, when synthesizing the polymer (B), the amount of the acidic group-containing monomer used is 0.12% by mass or less with respect to 100% by mass of the monomer component, or , preferably without substantially using an acidic group-containing monomer.
Examples of the acidic group-containing monomer include monomers similar to the acidic group-containing monomers described in the column of polymer (A).
［ポリマー（Ｂ）の含有量］
　本組成物は、１種または２種以上のポリマー（Ｂ）を含有することができる。
　本組成物におけるポリマー（Ｂ）の含有量は、ポリマー（Ａ）１００質量部に対し、１０質量部以上であり、好ましくは２５質量部以上、より好ましくは４０質量部以上であり、好ましくは３００質量部以下、より好ましくは２００質量部以下である。
　ポリマー（Ｂ）の含有量が前記範囲にあると、本組成物から得られる粘着剤層を、温度変化による収縮が大きい被着体（例：偏光板）に接して使用する場合であっても、被着体の収縮に対し充分な剪断応力を発現しつつ、内部応力を残留させずに緩和することが可能な粘着剤層を容易に形成することができる。 [Content of polymer (B)]
The composition can contain one or more polymers (B).
The content of the polymer (B) in the present composition is 10 parts by mass or more, preferably 25 parts by mass or more, more preferably 40 parts by mass or more, preferably 300 parts by mass with respect to 100 parts by mass of the polymer (A). It is not more than 200 parts by mass, more preferably not more than 200 parts by mass.
When the content of the polymer (B) is within the above range, even when the pressure-sensitive adhesive layer obtained from the present composition is used in contact with an adherend (e.g., polarizing plate) that undergoes large shrinkage due to temperature changes, Therefore, it is possible to easily form a pressure-sensitive adhesive layer that can be relieved without residual internal stress while exhibiting sufficient shear stress against shrinkage of the adherend.
＜イソシアネート系硬化剤（Ｃ）＞
　本組成物は、イソシアネート系硬化剤（Ｃ）（以下「硬化剤（Ｃ）」ともいう。）を含む。硬化剤（Ｃ）としては、例えば、１分子中のイソシアネート基数が２以上のイソシアネート化合物が挙げられる。 <Isocyanate curing agent (C)>
The composition contains an isocyanate-based curing agent (C) (hereinafter also referred to as “curing agent (C)”). Examples of the curing agent (C) include isocyanate compounds having two or more isocyanate groups in one molecule.
　硬化剤（Ｃ）としては、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、クロロ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等のイソシアネートモノマー；イソシアネートモノマーとトリメチロールプロパン等の２価以上のアルコール化合物等とを付加反応させたイソシアネート化合物；ビュレット型イソシアネート化合物；イソシアネートモノマーに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等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；イソシアヌレート化合物が挙げられる。 Examples of the curing agent (C) include isocyanate monomers such as xylylene diisocyanate, tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenylmethane diisocyanate; Isocyanate compounds obtained by addition reaction with divalent or higher alcohol compounds such as trimethylolpropane; buret-type isocyanate compounds; polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, etc. added to isocyanate monomers. and urethane prepolymer type isocyanates; isocyanurate compounds.
［硬化剤（Ｃ）の含有量］
　本組成物は、１種または２種以上の硬化剤（Ｃ）を含有することができる。
　本組成物における硬化剤（Ｃ）の含有量は、ポリマー（Ａ）とポリマー（Ｂ）との合計１００質量部に対し、６質量部を超えて３０質量部未満であり、好ましくは７質量部以上、より好ましくは８質量部以上であり、好ましくは２５質量部以下、より好ましくは２０質量部以下である。
　硬化剤（Ｃ）の含有量が前記範囲にあるということは、硬化剤（Ｃ）を、ポリマー（Ａ）の有する架橋性官能基の数に対し、イソシアネート基の量が過剰量となるような量で用いることを意味する。このような量で硬化剤（Ｃ）を用いると、ポリマー（Ａ）との架橋反応に寄与しなかった硬化剤（Ｃ）の自己縮合物が形成され、該縮合物がポリマー（Ａ）および／または（Ｂ）と絡み合うことによって、従来の粘着剤組成物から形成された粘着剤層と比較して高い凝集力を有する粘着剤層を容易に形成することができると考えられる。 [Content of curing agent (C)]
The composition may contain one or more curing agents (C).
The content of the curing agent (C) in the present composition is more than 6 parts by mass and less than 30 parts by mass, preferably 7 parts by mass, with respect to a total of 100 parts by mass of the polymer (A) and the polymer (B). Above, more preferably 8 parts by mass or more, preferably 25 parts by mass or less, more preferably 20 parts by mass or less.
The fact that the content of the curing agent (C) is within the above range means that the amount of the curing agent (C) is such that the amount of isocyanate groups is excessive with respect to the number of crosslinkable functional groups possessed by the polymer (A). means to use in quantity. When the curing agent (C) is used in such an amount, a self-condensate of the curing agent (C) that did not contribute to the cross-linking reaction with the polymer (A) is formed, and the condensate becomes the polymer (A) and/or Or it is thought that by entangling with (B), it is possible to easily form a pressure-sensitive adhesive layer having a higher cohesive strength than a pressure-sensitive adhesive layer formed from a conventional pressure-sensitive adhesive composition.
　＜その他の成分＞
　本組成物は、本発明の効果を損なわない範囲で、前記ポリマー（Ａ）、ポリマー（Ｂ）および硬化剤（Ｃ）以外のその他の成分、例えば、硬化剤（Ｃ）以外の硬化剤（Ｄ）、シランカップリング剤（Ｅ）、帯電防止剤（Ｆ）、粘着付与樹脂、酸化防止剤、光安定剤、金属腐食防止剤、可塑剤、架橋促進剤、界面活性剤、リワーク剤、有機溶媒を含有してもよい。
　これらその他の成分はそれぞれ、１種単独で用いてもよく、２種以上を用いてもよい。 <Other ingredients>
The present composition may contain other components other than the polymer (A), the polymer (B) and the curing agent (C), such as a curing agent (D ), silane coupling agent (E), antistatic agent (F), tackifying resin, antioxidant, light stabilizer, metal corrosion inhibitor, plasticizer, cross-linking accelerator, surfactant, reworking agent, organic solvent may contain.
Each of these other components may be used singly or in combination of two or more.
［硬化剤（Ｃ）以外の硬化剤（Ｄ）］
　本組成物は、硬化剤（Ｃ）以外の硬化剤（Ｄ）（以下「硬化剤（Ｄ）」ともいう。）を含んでもよい。
　硬化剤（Ｄ）としては、例えば、エポキシ系硬化剤、金属キレート系硬化剤が挙げられる。 [Curing agent (D) other than curing agent (C)]
The present composition may contain a curing agent (D) (hereinafter also referred to as "curing agent (D)") other than the curing agent (C).
Examples of the curing agent (D) include epoxy curing agents and metal chelate curing agents.
　前記硬化剤（Ｃ）と硬化剤（Ｄ）とを併用することで、本組成物の種々の性能を向上させることができる。特に、硬化剤（Ｃ）とエポキシ系硬化剤とを併用することで、耐湿熱性およびエージング性により優れる粘着剤層を容易に形成することができ、硬化剤（Ｃ）と金属キレート系硬化剤とを併用することで、エージング性により優れる粘着剤層を容易に形成することができる。 By using the curing agent (C) and the curing agent (D) together, various performances of the composition can be improved. In particular, by using the curing agent (C) and an epoxy-based curing agent in combination, it is possible to easily form a pressure-sensitive adhesive layer having excellent moist heat resistance and aging resistance. By using together, it is possible to easily form a pressure-sensitive adhesive layer that is more excellent in aging resistance.
　エポキシ系硬化剤としては、例えば、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、Ｎ，Ｎ，Ｎ'，Ｎ'－テトラグリジル－ｍ－キシリレンジアミン、Ｎ，Ｎ，Ｎ'，Ｎ'－テトラグリジルアミノフェニルメタン、トリグリシジルイソシアヌレート、ｍ－Ｎ，Ｎ－ジグリシジルアミノフェニルグリシジルエーテル、Ｎ，Ｎ－ジグリシジルトルイジン、Ｎ，Ｎ－ジグリシジルアニリン、ペンタエリスリトールポリグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテルが挙げられる。 Examples of epoxy-based curing agents include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N, N,N',N'-tetraglydyl-m-xylylenediamine, N,N,N',N'-tetraglydylaminophenylmethane, triglycidyl isocyanurate, mN,N-diglycidylaminophenylglycidyl ether , N,N-diglycidyltoluidine, N,N-diglycidylaniline, pentaerythritol polyglycidyl ether, 1,6-hexanediol diglycidyl ether.
　金属キレート系硬化剤としては、例えば、アルミニウム、鉄、銅、亜鉛、スズ、チタン、ニッケル、アンチモン、マグネシウム、バナジウム、クロム、ジルコニウム等の多価金属に、アルコキシド、アセチルアセトン、アセト酢酸エチル等が配位した化合物が挙げられる。その具体例としては、アルミニウムイソプロピレート、アルミニウムセカンダリーブチレート、アルミニウムエチルアセトアセテート・ジイソプロピレート、アルミニウムトリスエチルアセトアセテート、アルミニウムトリスアセチルアセトネートが挙げられる。 Examples of metal chelate curing agents include polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium combined with alkoxides, acetylacetone, ethyl acetoacetate, and the like. A compound with a Specific examples include aluminum isopropylate, aluminum secondary butyrate, aluminum ethylacetoacetate/diisopropylate, aluminum trisethylacetoacetate, and aluminum trisacetylacetonate.
