JP2007138057A - Adhesive composition for optical film and adhesive sheet, and optical member using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition for optical films, which can well maintain durability and a light leackage-preventing property, and can simultaneously prevent staining on repealing, and peeling under severe conditions. <P>SOLUTION: This adhesive composition for optical films is characterized by comprising (A) an acrylic polymer prepared by copolymerizing at least components (a1), (a2), (a3) and (a4) and having a weight-average mol.wt. of 800,000 to 1,600,000 and a weight-average mol.wt./number-average mol.wt. ratio (Mw/Mn) of 10 to 50, (B) an isocyanate-based cross-linking agent, (C) a silane coupling agent, and (D) a cross-linking accelerator. Therein, (a1) an alkyl (meth)acrylate and/or an alkyl (meth)acrylate, (a2) an aromatic ring-containing monomer, and (a3) a hydroxyl group-containing monomer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a pressure-sensitive adhesive composition, and more specifically, a pressure-sensitive adhesive composition that is excellent in reworkability while achieving both durability and light leakage prevention properties and is advantageously used as a pressure-sensitive adhesive for optical films and the like. It is about things.

  The adhesive for optical films has durability to prevent foaming, floating, peeling, etc. of the optical film even in a high temperature and high humidity atmosphere when the optical member is bonded to the adherend, For example, when the optical film is a polarizing film, the two polarizing films adhere to each other with a pressure-sensitive adhesive at right angles and are left under high temperature and high humidity. There is a need for light leakage prevention to prevent leakage. In addition, even when the optical film is adhered to an adherend such as a liquid crystal panel, the optical member (having an adhesive on the optical film) can be used without contaminating the adherend even if the position is shifted. There is also a demand for reworkability for re-peeling from the adherend.

  As such an adhesive for optical films, an acrylic adhesive has been mainly used conventionally. And what satisfy | fills the said request | requirement is known the acrylic adhesive which blended and bridge | crosslinked the high molecular weight acrylic polymer and the low molecular weight body. This improves cohesion by cross-linking high molecular weight acrylic polymers, provides durability that prevents floating and peeling, and does not cause light leakage by containing medium to low molecular weight substances. It is to make.

  However, with the recent increase in size of displays, light leakage due to dimensional changes of optical films, particularly polarizing films, in a high temperature atmosphere becomes a bigger problem, and the adhesive for optical films has more flexibility. It is getting demanded. Further, under severe conditions, there is a problem that the low molecular weight substance added for improving the light leakage prevention property bleeds, contaminates the adherend during re-peeling, and causes peeling.

  For example, in order to improve the heat durability and stress relaxation properties, a technique is disclosed in which the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 4 or more (patent document) 1). However, if Mw / Mn is merely 4 or more, the stress relaxation required for a large display is insufficient.

  In addition, as this (meth) acrylic polymer, a mixture having a weight average molecular weight of 200,000 or more and less than 200,000 is used to improve adhesion to plastics under high temperature and high humidity. Although it is also known (Patent Document 2), in this method, a component having a small weight average molecular weight bleeds to the surface, and problems such as contamination during re-peeling and peeling under harsh use environments cannot be solved. It was.

  In addition, it is known to use a polymer obtained by copolymerizing an aromatic-containing monomer as an adhesive for optical films (Patent Document 3 and Patent Document 4). However, these pressure-sensitive adhesives adjust the refractive index of the pressure-sensitive adhesive in order to suppress interfacial reflection between optical members such as polarizing plates and retardation plates, and pressure-sensitive adhesives, and between pressure-sensitive adhesives and adherends. It was intended to do. Moreover, since it was designed to show strong adhesiveness immediately after pasting, there was a problem that it was inferior in performance (reworkability) in which it could be pasted again even if a pasting mistake was made.

Moreover, it is known to use a high molecular weight polymer having an alicyclic monomer or an aromatic-containing monomer as a copolymerization component as a low-polarity film pressure-sensitive adhesive (Patent Document 5). However, this pressure-sensitive adhesive is designed to have a relatively small value (Mw / Mn) obtained by dividing the weight average molecular weight of the copolymer by the number average molecular weight. Further, there is a problem that the stress due to dimensional change of the polarizing film or the like cannot be alleviated and sufficient light leakage prevention property cannot be obtained. Furthermore, even when the alicyclic monomer was copolymerized, the light leakage prevention property was insufficient.
JP 2002-341141 A JP 2002-107507 A JP 2002-173656 A Japanese Patent Laid-Open No. 2003-13029 JP 2005-053976 A

  The present invention has been made in view of such a technical background, in particular, the stress due to dimensional changes of members such as a polarizing film, a retardation film, and an elliptically polarizing film having a large pasting area, Providing an acrylic pressure-sensitive adhesive composition for optical films that not only prevents peeling and foaming under high-humidity heat conditions but also suppresses color unevenness due to light leakage, and an optical member using the pressure-sensitive adhesive composition The issue is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have a weight average molecular weight of 800,000 to 1,600,000 having an aromatic-containing monomer as a copolymerization component, and the weight average molecular weight of the copolymer is a number average. The inventors have found that the above problem can be solved by selecting and using a specific (meth) acrylic polymer having a value (Mw / Mn) divided by molecular weight (Mw / Mn) of 10 to 50, and have reached the present invention.

