JP5594176B2 - Adhesive and adhesive film using the same - Google Patents

Description

  The present invention relates to an optical pressure-sensitive adhesive used for a member constituting a color display device such as a liquid crystal display device, particularly a polarizing plate.

  Conventionally, when an adhesive film or the like is bonded to an inorganic surface such as glass, ceramics, or metal, phenomena such as peeling off at the edge of the film or floating at the bonding portion due to changes over time are often observed. It is done.

  In order to solve such a phenomenon, in general, an adhesive film with improved adhesive properties is used by increasing the molecular weight of the polymer used in the adhesive film or increasing the crosslinking density of the adhesive layer. I came. However, when such an adhesive film is used, the adhesive force and cohesive force are improved. However, in a high temperature and high humidity environment, the adhesive layer cannot follow the shape change caused by the shrinkage and swelling of the base film and floats. Problems such as peeling and peeling could not be solved.

  Incidentally, some optical members used in liquid crystal display devices are used with a polarizing plate attached to the surface thereof, and a typical example is a liquid crystal cell. With respect to the adhesive used for bonding the polarizing plate and the liquid crystal cell, which are members of the liquid crystal display device, durability that prevents the polarizing plate from peeling or floating even under various environments, and the liquid crystal cell The performance which can prevent the light leak in is required. This light leakage results in non-uniform residual stress in the polarizing plate, particularly in a high-temperature and high-humidity environment, when the stress accompanying dimensional changes such as contraction and expansion of the polarizing plate cannot be relaxed by the adhesive layer. .

  In addition, when a polarizing plate is bonded to an optical component such as a liquid crystal cell in the manufacturing process of a liquid crystal display or the like, the polarizing plate is peeled off after a certain time has elapsed since the bonding position has shifted. It may be necessary to reuse expensive liquid crystal cells. Therefore, there is a need for a pressure-sensitive adhesive having re-peeling performance that can be peeled relatively easily from a liquid crystal cell even after a certain period of time after being bonded via a pressure-sensitive adhesive applied to a polarizing plate. It has been.

  Various pressure-sensitive adhesives have been proposed as pressure-sensitive adhesives that satisfy such requirements. For example, in order to solve the problem of light leakage, a technique for imparting stress relaxation properties by appropriately softening the adhesive layer by adding a plasticizer or the like to the adhesive is disclosed (see Patent Document 1). .

  In order to impart stress relaxation properties, the value (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) of the acrylic polymer by the number average molecular weight (Mn) is adjusted to 10-50, and the molecular weight distribution is broadened. Thus, a technique for enhancing the stress relaxation property of the coating film and preventing light leakage is disclosed (see Patent Document 2).

  On the other hand, in order to impart removability, a low molecular weight acrylic polymer having a high acid value and a weight average molecular weight of 0.2 to 100,000 is used for a high molecular weight acrylic polymer having a weight average molecular weight of 500,000 or more. A technique for blending is disclosed (see Patent Document 3).

Japanese Patent Laid-Open No. 9-87593 JP 2007-169329 A JP 2010-1000071 A

  However, in the pressure-sensitive adhesive of Patent Document 1, the addition of a plasticizer causes blisters that contaminate the adherend when the polarizing plate is peeled off and reduces cohesive force, so that floating and peeling over time occur. It becomes easy to do.

  Moreover, in the adhesive of patent document 2, white spot generate | occur | produced in light leakage evaluation and the effect as described in the said gazette was not seen.

  Moreover, in the adhesive of patent document 3, the acid value of a low molecular weight body is high, and the isocyanate compound currently used as a hardening | curing agent reacts preferentially with the water | moisture content which exists in the vicinity of a low molecular weight body, and deactivates. Therefore, a sufficient crosslinked structure cannot be formed. Therefore, it is necessary to use an organic peroxide crosslinking agent in combination. However, since the organic peroxide is decomposed by heat during drying to generate radicals to form a crosslinking agent, the drying conditions are limited.

  The present invention is an adhesive layer that is excellent in releasability when used for an adhesive tape, reduces floating and peeling from the adherend even after being exposed to a high temperature environment and a high temperature and high humidity environment, and has a good light leakage evaluation. The purpose is to provide a pressure-sensitive adhesive that can be used.

  In order to solve the above-mentioned problem, by crosslinking the functional group of the acrylic copolymer with a bifunctional isocyanate crosslinking agent synthesized using a linear compound so that the interval between the isocyanate groups is long, A pressure-sensitive adhesive capable of forming a pressure-sensitive adhesive layer having a cross-linked structure with a long distance between cross-linking points was invented.

  According to the present invention configured as described above, the pressure-sensitive adhesive layer is excellent in stress relaxation properties not only after high-temperature treatment but also after high-temperature and high-humidity treatment. Therefore, even when a polarizing plate that causes dimensional changes in a high-temperature and high-humidity environment is used as a base material, the possibility that the adhesive layer may float or peel over a long period can be reduced. In addition, when a polarizing film using this adhesive layer is used for a liquid crystal display device, stress concentration caused by contraction of the polarizing plate is alleviated, so that light leakage can be suppressed. As a result, even after being exposed to a high-temperature environment or a high-temperature and high-humidity environment, it is possible to reduce the floating or peeling off from the adherend, and it is possible to create an adhesive layer with good light leakage evaluation.

  The pressure-sensitive adhesive of the present invention will be described in detail. The pressure-sensitive adhesive of the present invention contains an acrylic copolymer (A) and a compound (B) having an isocyanate group. The compound (B) having an isocyanate group includes a bifunctional isocyanate compound (b1) and a compound (b2) having a number average molecular weight of 500 to 5000 having two or more functional groups capable of reacting with the isocyanate group [hereinafter, compound (b2) Sometimes it is. ] Is reacted.