　本組成物が硬化剤（Ｄ）を含有する場合、本組成物における硬化剤（Ｄ）の含有量は、前記効果がより発揮される等の点から、ポリマー（Ａ）とポリマー（Ｂ）との合計１００質量部に対し、好ましくは０．００５質量部以上、より好ましくは０．０１質量部以上であり、好ましくは６質量部以下、より好ましくは３質量部以下である。 When the present composition contains the curing agent (D), the content of the curing agent (D) in the present composition should be the same as the polymer (A) and the polymer (B) in terms of exhibiting the above effects more. It is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, preferably 6 parts by mass or less, and more preferably 3 parts by mass or less, relative to the total 100 parts by mass of .
［シランカップリング剤（Ｅ）］
　本組成物は、シランカップリング剤（Ｅ）を含んでもよい。
　本組成物がシランカップリング剤（Ｅ）を含むことにより、被着体に対する粘着力の高い粘着剤層を容易に形成することができる。 [Silane coupling agent (E)]
The composition may contain a silane coupling agent (E).
By including the silane coupling agent (E) in the present composition, it is possible to easily form a pressure-sensitive adhesive layer having high adhesion to an adherend.
　シランカップリング剤（Ｅ）としては、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、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シランカップリング剤；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トリエトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、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基含有シランカップリング剤；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、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シランカップリング剤；３－クロロプロピルトリメトキシシラン等のハロゲン含有シランカップリング剤が挙げられる。これらの中でも、応力緩和性に優れる粘着剤層を容易に形成することができる等の点からは、エポキシ基含有シランカップリング剤が好ましい。 Silane coupling agents (E) include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, silane coupling agents containing polymerizable unsaturated groups such as methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane; , 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and other epoxy groups Containing silane coupling agent; amino such as 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane Group-containing silane coupling agents; Halogen-containing silane coupling agents such as 3-chloropropyltrimethoxysilane can be mentioned. Among these, an epoxy group-containing silane coupling agent is preferable from the viewpoint that a pressure-sensitive adhesive layer having excellent stress relaxation properties can be easily formed.
　本組成物がシランカップリング剤（Ｅ）を含有する場合、本組成物におけるシランカップリング剤（Ｅ）の含有量は、ポリマー（Ａ）とポリマー（Ｂ）との合計１００質量部に対し、通常１質量部以下、好ましくは０．０１質量部以上、より好ましくは０．０５質量部以上であり、好ましくは１質量部以下、より好ましくは０．５質量部以下である。
　シランカップリング剤（Ｅ）の含有量が前記範囲にあると、高湿熱環境下でも、粘着剤層の被着体からの剥がれを容易に抑制することができ、高温環境下でも、シランカップリング剤（Ｅ）のブリードが起り難い粘着剤層を容易に形成することができる傾向にある。 When the composition contains the silane coupling agent (E), the content of the silane coupling agent (E) in the composition is It is usually 1 part by mass or less, preferably 0.01 mass part or more, more preferably 0.05 mass part or more, and preferably 1 mass part or less, more preferably 0.5 mass part or less.
When the content of the silane coupling agent (E) is within the above range, peeling of the pressure-sensitive adhesive layer from the adherend can be easily suppressed even in a high-humidity and heat environment, and even in a high-temperature environment, the silane coupling It tends to be possible to easily form a pressure-sensitive adhesive layer in which bleeding of the agent (E) is difficult to occur.
［帯電防止剤（Ｆ）］
　本組成物は、帯電防止剤（Ｆ）を含んでもよい。
　帯電防止剤（Ｆ）としては、例えば、界面活性剤、イオン性化合物、導電性ポリマーが挙げられる。 [Antistatic agent (F)]
The composition may contain an antistatic agent (F).
Antistatic agents (F) include, for example, surfactants, ionic compounds, and conductive polymers.
　界面活性剤としては、例えば、４級アンモニウム塩類、アミド４級アンモニウム塩類、ピリジウム塩類、第１級～第３級アミノ基等のカチオン性基を有するカチオン性界面活性剤；スルホン酸塩基、硫酸エステル塩基、リン酸エステル塩基等のアニオン性基を有するアニオン性界面活性剤；アルキルベタイン類、アルキルイミダゾリニウムベタイン類、アルキルアミンオキサイド類、アミノ酸硫酸エステル類等の両性界面活性剤；グリセリン脂肪酸エステル類、ソルビタン脂肪酸エステル類、ポリオキシエチレンアルキルアミン類、ポリオキシエチレンアルキルアミン脂肪酸エステル類、Ｎ－ヒドロキシエチル－Ｎ－２－ヒドロキシアルキルアミン類、アルキルジエタノールアミド類等の非イオン性界面活性剤が挙げられる。 Surfactants include, for example, quaternary ammonium salts, quaternary amide quaternary ammonium salts, pyridium salts, cationic surfactants having cationic groups such as primary to tertiary amino groups; sulfonate groups, sulfate esters Anionic surfactants having anionic groups such as bases and phosphate ester bases; Amphoteric surfactants such as alkylbetaines, alkylimidazolinium betaines, alkylamine oxides, amino acid sulfate esters; , sorbitan fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, N-hydroxyethyl-N-2-hydroxyalkylamines, alkyldiethanolamides and other nonionic surfactants. be done.
　また、界面活性剤としては、重合性基を有する反応性乳化剤も挙げられ、前記界面活性剤または反応性乳化剤を含むモノマー成分を高分子量化したポリマー系界面活性剤を用いることもできる。 In addition, the surfactant also includes a reactive emulsifier having a polymerizable group, and a polymer-based surfactant obtained by increasing the molecular weight of the monomer component containing the surfactant or reactive emulsifier can also be used.
　イオン性化合物は、カチオン部とアニオン部とから構成される化合物であり、常温（２３℃）、５０％ＲＨ下において、固体状の化合物であっても、液体状の化合物であってもよい。 The ionic compound is a compound composed of a cation portion and an anion portion, and may be a solid or liquid compound at room temperature (23°C) and 50% RH.
　イオン性化合物を構成するカチオン部としては、無機系カチオンまたは有機系カチオンのいずれか一方であっても双方であってもよい。無機系カチオンとしては、アルカリ金属イオンおよびアルカリ土類金属イオンが好ましく、帯電防止性に優れるＬｉ+、Ｎａ+およびＫ+がより好ましい。有機系カチオンとしては、例えば、ピリジニウムカチオン、ピペリジニウムカチオン、ピロリジニウムカチオン、ピロリンカチオン、ピロールカチオン、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、トリアルキルアルコキシ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およびこれらの誘導体が挙げられる。 The cation moiety constituting the ionic compound may be either one or both of inorganic cations and organic cations. As inorganic cations, alkali metal ions and alkaline earth metal ions are preferable, and Li + , Na + and K + which are excellent in antistatic properties are more preferable. Examples of organic cations include pyridinium cations, piperidinium cations, pyrrolidinium cations, pyrroline cations, pyrrole cations, imidazolium cations, tetrahydropyrimidinium cations, dihydropyrimidinium cations, pyrazolium cations, and pyrazolium cations. cations, tetraalkylammonium cations, trialkylalkoxyammonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations and derivatives thereof.
　イオン性化合物を構成するアニオン部としては、カチオン部とイオン結合してイオン性化合物を形成し得るものであれば特に制限されない。具体的には、例えば、Ｆ-、Ｃｌ-、Ｂｒ-、Ｉ-、ＡｌＣｌ4 -、Ａｌ2Ｃｌ7 -、ＢＦ4 -、ＰＦ6 -、ＳＣＮ-、ＣｌＯ4 -、ＮＯ3 -、ＣＨ3ＣＯＯ-、ＣＦ3ＣＯＯ-、ＣＨ3ＳＯ3 -、ＣＦ3ＳＯ3 -、（ＣＦ3ＳＯ2）2Ｎ-、（ＦＳＯ2）2Ｎ-、（ＣＦ3ＳＯ2）3Ｃ-、ＡｓＦ6 -、ＳｂＦ6 -、ＮｂＦ6 -、ＴａＦ6 -、Ｆ（ＨＦ）n -（ｎは１～３）、（ＣＮ）2Ｎ-、Ｃ4Ｆ9ＳＯ3 -、（Ｃ2Ｆ5ＳＯ2）2Ｎ-、Ｃ3Ｆ7ＣＯＯ-および（ＣＦ3ＳＯ2）（ＣＦ3ＣＯ）Ｎ-が挙げられる。 The anion portion constituting the ionic compound is not particularly limited as long as it can ionically bond with the cation portion to form an ionic compound. Specifically, for example, F − , Cl − , Br − , I − , AlCl 4 − , Al 2 Cl 7 − , BF 4 − , PF 6 − , SCN − , ClO 4 − , NO 3 − , CH 3 COO − , CF 3 COO − , CH 3 SO 3 − , CF 3 SO 3 − , (CF 3 SO 2 ) 2 N − , (FSO 2 ) 2 N − , (CF 3 SO 2 ) 3 C − , AsF 6 - , SbF 6 - , NbF 6 - , TaF 6 - , F(HF) n - (n is 1 to 3), (CN) 2 N - , C 4 F 9 SO 3 - , (C 2 F 5 SO 2 ) 2N- , C3F7COO- and ( CF3SO2 ) ( CF3CO ) N-.
　イオン性化合物としては、リチウムビス（トリフルオロメタンスルホニル）イミド、リチウムビス（フルオロスルホニル）イミド、リチウムトリス（トリフルオロメタンスルホニル）メタン、カリウムビス（トリフルオロメタンスルホニル）イミド、カリウムビス（フルオロスルホニル）イミド、１－エチルピリジニウムヘキサフルオロホスフェート、１－ブチルピリジニウムヘキサフルオロホスフェート、１－ヘキシル－４－メチルピリジニウムヘキサフルオロホスフェート、１－オクチル－４－メチルピリジニウムヘキサフルオロホスフェート、１－オクチル－４－メチルピリジニウムビス（フルオロスルホニル）イミド、１－オクチル－４－メチルピリジニウムビス（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）アンモニウムビス（トリフルオロメタンスルホニル）イミド、１－オクチルピリジニウムフルオロスルホニウムイミド、１－オクチル－３－メチルピリジニウムトリフルオロスルホニウムイミドが好ましい。 Ionic compounds include lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium tris(trifluoromethanesulfonyl)methane, potassium bis(trifluoromethanesulfonyl)imide, potassium bis(fluorosulfonyl)imide, 1 - ethylpyridinium hexafluorophosphate, 1-butylpyridinium hexafluorophosphate, 1-hexyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium bis(fluoro sulfonyl)imide, 1-octyl-4-methylpyridinium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate, N,N-diethyl-N -methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, 1-octylpyridinium fluorosulfonium imide, 1-octyl-3-methylpyridinium trifluorosulfonium imide are preferred.