  The compound (B) having an isocyanate group is a crosslinking agent for the acrylic copolymer (A), but the distance between the isocyanate groups in the compound (B) having an isocyanate group by reacting the compound (b2). Can be lengthened. By introducing the compound (b2) that serves as a spacer between the isocyanate groups, the distance between the crosslinking points when the isocyanate group and the functional group of the acrylic copolymer (A) are crosslinked can be increased. . Therefore, the adhesive layer formed from the said adhesive is excellent in the stress relaxation property after a high temperature process. Thus, for example, even when a polarizing plate that undergoes dimensional changes in a high-temperature and high-humidity environment is used as the base material, the adhesive layer is excellent in durability such that the adhesive layer can float for a long period of time and the possibility of peeling off can be reduced. Moreover, when the polarizing film using the adhesive of this invention for the adhesion layer is used for a liquid crystal display device, since the stress concentration which arises by shrinkage | contraction of a polarizing plate is eased, light leakage can be suppressed.

  In the present invention, the compound (B) having an isocyanate group was reacted with a bifunctional isocyanate compound (b1) and a compound (b2) having a number average molecular weight of 500 to 5000 having two or more functional groups capable of reacting with the isocyanate group. Is. The reaction ratio is that the isocyanate group of the bifunctional isocyanate compound (b1) is excessive with respect to the functional group of the compound (b2) having a number average molecular weight of 500 to 5000 having two or more functional groups capable of reacting with the isocyanate group. Specifically, it is preferable to react at a ratio of 1.0 mol or more of isocyanate groups to 1.0 mol or more of functional groups capable of reacting with isocyanate groups, and more preferably 2.0 mol or more. When the amount is less than 1.0 mol, all the isocyanate groups are reacted, and therefore the compound (B) having an isocyanate group does not function as a crosslinking agent, which is not preferable.

  Examples of the bifunctional isocyanate compound (b1) include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenyl. Monofunctional alcohols reacted with isocyanate monomers such as methane triisocyanate and polymethylene polyphenyl isocyanate, trifunctional isocyanates such as adducts, burettes, and nurates of these isocyanate monomers, Allophanate of methylene diisocyanate (Coronate 2770) Manufactured by Nippon Polyurethane Co., Ltd.) and the like. Among these, hexamethylene diisocyanate allophanate is preferable from the viewpoint of compatibility with the acrylic copolymer (A).

Specifically, trifunctional isocyanate is reacted with monofunctional alcohol to form bifunctional isocyanate. Specifically, trimethylolpropane adduct of tolylene diisocyanate or isocyanurate of isophorone diisocyanate is reacted with dodecyl alcohol or octyldodecyl alcohol. As reaction conditions, it is preferable to react at a reaction temperature of 60 to 100 ° C. for 2 to 6 hours in a nitrogen atmosphere.
Examples of the compound (b2) include polyols, polyamines, and polycarboxylic acids, and among these, the polyol (b3) is preferable.

  As the polyol (b3), polyether polyols, polyester polyols, polycarbonate diols and copolymers thereof are preferable.

Known polyether polyols can be used as the polyether polyols. For example, polymers, copolymers, and graft copolymers of alkylene oxides such as propylene oxide, tetrahydrofuran, ethylene oxide, butylene oxide;
Those having two or more hydroxyl groups such as hexanediol, methylhexanediol, heptanediol, octanediol or polyether diols obtained by condensation of a mixture thereof can be used. Furthermore, glycols obtained by adding alkylene oxide excluding propylene oxide such as ethylene oxide to bisphenols such as bisphenol A and bisphenol F can be used. Sanyox PP series manufactured by Sanyo Kasei Kogyo Co., Ltd., PTG series manufactured by Hodogaya Chemical Co., Ltd. can be used as a commercially available diol, and Sanniks GP Series manufactured by Sanyo Kasei Kogyo Co., Ltd. can be used as a triol.

  Known polyester polyols can be used as the polyester polyols. Examples of the polyester polyol include a polyester polyol obtained by condensation reaction of a polyfunctional alcohol component and a dibasic acid component. Examples of the polyfunctional alcohol component include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 3,3 ′. -Dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexane Examples include compounds having two hydroxyl groups such as diol, cyclohexanediol, bisphenol A, and bisphenol F, and three or more hydroxyl acids such as glycerin, trimethylolpropane, and pentaerythritol. Compounds having the like. As a commercially available diol, Kuraray polyol P series manufactured by Kuraray Co., Ltd., and as a triol, Kuraray polyol F series manufactured by Kuraray Co., Ltd. can be used.

  Examples of the dibasic acid component include aliphatic or aromatic dibasic acids such as terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid.

  Β-butyrolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-caprolactone, γ-heptanolactone, α-methyl-β-propiolactone, etc. Polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as lactones can also be used.

  Polycarbonate diols have a structure represented by the following general formula [1] in the molecule, and known polycarbonate diols can be used.

General formula [1]
− [— O—R ¹ —O—CO—] _m —
(In the formula, R ¹ represents a divalent organic residue, and m represents an integer of 1 or more.)
The polycarbonate diol can be obtained, for example, by (1) a reaction between glycol or bisphenol and a carbonate ester, or (2) a reaction in which phosgene is allowed to act on glycol or bisphenol in the presence of an alkali.

  Specific examples of the carbonic acid ester used in the production method (1) include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate.

  Examples of the glycol or bisphenol used in the production methods (1) and (2) include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3′-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, propanediol, 1,3-butanediol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, or Scan bisphenols such as bisphenol A, bisphenol F, ethylene oxide bisphenol, bisphenol obtained by adding alkylene oxide such as propylene oxide or the like can also be used. These compounds can be used as one kind or a mixture of two or more kinds. And as a commercial item, the Kuraray polyol C series etc. by a Kuraray company can be used.

  When synthesizing the compound (B) having an isocyanate group, two or more functional groups capable of reacting with the compound (b2) and an isocyanate group having a number average molecular weight of less than 500 are used as long as the stress relaxation property is not impaired. Compound (b4) [hereinafter sometimes referred to as compound (b4). ] May be used in combination.

  Compound (b4) is, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3′-dimethylolheptane, 2-methyl- 1,8-octanediol, 3,3′-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane Diol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecane dimethanol, cyclo Pentadienedimethanol, 1,3 Bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4′-methylenediphenol, 1,1,1- Trimethylolpropane, 1,1,1-trimethylolbutane, 1,1,1-trimethylolpentane, 1,1,1-trimethylolhexane, trimethylolbutene, trimethylolheptene, trimethylolpentene, trimethylolhexene , Trimethylol heptene, trimethylol octene, trimethylol decene, trimethylol dodecene, trimethylol tridecene, trimethylol pentadecene, trimethylol hexadecene, trimetrole heptadecene, trimethylol octadecene, 1,2,6-butane Triol 1,2,4-butanetriol, glycerol, pentaerythritol, dipentaerythritol, sorbitol, xylitol.

  As a manufacturing method of the compound (B) which has an isocyanate group, it can obtain by heating and making a bifunctional isocyanate compound (b1) and a compound (b2) react in nitrogen atmosphere. The reaction temperature is preferably in the range of 60 to 100 ° C., and the reaction time is preferably 6 to 10 hours. When the reaction temperature is lower than 60 ° C. or the reaction time is shorter than 6 hours, the reaction between the bifunctional isocyanate compound (b1) and the compound (b2) may not be completed. In addition, when the reaction temperature is higher than 100 ° C. or the reaction time is longer than 10 hours, side reactions such as allophanate reaction and burette reaction are caused, and the target compound (B) having two isocyanate groups cannot be obtained. There is a case.

  It is important that the pressure-sensitive adhesive of the present invention contains the compound (B) having an isocyanate group at a ratio of 1 to 300 mol of the isocyanate group with respect to 1 mol of the hydroxyl group of the acrylic copolymer (A). More preferably, the compound (B) having an isocyanate group is contained at a ratio of 2 to 200 mol. When the isocyanate group is less than 1 mole per mole of the hydroxyl group, the cohesive force of the adhesive layer is low, and foaming may occur under high temperature conditions. On the other hand, when the isocyanate group exceeds 300 moles, the compatibility between the isocyanate group-containing compound (B) and the acrylic copolymer (A) decreases, and the whitening of the adhesive layer and the cohesive force become excessive. Adhesive strength decreases, and there is a risk of floating, peeling or light leakage.

  If the adhesive of this invention is a grade which does not impair the stress relaxation property of an adhesion layer, crosslinking agents other than the compound (B) which has an isocyanate group can be used together. Trifunctional isocyanate compounds (C) and epoxy compounds, amine compounds, aziridine compounds, carbodiimide compounds, oxazoline compounds, melamine compounds and metal chelate compounds having two or more functional groups in the molecule are preferred. Compound (C) is particularly preferred.

  As the trifunctional isocyanate compound (C), an isocyanate compound other than the compound (B) having an isocyanate group can be used, but the trifunctional isocyanate compound (b1) and the compound (b4) are trifunctional (compounds) (B5)) [hereinafter sometimes referred to as compound (b5). ], A burette body having a burette bond formed by self-condensation of the bifunctional isocyanate compound (b1) via moisture, and a nurate body that is a trimer of the bifunctional isocyanate compound (b1). Etc. are preferably used.

  Compound (b5) is, for example, 1,1,1-trimethylolpropane, 1,1,1-trimethylolbutane, 1,1,1-trimethylolpentane, 1,1,1-trimethylolhexane, trimethylol. Butene, trimethylol heptene, trimethylol pentene, trimethylol hexene, trimethylol heptene, trimethylol octene, trimethylol decene, trimethylol dodecene, trimethylol tridecene, trimethylol pentadecene, trimethylol hexadecene, trimethylol hepta Examples include decene, trimethylol octadecene, 1,2,6-butanetriol, 1,2,4-butanetriol, glycerin, etc. Among them, 1,1,1-trimethylolpropane is preferable.

  Specific examples of the trifunctional isocyanate compound (C) include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, and naphthalene diisocyanate. , Adduct bodies, burette bodies, and nurate bodies of isocyanate monomers such as triphenylmethane triisocyanate and polymethylene polyphenyl isocyanate, etc., taking into consideration the crosslinking speed and compatibility with the acrylic copolymer (A) , Trimethylolpropane adduct of tolylene diisocyanate, trimethylol group of hexamethylene diisocyanate Preferred are pan adducts, trimethylolpropane adducts of isophorone diisocyanate, trimethylolpropane adducts of xylylene diisocyanate, isocyanurates of tolylene diisocyanate, isocyanurates of hexamethylene diisocyanate, isocyanurates of isophorone diisocyanate, xylylene diisocyanate And trimethylolpropane adduct of tolylene diisocyanate are particularly preferred. A trifunctional isocyanate compound (C) may be used independently and may be used in combination of 2 or more type.