　導電性ポリマーとしては、例えば、ポリチオフェン、ポリアニリン、ポリピロール、これらの誘導体が挙げられる。 Examples of conductive polymers include polythiophene, polyaniline, polypyrrole, and derivatives thereof.
　本組成物が帯電防止剤（Ｆ）を含有する場合、本組成物における帯電防止剤（Ｆ）の含有量は、ポリマー（Ａ）とポリマー（Ｂ）との合計１００質量部に対し、通常３質量部以下、好ましくは０．０１～３質量部、より好ましくは０．０５～２．５質量部である。 When the present composition contains an antistatic agent (F), the content of the antistatic agent (F) in the present composition is usually 3 parts per 100 parts by mass of the total of the polymer (A) and the polymer (B). parts by mass or less, preferably 0.01 to 3 parts by mass, more preferably 0.05 to 2.5 parts by mass.
［有機溶媒］
　本組成物は、本発明の効果を損なわない範囲で、有機溶媒を含有してもよい。
　有機溶媒としては、例えば、ポリマー（Ａ）の合成方法の欄に記載した重合溶媒が挙げられる。本組成物は、例えば、ポリマー（Ａ）および重合溶媒を含むポリマー溶液と、ポリマー（Ｂ）および重合溶媒を含むポリマー溶液と、硬化剤（Ｃ）とを混合することにより調製してもよい。
　本組成物における有機溶媒の含有量は、例えば０質量％以上、好ましくは１０質量％以上であり、例えば９０質量％以下、好ましくは８０質量％以下である。 [Organic solvent]
The composition may contain an organic solvent as long as the effects of the present invention are not impaired.
The organic solvent includes, for example, the polymerization solvents described in the section of the method for synthesizing the polymer (A). The composition may be prepared, for example, by mixing a polymer solution containing the polymer (A) and the polymerization solvent, a polymer solution containing the polymer (B) and the polymerization solvent, and the curing agent (C).
The content of the organic solvent in the present composition is, for example, 0% by mass or more, preferably 10% by mass or more, and is, for example, 90% by mass or less, preferably 80% by mass or less.
＜本組成物の製造方法＞
　本組成物は、例えば、ポリマー（Ａ）と、ポリマー（Ｂ）と、硬化剤（Ｃ）と、必要に応じて前記その他の成分とを、攪拌装置等を用いて公知の方法で混合することにより製造することができる。
　各成分を混合・撹拌する際には、各成分を一括混合・撹拌してもよく、順次混合・撹拌してもよい。
　撹拌条件は特に制限されないが、作業性および生産性の面から、室温にて１０～１２０分程度であればよい。 <Method for producing the present composition>
The present composition can be prepared, for example, by mixing the polymer (A), the polymer (B), the curing agent (C), and, if necessary, the other components by a known method using a stirring device or the like. can be manufactured by
When mixing and stirring each component, each component may be mixed and stirred all at once, or may be mixed and stirred sequentially.
The stirring conditions are not particularly limited, but from the standpoint of workability and productivity, the stirring may be performed at room temperature for about 10 to 120 minutes.
＜本組成物の用途＞
　本組成物の用途は特に制限されず、粘着剤層が用いられてきた用途に制限なく使用することができるが、本発明の効果がより発揮される等の点から、本組成物は、光学部材の貼り合わせに用いることが好ましく、タッチパネル式入出力装置等の表示装置を構成する部材の貼り合わせに用いることがより好ましい。本組成物を用いた貼り合わせの対象となる部材（被着体）は、例えば、偏光フィルム（楕円偏光フィルムを含む）、位相差フィルム、反射防止フィルム、輝度向上フィルム、光拡散フィルム、ハードコートフィルム等の光学フィルム、金属またはＩＴＯ層等の金属酸化物層、ガラスまたは樹脂製基材が挙げられる。 <Application of the present composition>
The application of the present composition is not particularly limited, and it can be used without limitation in the applications in which the pressure-sensitive adhesive layer has been used. It is preferably used for bonding members, and more preferably used for bonding members constituting a display device such as a touch panel type input/output device. Members (adherends) to be bonded using the present composition include, for example, polarizing films (including elliptical polarizing films), retardation films, antireflection films, brightness enhancement films, light diffusion films, and hard coats. Optical films such as films, metal or metal oxide layers such as ITO layers, and substrates made of glass or resin can be used.
≪粘着シート≫
　本発明の一実施形態に係る粘着シート（以下「本粘着シート」ともいう。）は、本組成物から得られた粘着剤層（以下「本粘着剤層」ともいう。）を有する。
　本粘着シートは、本粘着剤層のみからなるシートであってもよく、前記光学フィルム、金属または金属酸化物層および基材等から選ばれる少なくとも１種の被着体と、本粘着剤層とを含む積層体であってもよい。
　例えば、該積層体に含まれる本粘着剤層は、１層でもよく、２層以上でもよい。２層以上である場合、これらは、同一の層であってもよく、異なる層であってもよい。該積層体に含まれる被着体（光学フィルムなどの他の層）についても同様である。 ≪Adhesive sheet≫
A pressure-sensitive adhesive sheet according to an embodiment of the present invention (hereinafter also referred to as "the present pressure-sensitive adhesive sheet") has a pressure-sensitive adhesive layer (hereinafter also referred to as "the present pressure-sensitive adhesive layer") obtained from the present composition.
The present pressure-sensitive adhesive sheet may be a sheet consisting only of the present pressure-sensitive adhesive layer, and includes at least one adherend selected from the optical film, the metal or metal oxide layer, the substrate, etc., and the pressure-sensitive adhesive layer. It may be a laminate containing.
For example, the pressure-sensitive adhesive layer contained in the laminate may be one layer or two or more layers. When there are two or more layers, these may be the same layer or different layers. The same applies to adherends (other layers such as optical films) included in the laminate.
　本粘着シートの厚さは特に制限されない。
　本粘着シートが、本粘着剤層のみからなるシートである場合、下記本粘着剤層の厚さと同程度である。
　本粘着シートが前記積層体である場合、被着体の種類により変化し、また、用途に応じて適宜選択すればよいが、例えば５μｍ以上、好ましくは１０μｍ以上であり、例えば３００μｍ以下、好ましくは２００μｍ以下である。 The thickness of the adhesive sheet is not particularly limited.
When the pressure-sensitive adhesive sheet is a sheet consisting only of the pressure-sensitive adhesive layer, the thickness is approximately the same as the thickness of the pressure-sensitive adhesive layer described below.
When the pressure-sensitive adhesive sheet is the laminate, it varies depending on the type of the adherend and may be appropriately selected according to the application. 200 μm or less.
＜本粘着剤層＞
　本粘着剤層は、本組成物から形成され、具体的には、本組成物を架橋反応させることにより形成することができる。
　このように、本組成物を架橋反応させて得られる本粘着剤層の好適な態様の例としては、ポリマー（Ａ）の硬化剤（Ｃ）による架橋体を含む態様が挙げられ、さらには、架橋反応に寄与しなかった余剰の硬化剤（Ｃ）の自己縮合物が、ポリマー（Ａ）、ポリマー（Ａ）の架橋体およびポリマー（Ｂ）から選ばれる少なくとも１つと絡み合った態様が挙げられる。 <This adhesive layer>
The present pressure-sensitive adhesive layer is formed from the present composition, and specifically, can be formed by subjecting the present composition to a cross-linking reaction.
Examples of preferred aspects of the present pressure-sensitive adhesive layer obtained by subjecting the present composition to a cross-linking reaction include an aspect including a cross-linked product of the polymer (A) with the curing agent (C). Excess self-condensate of curing agent (C) that did not contribute to the cross-linking reaction is entangled with at least one selected from polymer (A), cross-linked polymer (A) and polymer (B).
　本組成物を架橋させて本粘着剤層を形成する場合、本粘着剤層のゲル分率は特に限定されないが、柔軟性に優れる粘着剤層を容易に形成することができる等の点から、好ましくは５０％以上、より好ましくは６０％以上であり、好ましくは９０％以下、より好ましくは８５％以下である。
　該ゲル分率は、具体的には下記実施例に記載の方法で測定できる。 When the present pressure-sensitive adhesive layer is formed by cross-linking the present composition, the gel fraction of the present pressure-sensitive adhesive layer is not particularly limited. It is preferably 50% or more, more preferably 60% or more, and preferably 90% or less, more preferably 85% or less.
Specifically, the gel fraction can be measured by the method described in Examples below.
　本粘着剤層の厚さは、本粘着シートの用途等に応じて適宜設定すればよく、特に制限されないが、通常５μｍ以上、好ましくは１０μｍ以上であり、通常１２５μｍ以下、好ましくは１００μｍ以下である。 The thickness of the pressure-sensitive adhesive layer may be appropriately set according to the application of the pressure-sensitive adhesive sheet, and is not particularly limited, but is usually 5 μm or more, preferably 10 μm or more, and usually 125 μm or less, preferably 100 μm or less. .