  It is preferable to contain a trifunctional isocyanate compound (C) in the ratio from which an isocyanate group becomes 0.5-100 mol with respect to 1 mol of hydroxyl groups of an acryl-type copolymer (A).

  Next, the acrylic copolymer (A) in the present invention will be described. In the present invention, the acrylic copolymer (A) is a copolymer of an ethylenically unsaturated monomer containing a (meth) acrylic acid ester monomer. In the present invention, the (meth) acrylic acid ester monomer means both an acrylic acid ester monomer and a methacrylic acid ester monomer.

  As monomers used for copolymerization, it is preferable to use a hydroxyl group-containing ethylenically unsaturated monomer (a1) and other ethylenically unsaturated monomers (a2). The hydroxyl group-containing ethylenically unsaturated monomer (a1) is preferably used in an amount of 0.005 to 0.25% by weight, more preferably 0.01 to 0.15% by weight, based on all monomers. When the amount used is less than 0.005% by weight, the crosslinking point of the acrylic copolymer (A) is too small, and there is a possibility that the adhesive layer is insufficient in cohesive force or the adhesive layer foams in a high temperature environment.

  For copolymerization, it is preferable not to use a carboxylic acid-containing ethylenically unsaturated monomer. If a carboxyl group is present in the acrylic copolymer (A), the reaction between the compound (B) having an isocyanate group in the adhesive layer and moisture tends to be promoted. For this reason, the reactivity between the isocyanate group of the compound (B) having an isocyanate group and the hydroxyl group of the acrylic copolymer (A) is lowered, which may make it difficult to obtain desired adhesive properties.

  Examples of the hydroxyl group-containing ethylenically unsaturated monomer (a1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid. (Meth) acrylic such as 2-hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate Glycol mono (meth) acrylates such as acid hydroxyalkyl esters, polyethylene glycol mono (meth) acrylates, polypropylene glycol mono (meth) acrylates, 1,4-cyclohexanedimethanol mono (meth) acrylates , Cap Lactone-modified (meth) acrylic acid esters, such as hydroxyethyl acrylamide. These may be used alone or in combination of two or more. Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable.

  Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, phthalic acid monohydroxyethyl acrylate ester, p-carboxybenzyl acrylate ester, ethylene oxide modified (added mole number: 2 to 18) phthalic acid acrylic acid. Ester, monohydroxypropyl acrylate ester, monohydroxyethyl acrylate succinate, β-carboxyethyl acrylate, 2- (4-benzoyl-3-hydroxyphenoxy) ethyl acrylate, maleic acid, monoethylmaleic acid , Itaconic acid, citraconic acid, fumaric acid and the like. These may be used alone or in combination of two or more. The amount used must be such that the reactivity between the isocyanate group of the compound (B) having an isocyanate group and the hydroxyl group of the acrylic copolymer (A) is not impaired, and is preferably 0.2% by weight or less.

  The other ethylenically unsaturated monomer (a2) is a monomer other than the carboxyl group-containing ethylenically unsaturated monomer, and includes an amide bond-containing ethylenically unsaturated monomer, an epoxy group-containing ethylenically unsaturated monomer, and an amino group-containing ethylenically unsaturated monomer. Saturated monomers, (meth) acrylic acid alkyl ester monomers, alkoxy (poly) alkylene oxide (meth) acrylic acid ester monomers, vinyl acetate, vinyl crotonic acid, styrene, acrylonitrile, etc. Absent.

  Examples of the amide bond-containing ethylenically unsaturated monomer include (meth) acrylamide, N-methylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminopropyl (meth) ) Heterocycles such as (meth) acrylamide compounds such as acrylamide, diacetone acrylamide, N- (hydroxymethyl) acrylamide, N- (butoxymethyl) acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, etc. , N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide and the like. These may be used alone or in combination of two or more.

  Examples of the epoxy group-containing ethylenically unsaturated monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 6-methyl (meth) acrylate. Examples include 3,4-epoxycyclohexylmethyl.

  Examples of the amino group-containing ethylenically unsaturated monomer include monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, and monoethylaminopropyl (meth) acrylate. And (meth) acrylic acid monoalkylamino esters.

  Examples of the alkoxy (poly) alkylene oxide (meth) acrylate monomer include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-phenoxyethyl acrylate, methoxypolyethylene glycol (meth) acrylate, and ethoxy. Examples include polyethylene glycol (meth) acrylic acid ester, methoxypolypropylene glycol methacrylic acid ester, ethoxypolypropylene glycol (meth) acrylic acid ester, phenoxypolyethylene glycol methacrylic acid ester, and phenoxypolypropylene glycol methacrylic acid ester.

  Examples of (meth) acrylic acid alkyl ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth ) Hexyl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, ( Examples include hexadecyl (meth) acrylate and octadecyl (meth) acrylate. These may be used alone or in combination of two or more. Among these compounds, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable from the viewpoint that good adhesive performance can be easily obtained.

  The acrylic copolymer (A) can be obtained by copolymerizing an ethylenically unsaturated monomer using a radical polymerization initiator. The copolymerization can be carried out by a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization or the like, but solution polymerization is preferred from the viewpoint of molecular weight control. The solution polymerization is preferably performed in the presence of a solvent such as acetone, methyl acetate, ethyl acetate, toluene, xylene, anisole, methyl ethyl ketone, cyclohexanone, and the like. The radical polymerization temperature is preferably in the range of 60 to 120 ° C., and the polymerization time is preferably 5 to 12 hours.