　本粘着剤層の粘着力は、被着体に対し十分に粘着できる等の点から、好ましくは１．０Ｎ／２５ｍｍ以上であり、被着体に粘着して使用する際には、被着体から剥がれたり、浮いたりせず、被着体から剥離したい時には、糊残り等が起こらずに被着体から剥離できる適度な粘着力となる等の点から、より好ましくは２．０～２０．０Ｎ／２５ｍｍである。
　該粘着力は、具体的には下記実施例に記載の方法で測定できる。 The adhesive strength of the present pressure-sensitive adhesive layer is preferably 1.0 N/25 mm or more in terms of sufficient adhesion to the adherend, etc., and when used by adhering to the adherend, It is more preferably 2.0 to 20.0 to 2.0 to 20.0, since it does not peel off or float from the adherend, and when it is desired to be peeled off from the adherend, it has an appropriate adhesive strength that allows it to be peeled off from the adherend without leaving an adhesive residue. 0 N/25 mm.
Specifically, the adhesive strength can be measured by the method described in Examples below.
［本粘着シートの製造方法］
　本粘着剤層は、例えば、本組成物を前記被着体や支持体に塗布し、塗布された本組成物を架橋反応させることにより、前記被着体や支持体上に本粘着剤層を形成することができる。本組成物を前記被着体や支持体上に塗布した後、必要に応じて、さらに該塗布面上に前記被着体や支持体上を配置して、本組成物を架橋反応させてもよい。 [Manufacturing method of this adhesive sheet]
The pressure-sensitive adhesive layer is formed on the adherend or support by, for example, applying the present composition to the adherend or support and causing a cross-linking reaction of the applied composition. can be formed. After coating the present composition on the adherend or support, if necessary, further arrange the adherend or support on the coated surface to allow the composition to undergo a cross-linking reaction. good.
　本粘着剤層のみからなる粘着シートを形成したい場合には、前記支持体から、本粘着剤層を剥離すればよい。本粘着剤層のみからなる粘着シートは、保管時、移動時等は、支持体と共に、保管、移動等し、使用時には、該支持体から剥離され、粘着剤層のみからなる粘着シートとして使用すればよい。
　該支持体としては、剥離処理された基材が挙げられる。 When it is desired to form a pressure-sensitive adhesive sheet consisting of only the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer may be peeled off from the support. The pressure-sensitive adhesive sheet consisting of only the pressure-sensitive adhesive layer is stored, transferred, etc. together with the support during storage, transfer, etc., and is peeled off from the support during use. Just do it.
The support includes a release-treated substrate.
　本粘着シートが、前記積層体である場合には、例えば、本組成物を前記被着体上に塗布し、さらに該塗布面上に支持体を配置することにより、被着体、本粘着剤層および支持体がこの順で積層された積層体を得ることができる。該積層体は、使用時には、支持体を剥がし、被着体および本粘着剤層からなる粘着シートとして使用できる。 When the pressure-sensitive adhesive sheet is the laminate, for example, the composition is applied onto the adherend, and a support is placed on the coated surface to obtain the adherend and the pressure-sensitive adhesive. A laminate in which a layer and a support are laminated in this order can be obtained. At the time of use, the laminate can be used as a pressure-sensitive adhesive sheet consisting of an adherend and the present pressure-sensitive adhesive layer after peeling off the support.
　前記被着体としての基材や、前記支持体として用いる基材としては特に制限されないが、樹脂製板、ガラス板、織布、不織布、紙等が挙げられる。
　該樹脂としては、透明な樹脂が好ましく、該透明な樹脂としては、ポリカーボネート（ＰＣ）、ポリメチルメタクリレート（ＰＭＭＡ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリプロピレン（ＰＰ）、アクリロニトリル－ブタジエン－スチレン共重合体（ＡＢＳ）、ポリアミド（ナイロン）等が挙げられる。 The substrate used as the adherend and the substrate used as the support are not particularly limited, and examples thereof include resin plates, glass plates, woven fabrics, non-woven fabrics, and paper.
The resin is preferably a transparent resin, and examples of the transparent resin include polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polypropylene (PP), acrylonitrile-butadiene-styrene copolymer ( ABS), polyamide (nylon), and the like.
　本組成物の塗布方法としては、公知の方法、例えば、スピンコート法、ナイフコート法、ロールコート法、バーコート法、ブレードコート法、ダイコート法、グラビアコート法により、得られる粘着剤層が所定の厚さになるように塗布する方法が挙げられる。
　また、場合によっては、塗布の代わりに、前記被着体や支持体を本組成物に浸漬することで、被着体や支持体上に本組成物を配置することもできる。 As the coating method of the composition, a known method such as a spin coating method, a knife coating method, a roll coating method, a bar coating method, a blade coating method, a die coating method, or a gravure coating method can be used to obtain a predetermined pressure-sensitive adhesive layer. and a method of coating so as to have a thickness of .
In some cases, instead of coating, the composition can be placed on the adherend or support by immersing the adherend or support in the composition.
　本組成物を被着体や支持体に塗布（配置）した後、必要により、該塗布（配置）された本組成物を乾燥させてもよい。該乾燥の条件としては、溶媒の種類によっても異なるが、通常５０℃以上、好ましくは６０℃以上、通常１５０℃以下、好ましくは１００℃以下で、通常１分間以上、好ましくは２分間以上、通常１０分間以下、好ましくは７分間以下乾燥する条件が挙げられる。 After applying (arranging) the composition on the adherend or support, the applied (arranging) composition may be dried, if necessary. The drying conditions vary depending on the type of solvent, but are generally 50° C. or higher, preferably 60° C. or higher, generally 150° C. or lower, preferably 100° C. or lower, and generally 1 minute or longer, preferably 2 minutes or longer. Conditions for drying for 10 minutes or less, preferably 7 minutes or less are included.
　前記のように、必要により本組成物を乾燥させた後、該本組成物を養生する工程を設けることが好ましい。該養生する条件としては、通常５℃以上、好ましくは１５℃以上、通常６０℃以下、好ましくは４０℃以下、通常５～７０％ＲＨ、好ましくは５～５０％ＲＨの環境下で、通常３日以上、好ましくは７日間以上、好ましくは１０日間以下養生する条件が挙げられる。このような条件で養生すると、架橋が十分に進み、物性の安定した粘着剤層を容易に形成することができる。 As described above, it is preferable to provide a step of curing the present composition after drying the present composition if necessary. The curing conditions are usually 5° C. or higher, preferably 15° C. or higher, usually 60° C. or lower, preferably 40° C. or lower, usually 5 to 70% RH, preferably 5 to 50% RH. Conditions for curing for 10 days or more, preferably 7 days or more, preferably 10 days or less. When cured under such conditions, cross-linking proceeds sufficiently, and a pressure-sensitive adhesive layer having stable physical properties can be easily formed.
≪光学部材≫
　本発明の一実施形態に係る光学部材は、本粘着剤層を有する。
　該光学部材の具体例としては、前記積層体が挙げられる。 ≪Optical components≫
An optical member according to one embodiment of the present invention has the pressure-sensitive adhesive layer.
A specific example of the optical member is the laminate.
　前記光学部材の例としてより具体的には、偏光板と、本粘着剤層と、液晶パネルと、本粘着剤層と、偏光板とがこの順で積層された積層体を含む液晶表示装置、飛散防止フィルムと、本粘着剤層と、ＩＴＯ層と、ガラスパネルとがこの順で積層された積層体を含むタッチパネルが挙げられる。 More specifically, as an example of the optical member, a liquid crystal display device including a laminate in which a polarizing plate, the present pressure-sensitive adhesive layer, a liquid crystal panel, the present pressure-sensitive adhesive layer, and a polarizing plate are laminated in this order, A touch panel includes a laminate in which a shatterproof film, the present pressure-sensitive adhesive layer, an ITO layer, and a glass panel are laminated in this order.
　以下、実施例に基づいて本発明の一実施形態をさらに具体的に説明するが、本発明はこれらの実施例に限定されない。 Hereinafter, one embodiment of the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
＜重量平均分子量（Ｍｗ）＞
　各ポリマーの重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法による分析を行い、下記条件でポリスチレン換算により算出した。
　・装置：ＧＰＣ－８２２０（東ソー（株）製）
　・カラム：ＴＳＫｇｅｌ　Ｇ７０００ＨXL／７．８ｍｍＩＤ×１本＋ＴＳＫｇｅｌ　ＧＭＨXL／７．８ｍｍＩＤ×２本＋ＴＳＫｇｅｌ　Ｇ２５００ＨXL／７．８ｍｍＩＤ×１本（いずれも東ソー（株）製）
　・媒体：テトラヒドロフラン
　・流速：１．０ｍＬ／ｍｉｎ
　・濃度：１．５ｍｇ／ｍＬ
　・注入量：３００μＬ
　・カラム温度：４０℃ <Weight average molecular weight (Mw)>
The weight average molecular weight (Mw) of each polymer was analyzed by a gel permeation chromatography (GPC) method and calculated by polystyrene conversion under the following conditions.
・ Apparatus: GPC-8220 (manufactured by Tosoh Corporation)
・ Column: TSKgel G7000H XL / 7.8 mm ID × 1 + TSKgel GMH XL / 7.8 mm ID × 2 + TSKgel G2500H XL / 7.8 mm ID × 1 (both manufactured by Tosoh Corporation)
・Medium: Tetrahydrofuran ・Flow rate: 1.0 mL/min
・Concentration: 1.5 mg/mL
・Injection volume: 300 μL
・Column temperature: 40°C
＜酸価＞
　各ポリマーの酸価（ｍｇＫＯＨ／ｇ）は、ポリマー１ｇを中和するのに必要な水酸化カリウムの量（ｍｇ）のことをいう。
　測定方法は、次のとおりである。まず、ポリマー約１ｇの試料にトルエン／エタノール（容積比：２／１）混合液５０ｍＬを加えて溶解したものを測定試料とした。次に、その測定試料を、自動滴定装置（東亜ディーケーケー（株）製、ＡＵＴ－５０１）を用いて、０．１Ｎ水酸化カリウムエタノール溶液で電位差滴定を行い、測定試料を中和するために必要な水酸化カリウムエタノール溶液の量を測定した。酸価は、下記式（Ｉ）により算出した。
　式（Ｉ）：酸価（ｍｇＫＯＨ／ｇ）＝（Ｂ×ｆ×５．６１１）／Ｓ
　Ｂ：滴定に用いた０．１Ｎ水酸化カリウムエタノール溶液の量（ｍＬ）
　ｆ：０．１Ｎ水酸化カリウムエタノール溶液のファクター
　Ｓ：測定試料の固形分の質量（ｇ） <Acid value>
The acid value (mgKOH/g) of each polymer refers to the amount (mg) of potassium hydroxide required to neutralize 1 g of polymer.