  The acrylic polymer (A) in the present invention preferably has a weight average molecular weight of 400,000 to 1,500,000. When the weight average molecular weight is less than 400,000, durability under a high-temperature and high-humidity environment is insufficient, and there is a possibility that the substrate may float or peel off. On the other hand, when the weight average molecular weight exceeds 1,500,000, the compatibility between the acrylic copolymer (A) and the compound (B) having an isocyanate group may be lowered.

  In the present invention, the weight average molecular weight is a value in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

  In the present invention, one type of acrylic copolymer (A) may be used, or two or more types may be used in combination.

  The pressure-sensitive adhesive of the present invention preferably contains a silane coupling agent. By using a silane coupling agent, the adhesiveness between the adhesive layer and the adherend is improved, and the heat resistance and heat-and-moisture resistance can be further improved. The amount of the silane coupling agent used is preferably in the range of 0.01 to 1 part by weight, particularly preferably in the range of 0.05 to 0.5 part by weight with respect to 100 parts by weight of the acrylic copolymer (A). .

Examples of the silane coupling agent include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltripropoxysilane, and 3- (meth). An alkoxysilane compound having a (meth) acryloxy group such as acryloxypropyltributoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane;
Alkoxysilane compounds having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane;
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltripropoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) Alkoxysilane compounds having an amino group, such as -3-aminopropylmethyldiethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane;
Alkoxysilane compounds having a mercapto group such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane;
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltripropoxysilane, 3-glycidoxypropyltributoxysilane, 3-glycidoxypropylmethyldimethoxysilane, Alkoxysilane compounds having an epoxy group such as 3-glycidoxypropylmethyldiethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane;
Tetraalkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane;
3-chloropropyltrimethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, styryltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, 1,3,5-tris (3-trimethoxysilylpropyl) isocyanurate, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyl Examples include triethoxysilane, hexamethyldisilazane, and a silicone resin having an alkoxysilyl group in the molecule (X-41-1056, manufactured by Shin-Etsu Chemical Co., Ltd., X-41-1810, manufactured by Shin-Etsu Chemical Co., Ltd.).

  The pressure-sensitive adhesive of the present invention preferably contains a tin catalyst in order to promote the crosslinking reaction of the compound (B) having a hydroxyl group and an isocyanate group of the acrylic copolymer (A).

  As the tin catalyst, known tin catalysts such as dibutyltin dilaurate and dioctyltin dilaurate can be used.

  In the pressure-sensitive adhesive of the present invention, various resins, oils, softeners, dyes, pigments, antioxidants, ultraviolet absorbers, weathering stabilizers, tackifiers, plasticizers, as long as the effects of the present invention are not impaired. You may mix | blend a filler, anti-aging agent, an antistatic agent, etc.

  In the present invention, the pressure-sensitive adhesive film has a base material and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive of the present invention. The pressure-sensitive adhesive film can be produced, for example, by applying a pressure-sensitive adhesive on a substrate and drying it. The adhesive layer should just be provided in the at least one surface of the base material.

  When applying the adhesive, an appropriate liquid medium, for example, a hydrocarbon solvent such as toluene, xylene, hexane, heptane; an ester solvent such as ethyl acetate or butyl acetate; a ketone solvent such as acetone or methyl ethyl ketone; dichloromethane , Halogenated hydrocarbon solvents such as chloroform; ether solvents such as diethyl ether, methoxytoluene, dioxane, and other organic solvents such as hydrocarbon solvents can be added to adjust the viscosity and pressure-sensitive adhesive The viscosity can also be reduced by heating. However, since water, alcohol, etc. may cause reaction inhibition with an acrylic copolymer (A) and the compound (B) which has two isocyanate groups, it is preferable not to use it.

  Examples of the substrate include cellophane, plastic sheet, rubber, foam, cloth, rubber cloth, resin-impregnated cloth, glass plate, wood and the like, and may be plate-like or film-like. Among these, when used for a liquid crystal display device, the substrate is preferably a film. Furthermore, the base material can be used alone, or a base material in a multilayer state formed by laminating a plurality of base materials can be used. Furthermore, what carried out the peeling process of the surface of a base material (henceforth a peeling sheet) can also be used.

  The plastic sheet is also called a plastic film. Polyvinyl alcohol film, triacetyl cellulose film, polypropylene, polyethylene, polycycloolefin, polyolefin resin film such as ethylene-vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate, polyethylene Polyester resin film such as naphthalate, polycarbonate resin film, polynorbornene resin film, polyarylate resin film, acrylic resin film, polyphenylene sulfide resin film, polystyrene resin film, vinyl resin Film, polyamide resin film, polyimide resin film, epoxy resin film, etc. It is.

  In the present invention, the method of applying the adhesive is not particularly limited, and may be a Mayer bar, applicator, brush, spray, roller, gravure coater, die coater, lip coater, comma coater, knife coater, reverse coater, spin coater, etc. Can be mentioned. There is no restriction | limiting in particular in a drying method, The thing using hot air drying, infrared rays, and the pressure reduction method is mentioned. As drying conditions, although depending on the cured form of the pressure-sensitive adhesive, the film thickness, and the selected solvent, heating with hot air at about 60 to 180 ° C. is usually sufficient.

  The pressure-sensitive adhesive film of the present invention can be obtained by: (a) applying a pressure-sensitive adhesive to the release-treated surface of the release-treated sheet, drying it, and laminating a sheet-like optical member on the surface of the adhesive layer; It can be obtained by applying a pressure-sensitive adhesive to the optical member, drying it, and laminating the release-treated surface of the release-treated sheet on the surface of the adhesive layer.

  0.1-200 micrometers is preferable and, as for the thickness of the adhesion layer, 1-100 micrometers is more preferable. When the thickness is less than 0.1 μm, sufficient adhesive strength may not be obtained, and even when the thickness exceeds 200 μm, characteristics such as adhesive strength are often not improved further.

  Furthermore, the adhesive film of the present invention preferably has an adhesive force of 2 to 15 N / 25 mm after 1 day at 23 ° C., more preferably 3 to 10 N / 25 mm, after being bonded to non-alkali glass. If the adhesive strength is less than 2 N / 25 mm, the adhesive strength is insufficient as an adhesive, and there is a risk of floating or peeling. When the adhesive strength is 2 N / 25 mm or more, the adhesive strength is sufficient as an adhesive, and it can be sufficiently fixed to an adherend. Moreover, when this adhesive force is larger than 15 N / 25 mm, there exists a possibility of destroying a to-be-adhered body when it peels again after bonding an adhesive film to an to-be-adhered body.

  In the present invention, the gel fraction of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film is preferably 40 to 90% by weight, particularly preferably 50 to 80% by weight. When the gel fraction is less than 40% by weight, sufficient cohesive force may not be obtained, and when it is 90% by weight or more, the stress relaxation property is lowered and light leakage occurs. In addition, the gel fraction as used in the field of this invention is the numerical value which computed the weight of the adhesive tape by following formula (2), after carrying out reflux extraction of the adhesive tape in ethyl acetate for 5 hours.

Formula (2) Gel fraction (% by weight) = (M2 / M1) × 100
M1: Weight of the adhesive layer before extraction with ethyl acetate
M2: Weight of the adhesive layer after extraction and drying with ethyl acetate

  The pressure-sensitive adhesive of the present invention can be suitably used for laminating optical members. That is, in the pressure-sensitive adhesive film of the present invention, an optical member can be preferably used as a substrate. Specific examples of the optical member include a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, and a brightness enhancement film. A release sheet can be laminated on the other surface of the adhesive layer. In addition, a polarizing film may be called a polarizing plate.

  By peeling off the release sheet covering the surface of the pressure-sensitive adhesive layer from the pressure-sensitive adhesive film thus obtained, for example, by sticking the pressure-sensitive adhesive layer to a glass member for a liquid crystal cell, “sheet-like optical member / pressure-sensitive adhesive layer / liquid crystal A liquid crystal cell member having a configuration of “cell glass member” can be obtained. In the present invention, when the optical member is a polarizing plate, it is particularly useful, and an adhesive film that does not float or peel off can be obtained by heat treatment and high-humidity treatment.

  As described above, the polarizing plate may be composed of a polarizing film alone, but a polarizing film and a viewing angle widening film are preferably integrated. In this case, the thickness of the adhesive layer is usually about 5 to 100 μm, preferably 10 to 50 μm.

  The pressure-sensitive adhesive of the present invention is suitable as a pressure-sensitive adhesive for optical members, as well as general labels and seals, paints, elastic wall materials, waterproof coating materials, flooring materials, tackifiers, pressure-sensitive adhesives, and pressure-sensitive adhesives for laminated structures. Agent, sealing agent, molding material, coating agent for surface modification, binder (magnetic recording medium, ink binder, casting binder, fired brick binder, graft material, microcapsule, glass fiber sizing, etc.), urethane foam (rigid, semi-rigid) , Soft), urethane RIM, UV / EB curable resin, high solid paint, thermosetting elastomer, microcellular, textile processing agent, plasticizer, sound absorbing material, vibration damping material, surfactant, gel coat agent, resin for artificial marble , Impact resistance agent for artificial marble, resin for ink, film (laminate adhesive, protective film, etc.), for laminated glass Fat, reactive diluent, various molding materials, elastic fiber, artificial leather, as a raw material for synthetic leather, can also very effectively used as various resin additives and a raw material thereof or the like.

  Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

[Synthesis of acrylic polymer (A)]
(Synthesis Example 1-1)
In a polymerization reactor equipped with a polymerization tank, a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 69.9 parts of butyl acrylate, 30 parts of ethyl acrylate, 0.1 part of 2-hydroxyethyl acrylate 100 parts of ethyl acetate was charged. The reaction vessel was heated to 85 ° C. with stirring, 0.02 part of 2,2′-azobisisobutyronitrile was added and reacted for 2 hours. Further, 0.02 part of 2,2′-azobisisobutyronitrile was added and reacted for 6 hours. After completion of the reaction, the reaction vessel was cooled and 110 parts of ethyl acetate was added to obtain an acrylic copolymer solution.

(Synthesis Examples 1-2 to 1-7)
Various raw materials were charged according to the weight ratios in Table 1, and an acrylic copolymer was synthesized in the same manner as in Synthesis Example 1.

(Synthesis Example 1-8)
In a reaction vessel of a reactor equipped with a reaction vessel, a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 69.9 parts of butyl acrylate, 30 parts of ethyl acrylate, 0.1 part of 2-hydroxyethyl acrylate, 30 parts of ethyl acetate and 70 parts of methyl acetate were charged. The reaction vessel was heated to 75 ° C. with stirring, 0.02 part of 2,2′-azobisisobutyronitrile was added and reacted for 2 hours. Further, 0.02 part of 2,2′-azobisisobutyronitrile and 30 parts of ethyl acetate were added and reacted for 6 hours. After completion of the reaction, the reaction vessel was cooled and 130 parts of ethyl acetate was added to obtain an acrylic copolymer solution.