The measurement method is as follows. First, a measurement sample was prepared by adding 50 mL of a toluene/ethanol (volume ratio: 2/1) mixed solution to a sample of about 1 g of polymer and dissolving it. Next, the measurement sample is subjected to potentiometric titration with a 0.1 N potassium hydroxide ethanol solution using an automatic titrator (AUT-501, manufactured by Toa DKK Co., Ltd.). Necessary for neutralizing the measurement sample amount of potassium hydroxide ethanol solution was measured. The acid value was calculated by the following formula (I).
Formula (I): Acid value (mgKOH/g) = (B x f x 5.611)/S
B: Amount (mL) of 0.1N potassium hydroxide ethanol solution used for titration
f: factor of 0.1N potassium hydroxide ethanol solution S: mass (g) of solid content of measurement sample
［製造例Ａ－１］
　撹拌機、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、ｎ－ブチルアクリレート（ＢＡ）９９．９質量部、４－ヒドロキシブチルアクリレート（４ＨＢＡ）０．１質量部、および酢酸エチル１００質量部を仕込み、窒素ガスを導入しながら７０℃に昇温した。次いで、２，２’－アゾビスイソブチロニトリル（以下「ＡＩＢＮ」ともいう。）０．０５質量部を加え、窒素雰囲気下、７５～７６℃で４時間重合反応を行うことで、アクリル系ポリマー（Ａ－１）を合成した。反応終了後、反応液を酢酸エチルで希釈し、ポリマー溶液を調製した。
　得られたアクリル系ポリマー（Ａ－１）のＭｗは１５０万であった。 [Production Example A-1]
99.9 parts by weight of n-butyl acrylate (BA), 0.1 parts by weight of 4-hydroxybutyl acrylate (4HBA), and ethyl acetate were placed in a reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube. 100 parts by mass was charged, and the temperature was raised to 70° C. while nitrogen gas was introduced. Next, 0.05 part by mass of 2,2′-azobisisobutyronitrile (hereinafter also referred to as “AIBN”) is added, and a polymerization reaction is performed at 75 to 76 ° C. for 4 hours under a nitrogen atmosphere to obtain an acrylic A polymer (A-1) was synthesized. After completion of the reaction, the reaction solution was diluted with ethyl acetate to prepare a polymer solution.
Mw of the obtained acrylic polymer (A-1) was 1,500,000.
［製造例Ｂ－１］
　撹拌機、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、ＢＡを１００質量部、および酢酸エチル１００質量部を仕込み、窒素ガスを導入しながら７０℃に昇温した。次いで、ＡＩＢＮ　０．１質量部を加え、窒素雰囲気下、７５～７６℃で４時間重合反応を行った。反応終了後、反応液を酢酸エチルで希釈し、ポリマー溶液を調製した。得られたアクリル系ポリマー（Ｂ－１）のＭｗは７０万であった。 [Production Example B-1]
100 parts by mass of BA and 100 parts by mass of ethyl acetate were introduced into a reactor equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube, and the temperature was raised to 70° C. while introducing nitrogen gas. Then, 0.1 part by mass of AIBN was added, and a polymerization reaction was carried out at 75 to 76° C. for 4 hours under nitrogen atmosphere. After completion of the reaction, the reaction solution was diluted with ethyl acetate to prepare a polymer solution. Mw of the obtained acrylic polymer (B-1) was 700,000.
［製造例Ａ－３～Ａ－２１、Ａ－２３、Ａ－２４、ｃＡ－１～ｃＡ－３、ｃＡ－５、Ｂ－３～Ｂ－１９およびｃＢ－１～ｃＢ－３］
　使用したモノマーの種類とその使用量を表１～３に記載したとおりに変更したこと以外は製造例Ａ－１と同様にして、ポリマー（Ａ－３）～（Ａ－２１）、（Ａ－２３）、（Ａ－２４）、ポリマー（ｃＡ－１）～（ｃＡ－３）、（ｃＡ－５）を合成した。
　また、製造例Ｂ－１と同様にして、ポリマー（Ｂ－３）～（Ｂ－１９）、ポリマー（ｃＢ－１）～（ｃＢ－３）を合成した。
　得られた各ポリマーのＭｗを表１～３に示す。
　なお、表１～３の各モノマーの欄に記載の数値は、質量部を示す。 [Production Examples A-3 to A-21, A-23, A-24, cA-1 to cA-3, cA-5, B-3 to B-19 and cB-1 to cB-3]
Polymers (A-3) to (A-21), (A- 23), (A-24), polymers (cA-1) to (cA-3), and (cA-5) were synthesized.
Polymers (B-3) to (B-19) and polymers (cB-1) to (cB-3) were synthesized in the same manner as in Production Example B-1.
Tables 1 to 3 show the Mw of each polymer obtained.
In addition, the numerical values described in the column of each monomer in Tables 1 to 3 indicate parts by mass.
［製造例Ａ－２］
　使用したモノマーの種類とその使用量を表１に記載したとおりに変更し、ＡＩＢＮの使用量を０．０４５質量部に変更したこと以外は製造例Ａ－１と同様にして、ポリマー（Ａ－２）を合成した。得られたポリマー（Ａ－２）のＭｗは２００万であった。 [Production Example A-2]
Polymer (A- 2) was synthesized. The Mw of the obtained polymer (A-2) was 2,000,000.
［製造例Ａ－２２］
　使用したモノマーの種類とその使用量を表２に記載したとおりに変更し、ＡＩＢＮの使用量を０．０３質量部に変更したこと以外は製造例Ａ－１と同様にして、ポリマー（Ａ－２２）を合成した。得られたポリマー（Ａ－２２）のＭｗは２６０万であった。 [Production Example A-22]
Polymer (A- 22) was synthesized. The Mw of the obtained polymer (A-22) was 2.6 million.
［製造例Ａ－２５］
　使用したモノマーの種類とその使用量を表２に記載したとおりに変更し、ＡＩＢＮの使用量を０．０４５質量部に変更したこと以外は製造例Ａ－１と同様にして、ポリマー（Ａ－２５）を合成した。得られたポリマー（Ａ－２５）のＭｗは１８０万であった。 [Production Example A-25]
Polymer (A- 25) was synthesized. Mw of the obtained polymer (A-25) was 1,800,000.
［製造例ｃＡ－４］
　使用したモノマーの種類とその使用量を表３に記載したとおりに変更し、ＡＩＢＮの使用量を０．２質量部に変更したこと以外は製造例Ａ－１と同様にして、ポリマー（ｃＡ－４）を合成した。得られたポリマー（ｃＡ－４）のＭｗは５０万であった。 [Production Example cA-4]
Polymer (cA- 4) was synthesized. Mw of the obtained polymer (cA-4) was 500,000.
［製造例Ｂ－２］
　使用したモノマーの種類とその使用量を表１に記載したとおりに変更し、ＡＩＢＮの使用量を０．４質量部に変更したこと以外は製造例Ｂ－１と同様にして、ポリマー（Ｂ－２）を合成した。得られたポリマー（Ｂ－２）のＭｗは３０万であった。 [Production Example B-2]
Polymer (B- 2) was synthesized. Mw of the obtained polymer (B-2) was 300,000.
［製造例Ｂ－２０］
　使用したモノマーの種類とその使用量を表３に記載したとおりに変更し、ＡＩＢＮの使用量を０．２質量部に変更したこと以外は製造例Ｂ－１と同様にして、ポリマー（Ｂ－２０）を合成した。得られたポリマー（Ｂ－２０）のＭｗは５０万であった。 [Production Example B-20]
Polymer (B- 20) was synthesized. Mw of the obtained polymer (B-20) was 500,000.
［製造例Ｂ－２１］
　使用したモノマーの種類とその使用量を表３に記載したとおりに変更し、ＡＩＢＮの使用量を０．０５質量部に変更したこと以外は製造例Ｂ－１と同様にして、ポリマー（Ｂ－２１）を合成した。得られたポリマー（Ｂ－２１）のＭｗは１５０万であった。 [Production Example B-21]
Polymer (B- 21) was synthesized. Mw of the obtained polymer (B-21) was 1,500,000.
［製造例ｃＢ－４］
　使用したモノマーの種類とその使用量を表３に記載したとおりに変更し、ＡＩＢＮの使用量を０．５質量部に変更したこと以外は製造例Ｂ－１と同様にして、ポリマー（ｃＢ－４）を合成した。得られたポリマー（ｃＢ－４）のＭｗは２０万であった。 [Production Example cB-4]
Polymer (cB- 4) was synthesized. Mw of the resulting polymer (cB-4) was 200,000.
［実施例１］
　製造例Ａ－１で得られたポリマー（Ａ－１）のポリマー溶液に、製造例Ｂ－１で得られたポリマー（Ｂ－１）のポリマー溶液を混合し、ポリマー混合液を得た。なお、ポリマー（Ｂ－１）の配合量は、製造例Ａ－１で得られたポリマー溶液中のポリマー（Ａ－１）１００質量部に対して、ポリマー（Ｂ－１）が６０質量部となる量である。次いで、得られたポリマー混合液に、イソシアネート系硬化剤　Ｌ－４５（綜研化学（株）製）を添加して混合し、粘着剤組成物を得た。Ｌ－４５の配合量は、ポリマー（Ａ－１）とポリマー（Ｂ－１）との合計１００質量部に対してＬ－４５の固形分が１２質量部となる量である。 [Example 1]
The polymer solution of the polymer (A-1) obtained in Production Example A-1 was mixed with the polymer solution of the polymer (B-1) obtained in Production Example B-1 to obtain a polymer mixture. The blending amount of the polymer (B-1) is 60 parts by mass of the polymer (B-1) with respect to 100 parts by mass of the polymer (A-1) in the polymer solution obtained in Production Example A-1. is the amount. Next, an isocyanate curing agent L-45 (manufactured by Soken Chemical Co., Ltd.) was added to the resulting polymer mixture and mixed to obtain an adhesive composition. The amount of L-45 is such that the solid content of L-45 is 12 parts by mass with respect to the total of 100 parts by mass of polymer (A-1) and polymer (B-1).