  For the acrylic polymer solutions obtained in Synthesis Examples 1-1 to 1-8, the weight average molecular weight (Mw) was determined according to the following method. The results are shown in Table 1.

<Measurement of weight average molecular weight (Mw)>
For measurement of Mw and Mn, GPC (gel permeation chromatography) “HPC-8020” manufactured by Tosoh Corporation was used. GPC is liquid chromatography in which a substance dissolved in a solvent (THF; tetrahydrofuran) is separated and quantified by the difference in molecular size, and the weight average molecular weight (Mw) is determined in terms of polystyrene.

［イソシアネート基を有する化合物（Ｂ）の合成］
（合成例２−１）
反応槽、攪拌機、温度計、還流冷却器、窒素導入管を備えた反応装置の反応槽に、コロネート２７７０（ヘキサメチレンジイソシアネートのアロファネート体でイソシアネート基を２個有する、ＮＣＯ価＝１９．４、不揮発分＝１００％、日本ポリウレタン工業社製）１００部、ＰＰ−１０００（ポリプロピレングリコール、ＯＨ価＝１１２、三洋化成工業社製）を仕込んだ。この重合槽を攪拌しながら８０℃に加熱し、更に８時間反応させた。反応溶液のＮＣＯ価を測定し、ＮＣＯ価を確認して反応を終了した。このイソシアネート化合物は淡黄色透明な粘稠の液体であった。その結果を表２に示す。

[Synthesis of Compound (B) Having Isocyanate Group]
(Synthesis Example 2-1)
Coronate 2770 (hexamethylene diisocyanate allophanate having two isocyanate groups, NCO value = 19.4, non-volatile) in a reaction vessel equipped with a reaction vessel, a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube Min = 100%, manufactured by Nippon Polyurethane Industry Co., Ltd.) 100 parts, PP-1000 (polypropylene glycol, OH number = 112, manufactured by Sanyo Chemical Industries Co., Ltd.) were charged. The polymerization tank was heated to 80 ° C. with stirring and further reacted for 8 hours. The NCO value of the reaction solution was measured, and the reaction was completed after confirming the NCO value. This isocyanate compound was a pale yellow transparent viscous liquid. The results are shown in Table 2.

(Synthesis Examples 2-2 to 2-10)
Various raw materials were charged according to the weight ratio in Table 2, and a compound (B) having an isocyanate group was synthesized in the same manner as in Synthesis Example 2-1. The results are shown in Table 2.

  In addition, the NCO value of the compound (B) having an isocyanate group obtained in Synthesis Examples 2-1 to 2-10 was determined by the method shown below.

[NCO value of compound (B) having two isocyanate groups]
Precisely weigh the sample in a stoppered Erlenmeyer flask and add 25 ml of chlorobenzene and 10 ml of a mixture of di-n-butylamine / orthodichlorobenzene (weight ratio: di-n-butylamine / orthodichlorobenzene = 1 / 24.8). Dissolve. To this, 80 g of methanol and bromophenol blue reagent were added as indicators and titrated with a 0.1N alcoholic hydrochloric acid solution. Titration was continued until the solution was yellowish green and held for 30 seconds. The NCO value was determined by the following formula.

NCO value (%) = [0.42 × (BC) × F] / W
However, W: Sample collection amount (g)
B: Consumption of 0.1N alcoholic hydrochloric acid solution required for sample titration (ml)
C: Consumption of 0.1N alcoholic hydrochloric acid solution required for titration of blank test (ml)
F: Potency of 0.1N alcoholic hydrochloric acid solution

Example 1
To 100 parts of the acrylic copolymer in the acrylic copolymer solution obtained in Synthesis Example 1-1, 3 parts of the compound having an isocyanate group of Synthesis Example 2-1 is blended, and ethyl acetate is used as a solvent. Was added to adjust the nonvolatile content to 25% to obtain an adhesive.

  The pressure-sensitive adhesive was applied on a release layer of a release sheet made of polyethylene terephthalate having a thickness of 38 μm and dried to a thickness of 25 μm, and then dried at 100 ° C. for 2 minutes for adhesion. A layer was formed. Next, one surface of a polarizing film having a multilayer structure in which both surfaces of a polyvinyl alcohol (PVA) polarizer are sandwiched between triacetyl cellulose-based protective films (hereinafter referred to as “TAC film”) is bonded to this adhesive layer. An adhesive film having a configuration of “/ adhesive layer / TAC film / PVA / TAC film” was obtained. Subsequently, the obtained adhesive film was aged for one week under the conditions of a temperature of 35 ° C. and a relative humidity of 55%, to obtain an adhesive film in which the adhesive layer was covered with a release film.

(Examples 2 to 23, Comparative Examples 1 to 5)
According to the weight ratios in Table 3 and Table 4, pressure-sensitive adhesives were obtained in the same manner as in Example 1. Further, an adhesive film in which the adhesive layer was coated with a release film was obtained in the same manner as in Example 1.

  The adhesive films obtained in Examples 1 to 23 and Comparative Examples 1 to 5 were evaluated by the following methods. The results are shown in Tables 5 and 6.

(1) Adhesive strength The adhesive film is cut to a size of 25 mm width and 150 mm length, the release sheet is peeled off (adhesion layer thickness is 25 μm), and a laminator is used for alkali-free glass [Corning “1737”]. Stuck. Subsequently, it was kept in an autoclave at 50 ° C. and 5 atm for 20 minutes and adhered to a glass plate. After that, it was allowed to stand for 1 day in an environment of 23 ° C. and a relative humidity of 50%. Using a tensile tester, the adhesive force was measured under the conditions of a peeling speed of 300 mm / min and a peeling angle of 180 °, and the evaluation was performed based on the following three evaluation criteria.
○: “Adhesive strength is 3 to 10 N / 25 mm and there is no practical problem”
Δ: “Adhesive strength is 2 to 3 N / 25 mm or 10 to 15 N / 25 mm.
No problem in practice "
X: “Adhesive strength is outside the range of 2 to 15 N / 25 mm, impractical”

(2) Coating film appearance The appearance of the adhesive layer was visually evaluated. The appearance of the adhesive layer was evaluated based on the following two-stage evaluation criteria.
○: “The coating is transparent and has no practical problems”
×: “The coating film is whitened and cannot be used practically”

(3) Heat resistance and heat-and-moisture resistance The adhesive film was cut into 160 mm width and 120 mm length, the release sheet was peeled off, and it was attached to non-alkali glass using a laminator. Subsequently, the glass plate to which the adhesive film was attached was held in an autoclave at 50 ° C. and 5 atm for 20 minutes to adhere to the glass plate to obtain a laminate of the adhesive film and the glass plate.
As an evaluation of heat resistance, foaming, floating, and peeling after the laminate was allowed to stand at 85 ° C. for 500 hours were visually observed. In addition, as an evaluation of heat and moisture resistance, foaming, floating, and peeling were observed visually after the laminate was left at 60 ° C. and a relative humidity of 95% for 500 hours. The heat resistance and heat-and-moisture resistance were evaluated based on the following three-stage evaluation criteria.
A: “No foaming, floating or peeling is observed, and there is no problem in practical use”
○: “Both foaming, floating and peeling of 0.5 mm or less are observed.
No problem in practice "
×: “There is foaming, floating and peeling on the whole surface, which is not practical”

(4) Light leakage (white spots)
The adhesive film was cut into 160 mm width and 120 mm length, and the release sheet was peeled off, and pasted using a laminator so that the absorption axes of the polarizing plates of the two adhesive films were orthogonal to both surfaces of the alkali-free glass. Subsequently, the glass plate to which the adhesive film was attached was held in an autoclave at 50 ° C. and 5 atm for 20 minutes to adhere to the glass plate to obtain a laminate of the adhesive film and the glass plate.
After this laminate was left at 85 ° C. for 500 hours, light leakage (white spots) when light was transmitted through the polarizing plate was visually observed. The light leakage was evaluated based on the following four evaluation criteria.
A: “No whitening is observed and there is no practical problem at all”
○: “Slight whitening is recognized, but there is no practical problem”
Δ: “White spots are recognized, but there is no practical problem”
×: “There is whitening on the entire surface and is not practical”

(5) Removability (reworkability)
The pressure-sensitive adhesive film was cut to a size of 25 mm wide and 150 mm long, the release sheet was peeled off, and attached to non-alkali glass using a laminator. Subsequently, it was held in an autoclave at 50 ° C. and 5 atm for 20 minutes to be in close contact with the glass plate. After leaving this test piece at 85 ° C. for 3 hours, a 180 ° peel test is performed in a 23 ° C. and 50% relative humidity environment using a tensile tester to peel it off at a rate of 300 mm / min in the direction of 180 °. Then, the fogging of the glass surface after peeling was visually observed and evaluated based on the following two-stage evaluation criteria.
○: “No glue residue or cloudiness is observed and there is no practical problem”
×: “Adhesive residue, cloudiness is recognized and impractical”

From the results of Tables 5 and 6, as shown in Examples 1 to 23, it can be seen that the pressure-sensitive adhesive of the present invention is excellent in coating film appearance, heat resistance, moist heat resistance, removability, and light leakage. On the other hand, in Comparative Examples 1-5, since one of the items is defective, it turns out that there is a problem in practical use or impracticality.
The pressure-sensitive adhesive of the present invention has excellent properties such as heat resistance, moist heat resistance, optical properties, and removability required for optical films. In particular, in the use of optical films, light leakage, which is an optical property, is regarded as important, and the required performance has become increasingly severe with the recent increase in size of displays. Therefore, the pressure-sensitive adhesive of the present invention is particularly useful because it can exhibit pressure-sensitive adhesive properties that have been difficult so far as described above.

Claims (5)

A substrate, and an adhesive layer;
The substrate is an optical member;
The pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive containing an acrylic copolymer (A) and a compound (B) having an isocyanate group ,
The compound (B) having an isocyanate group is obtained by reacting a bifunctional isocyanate compound (b1) with a compound (b2) having a number average molecular weight of 500 to 5000 having two or more functional groups capable of reacting with the isocyanate group. Adhesive film characterized by The pressure-sensitive adhesive film according to claim 1, wherein the compound (b2) is a polyol (b3). The acrylic copolymer (A) is a copolymer of a hydroxyl group-containing ethylenically unsaturated monomer (a1) 0.005 to 0.25% by weight and another ethylenically unsaturated monomer (a2). ,
3. The compound (B) having an isocyanate group is contained at a ratio of 1 to 300 mol of the isocyanate group with respect to 1 mol of the hydroxyl group of the acrylic copolymer (A). Adhesive film . The pressure-sensitive adhesive film according to claim 1 , wherein the pressure-sensitive adhesive further contains a trifunctional isocyanate compound (C) other than the compound (B) having an isocyanate group. Adhesive film of the optical member, according to any one of claims 1 to 4 is a polarizing plate.