［実施例２～３６および比較例１～１１］
　配合組成を表１～３に記載したとおりに変更したこと以外は実施例１と同様にして、粘着剤組成物を得た。
　なお、表１～３中の添加量［質量部］は、ポリマー（Ａ）またはポリマー（Ａ）の対比用ポリマー１００質量部に対する、ポリマー（Ｂ）またはポリマー（Ｂ）の対比用ポリマーの添加量である。
　また、各硬化剤、シランカップリング剤、帯電防止剤の欄の数値は、ポリマー（Ａ）（またはポリマー（Ａ）の対比用ポリマー）と、ポリマー（Ｂ）（またはポリマー（Ｂ）の対比用ポリマー）との合計１００質量部に対する、これら各成分の固形分の添加量（質量部）を示す。 [Examples 2 to 36 and Comparative Examples 1 to 11]
A pressure-sensitive adhesive composition was obtained in the same manner as in Example 1, except that the formulation composition was changed as shown in Tables 1 to 3.
The added amount [parts by mass] in Tables 1 to 3 is the added amount of the polymer (B) or the polymer for comparison of the polymer (B) with respect to 100 parts by mass of the polymer (A) or the polymer for comparison of the polymer (A). is.
In addition, the numerical values in the columns of each curing agent, silane coupling agent, and antistatic agent are polymer (A) (or polymer for comparison of polymer (A)) and polymer (B) (or polymer (B) for comparison). The amount (parts by mass) of the solid content of each of these components added to a total of 100 parts by mass with the polymer) is shown.
［粘着剤組成物の評価］
　得られた粘着剤組成物は、次の方法で評価を行った。評価結果を表１～３に示す。 [Evaluation of adhesive composition]
The pressure-sensitive adhesive compositions obtained were evaluated by the following methods. The evaluation results are shown in Tables 1-3.
［積層体の作製］
　実施例および比較例で得られた粘着剤組成物を離型処理されたＰＥＴフィルム上に塗布し、９０℃で４分間乾燥させ、乾燥後の厚さが２０μｍの粘着剤層を形成した。次いで、形成した粘着剤層上にさらに離型処理されたＰＥＴフィルムを貼り合わせ、２枚のＰＥＴフィルムに挟まれた粘着剤層を有する積層体を作製した。 [Preparation of laminate]
The pressure-sensitive adhesive compositions obtained in Examples and Comparative Examples were applied onto a release-treated PET film and dried at 90° C. for 4 minutes to form a pressure-sensitive adhesive layer having a thickness of 20 μm after drying. Next, a release-treated PET film was laminated on the formed adhesive layer to prepare a laminate having an adhesive layer sandwiched between two PET films.
［粘着剤層付偏光板の作製］
　実施例および比較例で得られた粘着剤組成物を離型処理されたＰＥＴフィルム上に塗布し、９０℃で４分間乾燥させ、乾燥後の厚さが２０μｍの粘着剤層を形成した。次いで、形成した粘着剤層上に偏光板を重ねて貼り合わせ、２３℃／５０％ＲＨの環境下で７日間養生し、ＰＥＴフィルムを有する粘着剤層付偏光板を作製した。 [Preparation of polarizing plate with adhesive layer]
The pressure-sensitive adhesive compositions obtained in Examples and Comparative Examples were applied onto a release-treated PET film and dried at 90° C. for 4 minutes to form a pressure-sensitive adhesive layer having a thickness of 20 μm after drying. Next, a polarizing plate was superimposed on the formed adhesive layer and bonded together, and cured in an environment of 23° C./50% RH for 7 days to prepare a polarizing plate with an adhesive layer having a PET film.
［高温耐久性、湿熱耐久性およびリワーク性評価用サンプルの作製］
　作製した粘着剤層付偏光板を１５０ｍｍ×２５０ｍｍに裁断し、ＰＥＴフィルムを剥がして厚さ１．１ｍｍのガラス板に貼付し、圧着した。この粘着剤層付偏光板を貼付したガラス板を、５０℃、５気圧の条件で、２０分間オートクレーブ処理をし、その後、２３℃／５０％ＲＨの環境下で２４時間放置することで、評価用サンプルを作製した。 [Preparation of samples for evaluation of high temperature durability, wet heat durability and reworkability]
The pressure-sensitive adhesive layer-attached polarizing plate thus prepared was cut into a size of 150 mm×250 mm, the PET film was peeled off, and the plate was adhered to a glass plate having a thickness of 1.1 mm and pressure-bonded. The glass plate to which the pressure-sensitive adhesive layer-attached polarizing plate was attached was autoclaved under conditions of 50° C. and 5 atm for 20 minutes, and then left in an environment of 23° C./50% RH for 24 hours. A sample for
＜ゲル分率＞
　前記のとおり作製した積層体を２３℃／５０％ＲＨの環境下で７日間養生し、養生後の積層体の粘着剤層を乾燥質量で０．１ｇ（乾燥質量（１））サンプル瓶に採取し、該サンプル瓶に酢酸エチル３０ｇを加えて２３℃の環境下で２４時間放置した。その後、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濾過し、金網上の残留物を１００℃で２時間乾燥して得られる乾燥質量（乾燥質量（２））を測定し、ゲル分率を次式により求めた。
　ゲル分率（％）＝（乾燥質量（２）／乾燥質量（１））×１００ <Gel fraction>
The laminate prepared as described above was cured in an environment of 23° C./50% RH for 7 days, and 0.1 g of the adhesive layer of the laminate after curing was dried (dry weight (1)) and collected in a sample bottle. Then, 30 g of ethyl acetate was added to the sample bottle and allowed to stand in an environment of 23° C. for 24 hours. After that, the contents of the sample bottle were filtered through a 200-mesh stainless steel wire mesh, and the dry mass obtained by drying the residue on the wire mesh at 100 ° C. for 2 hours (dry mass (2)) was measured, and the gel fraction was was obtained from the following equation.
Gel fraction (%) = (dry mass (2) / dry mass (1)) x 100
＜エージング性＞
　前記のとおり作製した積層体を、２３℃／５０％ＲＨの環境下に置き、該積層体のゲル分率の値を経時的に測定した。積層体を作製してからＸ時間後のゲル分率と、Ｘ＋２４時間後のゲル分率との差が１％未満になる時間を確認し、下記の基準に従って評価した。
　（評価基準）
　◎：前記時間Ｘが１６８時間未満である。
　○：前記時間Ｘが１６８時間以上である。
　なお、表３中の「－」は、粘着剤組成物が硬化しなかったためエージング性を評価していないことを示す。 <Aging property>
The laminate produced as described above was placed in an environment of 23° C./50% RH, and the gel fraction value of the laminate was measured over time. The time at which the difference between the gel fraction after X hours from the production of the laminate and the gel fraction after X+24 hours became less than 1% was confirmed and evaluated according to the following criteria.
(Evaluation criteria)
A: The time X is less than 168 hours.
Good: The time X is 168 hours or longer.
Note that "-" in Table 3 indicates that the adhesive composition was not cured and therefore the aging property was not evaluated.
＜高温耐久性（１１５℃）＞
　前記のとおり作製した評価用サンプルを、１１５℃の環境下で５００時間放置した。その後、２３℃／５０％ＲＨの環境下に取り出して２４時間放置し、下記の基準に従って外観を目視により評価した。
　（評価基準）
　◎：発泡、浮き等の不具合がない。
　△：僅かに発泡、浮きが発生しており、実用上問題が生じる可能性がある。
　×：著しい発泡、浮き、剥がれが発生している。 <High temperature durability (115°C)>
The evaluation sample prepared as described above was left in an environment of 115° C. for 500 hours. After that, it was taken out in an environment of 23° C./50% RH and allowed to stand for 24 hours, and the appearance was visually evaluated according to the following criteria.
(Evaluation criteria)
⊚: No defects such as foaming or floating.
Δ: Slight foaming and floating occurred, which may cause practical problems.
x: Significant bubbling, floating, and peeling occurred.
＜湿熱耐久性（６５℃／９５％ＲＨ）＞
　前記のとおり作製した評価用サンプルを、６５℃／９５％ＲＨの環境下で５００時間放置した。その後、２３℃／５０％ＲＨの環境下に取り出して２４時間放置し、下記の基準に従って外観を目視により評価した。
　（評価基準）
　◎：発泡等の不具合がない。
　○：微小な発泡が発生しているが、実用上問題のない程度である。
　△：発泡等の不具合が発生しており、実用上問題が生じる可能性がある。
　×：著しい発泡が発生している。 <Wet heat durability (65° C./95% RH)>
The evaluation sample prepared as described above was left in an environment of 65° C./95% RH for 500 hours. After that, it was taken out in an environment of 23° C./50% RH and allowed to stand for 24 hours, and the appearance was visually evaluated according to the following criteria.
(Evaluation criteria)
(double-circle): There is no defect, such as foaming.
◯: Fine foaming occurs, but it is of a degree that poses no practical problem.
Δ: Problems such as foaming occurred, and there is a possibility that problems will occur in practical use.
x: Remarkable foaming occurs.
＜リワーク性＞
　前記のとおり作製した評価用サンプルから粘着剤層付偏光板を手で剥がし、ガラス板表面の汚染の程度および剥離性を評価した。
　（評価基準）
　◎：容易に剥がすことができ、かつガラス板表面に汚染がない。
　○：やや剥離し難いが、ガラス板表面に汚染はない。
　△：やや剥離し難く、ガラス板表面に微かな汚染（糊残り）が見られる。
　×：剥離し難く、ガラス板表面に明らかな汚染（糊残り）が見られる。 <Reworkability>
The pressure-sensitive adhesive layer-attached polarizing plate was manually peeled off from the sample for evaluation prepared as described above, and the degree of contamination on the surface of the glass plate and the releasability were evaluated.
(Evaluation criteria)
⊚: It can be easily peeled off and the surface of the glass plate is free from contamination.
◯: Slightly difficult to peel off, but no contamination on the surface of the glass plate.
Δ: Slightly difficult to peel, slight contamination (adhesive residue) is observed on the surface of the glass plate.
x: It is difficult to peel off, and clear contamination (adhesive residue) is observed on the surface of the glass plate.
＜光漏れ試験＞
　前記のとおり作製したＰＥＴフィルムを有する粘着剤層付偏光板を１５０ｍｍ×２５０ｍｍに裁断し、ＰＥＴフィルムを剥がし、互いに偏光軸が直交するように、厚さ１．１ｍｍのガラス板の両面に貼付・圧着することで光漏れ試験用積層体を作製した。作製した光漏れ試験用積層体を、５０℃、５気圧の条件で、２０分間オートクレーブ処理をし、その後８０℃の環境下で５００時間放置した。得られた光漏れ試験用積層体に、液晶モニターのバックライトの光を照射し、その時の光漏れの様子を下記の基準に従って目視により評価した。
　（評価基準）
　◎：光漏れが見られない。
　○：僅かに光漏れが見られるが、実用上問題のない程度である。
　△：光漏れが見られ、実用上問題が生じる可能性がある。
　×：著しい光漏れが見られる。 <Light leakage test>
The pressure-sensitive adhesive layer-attached polarizing plate having the PET film produced as described above was cut into 150 mm × 250 mm, the PET film was peeled off, and the polarizing axes were perpendicular to each other. A laminated body for a light leakage test was produced by crimping. The produced laminate for light leakage test was autoclaved under conditions of 50° C. and 5 atm for 20 minutes, and then left in an environment of 80° C. for 500 hours. The obtained laminate for light leakage test was irradiated with light from a backlight of a liquid crystal monitor, and the state of light leakage at that time was visually evaluated according to the following criteria.
(Evaluation criteria)
A: No light leakage is observed.
◯: Light leakage is slightly observed, but it is practically no problem.
Δ: Light leakage is observed, and there is a possibility that a practical problem will occur.
x: Significant light leakage is observed.
＜粘着力試験＞
　前記のとおり作製したＰＥＴフィルムを有する粘着剤層付偏光板を２５ｍｍ幅に裁断し、離型処理されたＰＥＴフィルムを剥がし、２３℃／５０％のＲＨの環境下で、ガラス板に貼り合わせ、５０℃、５気圧の条件で、２０分間オートクレーブ処理をした。その後、２３℃／５０％ＲＨの環境下に取り出して１時間静置し、粘着剤層付偏光板をガラス板から、剥離角度１８０°、引張速度３００ｍｍ／分で剥離した際の粘着力を測定した。 <Adhesion test>
The pressure-sensitive adhesive layer-attached polarizing plate having the PET film produced as described above was cut to a width of 25 mm, the release-treated PET film was peeled off, and the plate was laminated to a glass plate in an environment of 23°C/50% RH, Autoclave treatment was performed for 20 minutes under conditions of 50° C. and 5 atm. After that, it was taken out in an environment of 23° C./50% RH and allowed to stand still for 1 hour, and the adhesive force was measured when the polarizing plate with an adhesive layer was peeled off from the glass plate at a peeling angle of 180° and a tensile speed of 300 mm/min. did.
＜腐食性＞
　前記のとおり作製したＰＥＴフィルムを有する粘着剤層付偏光板のＰＥＴフィルムを剥がし、粘着剤層上に１０ｍｍ×６０ｍｍに裁断したＩＴＯ蒸着フィルムを貼り合わせ、５０℃、５気圧の条件で、２０分間オートクレーブ処理を行った。次いで、２３℃／５０％ＲＨの環境下で１時間放置した後、６０℃／９０％ＲＨの環境下で５００時間放置した。次いで、２３℃／５０％ＲＨの環境下で１時間放置した後、ＩＴＯ蒸着フィルムの抵抗値（試験後の抵抗値）を測定した。予め測定しておいた、粘着剤層に貼り合わせる前のＩＴＯ蒸着フィルムの抵抗値（試験前の抵抗値）と比較し、試験前の抵抗値に対する試験後の抵抗値の変化率を求め、下記の基準に従って評価した。
　ここで、前記抵抗値の変化は、ＩＴＯの腐食により生じると考えられるため、変化率が１２０％を超える場合をＩＴＯ腐食性があると判定し、変化率が１２０％以下である場合をＩＴＯ腐食性なしと判定した。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。
　（評価基準）
　◎：変化率（試験後の抵抗値×１００／試験前の抵抗値）が１２０％以下である。
　×：変化率（試験後の抵抗値×１００／試験前の抵抗値）が１２０％を超える。 <Corrosiveness>
The PET film of the adhesive layer-attached polarizing plate having the PET film prepared as described above was peeled off, and an ITO vapor deposition film cut to 10 mm × 60 mm was pasted on the adhesive layer, and the pressure was applied at 50°C and 5 atm for 20 minutes. It was autoclaved. Then, it was left under an environment of 23° C./50% RH for 1 hour, and then left under an environment of 60° C./90% RH for 500 hours. Then, after being left for 1 hour in an environment of 23° C./50% RH, the resistance value of the ITO deposited film (resistance value after the test) was measured. Compared with the previously measured resistance value of the ITO deposited film before bonding to the adhesive layer (resistance value before the test), the rate of change in the resistance value after the test with respect to the resistance value before the test was obtained. was evaluated according to the criteria of
Here, since the change in the resistance value is considered to be caused by corrosion of ITO, it is determined that there is ITO corrosiveness when the rate of change exceeds 120%, and ITO corrosion when the rate of change is 120% or less. determined to be non-sexual. A tester (manufactured by Sanwa Electric Instrument Co., Ltd., digital multimeter PC510) was used to measure the resistance value.
(Evaluation criteria)
A: Change rate (resistance value after test×100/resistance value before test) is 120% or less.
x: Change rate (resistance value after test×100/resistance value before test) exceeds 120%.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１～３中の各成分の記号の意味は以下のとおりである。
　・ＢＡ：ｎ－ブチルアクリレート
　・２ＥＨＡ：２－エチルヘキシルアクリレート
　・ＭＡ：メチルアクリレート
　・ＭＥＡ：２－メトキシエチルアクリレート
　・ＬＡ：ラウリルアクリレート
　・ＩＢＸＡ：イソボルニルアクリレート
　・ＢｚＡ：ベンジルアクリレート
　・ＡＭ：アクリルアミド
　・ＮＶＰ：Ｎ－ビニルピロリドン
　・４ＨＢＡ：４－ヒドロキシブチルアクリレート
　・２ＨＥＡ：２－ヒドロキシエチルアクリレート
　・ＡＡ：アクリル酸
　・２ＥＨＭＡ：２－エチルヘキシルメタクリレート
　・ＤＭＡ：ジメチルアミノエチルアクリレート
　・Ｌ－４５：トリレンジイソシアネートのトリメチロールプロパン付加体（綜研化学（株）製）
　・Ｙ－７５：ヘキサメチレンジイソシアネートのイソシアヌレート体（綜研化学（株）製）
　・ＴＤ－７５：キシリレンジイソシアネートのトリメチロールプロパン付加体（綜研化学（株）製）
　・Ｅ－５ＣＭ：エポキシ系硬化剤（綜研化学（株）製）
　・Ｍ－１２ＡＴ：アルミキレート硬化剤（綜研化学（株）製）
　・Ａ－５０：シランカップリング剤（綜研化学（株）製）
　・ＡＳ－Ｂ：帯電防止剤（綜研化学（株）製） The symbols for each component in Tables 1 to 3 have the following meanings.
BA: n-butyl acrylate 2EHA: 2-ethylhexyl acrylate MA: methyl acrylate MEA: 2-methoxyethyl acrylate LA: lauryl acrylate IBXA: isobornyl acrylate BzA: benzyl acrylate AM: acrylamide NVP : N-vinylpyrrolidone 4HBA: 4-hydroxybutyl acrylate 2HEA: 2-hydroxyethyl acrylate AA: acrylic acid 2EHMA: 2-ethylhexyl methacrylate DMA: dimethylaminoethyl acrylate L-45: tolylene diisocyanate Methylolpropane adduct (manufactured by Soken Chemical Co., Ltd.)
・ Y-75: isocyanurate form of hexamethylene diisocyanate (manufactured by Soken Chemical Co., Ltd.)
・ TD-75: Trimethylolpropane adduct of xylylene diisocyanate (manufactured by Soken Chemical Co., Ltd.)
・ E-5CM: Epoxy curing agent (manufactured by Soken Chemical Co., Ltd.)
・M-12AT: aluminum chelate curing agent (manufactured by Soken Chemical Co., Ltd.)
· A-50: Silane coupling agent (manufactured by Soken Chemical Co., Ltd.)
・ AS-B: Antistatic agent (manufactured by Soken Chemical Co., Ltd.)
　表１および表２に示すとおり、各実施例における粘着剤層は、適度な粘着力を有し、高温や高湿環境下での耐久性および腐食性に優れる結果となった。
　一方で、酸化が１．０ｍｇＫＯＨ／ｇを超えているポリマー（Ａ）やポリマー（Ｂ）を用いた比較例１および比較例２は、高温耐久性、湿熱耐久性および腐食性が不十分であった。
　構成成分として水酸基含有モノマーまたはアミノ基含有モノマー由来の構成単位を０．０５質量％を超えて含んでいるポリマー（Ｂ）を用いた比較例３および比較例４は、高温耐久性および湿熱耐久性が不十分であった。
　構成成分として水酸基含有モノマー由来の構成単位を０．４質量％を超えて含んでいるポリマー（Ａ）を用いた比較例５および比較例６は、高温耐久性および湿熱耐久性が不十分であった。
　Ｍｗが２５万以下であるポリマー（Ｂ）を用いた比較例７は、高温耐久性および湿熱耐久性が不十分であった。
　ポリマー（Ａ）１００質量部に対してポリマー（Ｂ）の含有量が１０質量部未満である比較例８は、高温耐久性および湿熱耐久性が不十分であった。
　ポリマー（Ａ）とポリマー（Ｂ）の合計１００質量部に対し、硬化剤（Ｃ）の含有量が６質量部以下または３０質量部以上である比較例９および比較例１０は、高温耐久性および湿熱耐久性が不十分であった。
　構成成分として水酸基含有モノマーおよびアミノ基含有モノマー由来の構成単位が０質量％であるポリマー（Ａ）を用いた比較例１１は、高温耐久性、湿熱耐久性、リワーク性および光漏れ防止性能が不十分であった。 As shown in Tables 1 and 2, the pressure-sensitive adhesive layer in each example had appropriate adhesive strength, and was excellent in durability and corrosion resistance under high-temperature and high-humidity environments.
On the other hand, Comparative Examples 1 and 2 using polymer (A) and polymer (B) with oxidation exceeding 1.0 mg KOH / g had insufficient high temperature durability, wet heat durability and corrosiveness. rice field.
Comparative Examples 3 and 4 using a polymer (B) containing more than 0.05% by mass of structural units derived from a hydroxyl group-containing monomer or an amino group-containing monomer as a constituent show high temperature durability and wet heat durability. was insufficient.
Comparative Example 5 and Comparative Example 6 using the polymer (A) containing more than 0.4% by mass of structural units derived from a hydroxyl group-containing monomer as a structural component had insufficient high temperature durability and wet heat durability. rice field.
Comparative Example 7 using the polymer (B) having an Mw of 250,000 or less had insufficient high temperature durability and wet heat durability.
Comparative Example 8, in which the content of the polymer (B) was less than 10 parts by mass with respect to 100 parts by mass of the polymer (A), was insufficient in high temperature durability and wet heat durability.
Comparative Examples 9 and 10, in which the content of the curing agent (C) is 6 parts by mass or less or 30 parts by mass or more with respect to a total of 100 parts by mass of the polymer (A) and the polymer (B), are excellent in high temperature durability and The wet heat durability was insufficient.
Comparative Example 11 using the polymer (A) in which the structural units derived from the hydroxyl group-containing monomer and the amino group-containing monomer are 0% by mass as the constituent components has poor high temperature durability, wet heat durability, reworkability, and light leakage prevention performance. was enough.

Claims (12)

  1. 　水酸基含有モノマー（ａ１）由来の構成単位およびアミノ基含有モノマー（ａ２）由来の構成単位を合計して０質量％を超えて０．４質量％以下の量で含み、酸価が１．０ｍｇＫＯＨ／ｇ以下である、重量平均分子量が６０万以上のアクリル系ポリマー（Ａ）と、
    　水酸基含有モノマー（ｂ１）由来の構成単位およびアミノ基含有モノマー（ｂ２）由来の構成単位の合計含有量が０．０５質量％以下であり、酸価が１．０ｍｇＫＯＨ／ｇ以下である、重量平均分子量が２５万超であり、かつ、前記アクリル系ポリマー（Ａ）の重量平均分子量よりも小さいアクリル系ポリマー（Ｂ）と、
    　イソシアネート系硬化剤（Ｃ）と
    を含み、
    　前記アクリル系ポリマー（Ａ）１００質量部に対し、前記アクリル系ポリマー（Ｂ）を１０質量部以上の量で含み、
    　前記アクリル系ポリマー（Ａ）とアクリル系ポリマー（Ｂ）との合計１００質量部に対し、前記イソシアネート系硬化剤（Ｃ）を６質量部を超えて３０質量部未満の量で含む、
    粘着剤組成物。     The total amount of structural units derived from the hydroxyl group-containing monomer (a1) and the amino group-containing monomer (a2) is more than 0% by mass and not more than 0.4% by mass, and the acid value is 1.0 mgKOH / an acrylic polymer (A) having a weight average molecular weight of 600,000 or more, which is g or less;
    The total content of the structural units derived from the hydroxyl group-containing monomer (b1) and the structural units derived from the amino group-containing monomer (b2) is 0.05% by mass or less, and the acid value is 1.0 mgKOH/g or less, weight average an acrylic polymer (B) having a molecular weight of more than 250,000 and lower than the weight average molecular weight of the acrylic polymer (A);
    and an isocyanate curing agent (C),
    The acrylic polymer (B) is contained in an amount of 10 parts by mass or more with respect to 100 parts by mass of the acrylic polymer (A),
    The isocyanate curing agent (C) is contained in an amount of more than 6 parts by mass and less than 30 parts by mass with respect to a total of 100 parts by mass of the acrylic polymer (A) and the acrylic polymer (B).
    Adhesive composition.
  2. 　前記アクリル系ポリマー（Ａ）が、アルキル（メタ）アクリレートおよびアルコキシアルキル（メタ）アクリレートから選ばれる少なくとも１種のモノマー（ａ３）由来の構成単位を２５～９９．９９質量％含む、請求項１に記載の粘着剤組成物。 According to claim 1, wherein the acrylic polymer (A) contains 25 to 99.99% by mass of structural units derived from at least one monomer (a3) selected from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates. The adhesive composition described.
  3. 　前記アクリル系ポリマー（Ｂ）が、アルキル（メタ）アクリレートおよびアルコキシアルキル（メタ）アクリレートから選ばれる少なくとも１種のモノマー（ｂ３）由来の構成単位を２５～１００質量％含む、請求項１または２に記載の粘着剤組成物。 3. According to claim 1 or 2, wherein the acrylic polymer (B) contains 25 to 100% by mass of constitutional units derived from at least one monomer (b3) selected from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates. The adhesive composition described.
  4. 　前記アクリル系ポリマー（Ａ）が、前記水酸基含有モノマー（ａ１）由来の構成単位を０質量％を超えて０．４質量％以下の量で含む、請求項１～３のいずれか１項に記載の粘着剤組成物。 4. The acrylic polymer (A) according to any one of claims 1 to 3, wherein the hydroxyl group-containing monomer (a1)-derived structural unit is contained in an amount of more than 0% by mass and 0.4% by mass or less. adhesive composition.
  5. 　前記アクリル系ポリマー（Ａ）が、アルキル（メタ）アクリレートおよびアルコキシアルキル（メタ）アクリレートから選ばれる少なくとも１種のモノマー（ａ３）由来の構成単位を２５～９８質量％含み、脂環式炭化水素基含有（メタ）アクリレートおよび芳香族炭化水素基含有（メタ）アクリレートから選ばれる少なくとも１種のモノマー（ａ４）由来の構成単位を１～５０質量％含む、請求項１～４のいずれか１項に記載の粘着剤組成物。 The acrylic polymer (A) contains 25 to 98% by mass of structural units derived from at least one monomer (a3) selected from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates, and has an alicyclic hydrocarbon group Any one of claims 1 to 4, comprising 1 to 50% by mass of structural units derived from at least one monomer (a4) selected from containing (meth)acrylates and aromatic hydrocarbon group-containing (meth)acrylates. The adhesive composition described.
  6. 　前記アクリル系ポリマー（Ｂ）が、アルキル（メタ）アクリレートおよびアルコキシアルキル（メタ）アクリレートから選ばれる少なくとも１種のモノマー（ｂ３）由来の構成単位を２５～９８質量％含み、脂環式炭化水素基含有（メタ）アクリレートおよび芳香族炭化水素基含有（メタ）アクリレートから選ばれる少なくとも１種のモノマー（ｂ４）由来の構成単位を１～５０質量％含む、請求項１～５のいずれか１項に記載の粘着剤組成物。 The acrylic polymer (B) contains 25 to 98% by mass of structural units derived from at least one monomer (b3) selected from alkyl (meth)acrylates and alkoxyalkyl (meth)acrylates, and has an alicyclic hydrocarbon group. Any one of claims 1 to 5, comprising 1 to 50% by mass of structural units derived from at least one monomer (b4) selected from containing (meth)acrylates and aromatic hydrocarbon group-containing (meth)acrylates. The adhesive composition described.
  7. 　前記イソシアネート系硬化剤（Ｃ）以外の硬化剤（Ｄ）をさらに含む、請求項１～６のいずれか１項に記載の粘着剤組成物。 The adhesive composition according to any one of claims 1 to 6, further comprising a curing agent (D) other than the isocyanate curing agent (C).
  8. 　シランカップリング剤（Ｅ）をさらに含む、請求項１～７のいずれか１項に記載の粘着剤組成物。 The adhesive composition according to any one of claims 1 to 7, further comprising a silane coupling agent (E).
  9. 　帯電防止剤（Ｆ）をさらに含む、請求項１～８のいずれか１項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 8, further comprising an antistatic agent (F).
  10. 　光学部材に用いられる、請求項１～９のいずれか１項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 9, which is used for optical members.
  11. 　請求項１～１０のいずれか１項に記載の粘着剤組成物から得られた粘着剤層を有する粘着シート。 A pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition according to any one of claims 1 to 10.
  12. 　請求項１～１０のいずれか１項に記載の粘着剤組成物から得られた粘着剤層を有する光学部材。 An optical member having an adhesive layer obtained from the adhesive composition according to any one of claims 1 to 10.
PCT/JP2022/000694 2021-03-03 2022-01-12 Adhesive agent composition, adhesive sheet, and optical member WO2022185715A1 (en)

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