That is, the present invention includes the following components (A), (B), (C) and (D):
(A) The weight average molecular weight obtained by copolymerizing at least the following components (a1), (a2) and (a3) is 800,000 to 1,600,000, and the weight average molecular weight of the copolymer is divided by the number average molecular weight. An acrylic polymer having a value (Mw / Mn) of 10 to 50; (a1) (meth) acrylic acid alkyl ester and / or (meth) acrylic acid alkoxyalkyl ester 5 to 89.5% by weight,
(A2) 10 to 85% by weight of aromatic ring-containing monomer, (a3) 0.5 to 10% by weight of hydroxyl group-containing monomer, and (B) 0.005 to 5 parts by weight of isocyanate-based crosslinking agent with respect to 100 parts by weight of acrylic polymer. (C) 0.05 to 1.0 parts by weight of the silane coupling agent with respect to 100 parts by weight of the acrylic polymer (D) 0.001 to 0.5 parts by weight of the crosslinking accelerator with respect to 100 parts by weight of the acrylic polymer, The adhesive composition for optical films containing this is provided.
Moreover, the adhesive sheet which provided the adhesive layer obtained from the said adhesive composition on the at least single side | surface on a support body is provided.
Furthermore, the optical member which provided the adhesive layer obtained from the said adhesive composition on the at least single side | surface of an optical film is provided.

According to the present invention, while maintaining both durability and light leakage prevention, there is no bleeding of low molecular weight components, contamination during re-peeling, suppression of peeling under harsh conditions, and excellent reworkability An agent composition can be provided.
An optical member in which a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive for optical members of the present invention is formed on a polarizing film, a retardation film, or an elliptical polarizing film, the pressure-sensitive adhesive layer sufficiently relieves thermal stress when attached to a glass substrate or the like Therefore, light leakage does not occur.

  The pressure-sensitive adhesive composition for an optical film of the present invention comprises an acrylic polymer (component (A)), a crosslinking agent (component (B)), a silane coupling agent (component (C)) and a crosslinking accelerator (component (D). ).

  The (meth) acrylic acid alkyl ester and (meth) acrylic acid alkoxyalkyl ester (component (a1)), which are one of the copolymer components constituting the component (A) of the acrylic polymer, have a chain alkyl group. It is a (meth) acrylic acid ester having an aromatic ring in its structure.

Among these, preferable examples of the (meth) acrylic acid alkyl ester include those having an alkyl group having 1 to 12 carbon atoms which may be branched. Specifically, methyl (meth) acrylate, ethyl (meta) ) Acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) ) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate. (Meth) acrylic acid means both acrylic acid and methacrylic acid, and (meth) acrylate means both acrylate and methacrylate.

  Moreover, as a preferable example of (meth) acrylic-acid alkoxyalkyl ester, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, etc. can be mentioned.

  The aromatic ring-containing monomer (component (a2)), which is another essential copolymerization component of component (A), is a copolymerizable compound containing an aromatic group in its structure. Examples of the monomer mixture component (a2) aromatic ring-containing monomer include phenyl acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide-modified nonylphenol (meth) acrylate, Examples thereof include hydroxyethylated β-naphthol acrylate, biphenyl (meth) acrylate, styrene, vinyl toluene, α-methyl styrene and the like.

  Examples of the monomer (component (a3)) having a hydroxyl group in the molecule which is another essential copolymerization component of component (A) include 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate. , 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, chloro-2-hydroxypropyl acrylate, diethylene glycol Examples thereof include mono (meth) acrylate and allyl alcohol.

  The compounding quantity of the monomer mixture of the component (A) of the adhesive composition for optical films of this invention is component (a1) (meth) acrylic-acid alkylester and / or (meth) acrylic-acid alkoxyalkylester 5-89. 0.5% by weight, (a2) 10-85% by weight of aromatic ring-containing monomer, and component (a3) 1-10% by weight, preferably 23-69% by weight of component (a1), (a2) containing aromatic ring They are 30 to 70% by weight of monomer and 1 to 7% by weight of component (a3).

  If the amount of the component (a2) aromatic ring-containing monomer deviates and is small, light leakage may not be sufficiently prevented, and if it deviates too much, the reworkability may be deteriorated. Further, if the amount of the component (a3) deviates and is small, the durability performance level may be lowered, and if it is too much, the durability performance and light leakage prevention property cannot be balanced.

  The monomer mixture may be mixed with other monomers as necessary. Examples of other monomers include epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate; acetoacetyl group-containing (meth) acrylates such as acetoacetoxyethyl (meth) acrylate; vinyl acetate, vinyl chloride and ( And (meth) acrylonitrile. The mixing ratio of other monomers can be included at a ratio of 0 to 10% by weight.

  The acrylic polymer used for the pressure-sensitive adhesive for optical members of the present invention can be produced by a conventionally known polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method and a suspension polymerization method. What was manufactured by the solution polymerization method and bulk polymerization method which do not contain polymerization stabilizers, such as a suspension agent, is preferable. Moreover, the weight average molecular weight (Mw) by the gel permeation chromatography (GPC) of the said acrylic polymer is 800,000-1,600,000, Preferably it is 800,000-1,500,000. If the Mw is less than 800,000, the cohesive strength of the pressure-sensitive adhesive is not sufficient even when the curing agent is blended in a suitable range, and foaming tends to occur under high temperature conditions, exceeding 1.6 million. When the adhesive is used for bonding a glass substrate and a polarizing plate, for example, a light leakage phenomenon is likely to occur at the peripheral edge of the bonding surface.

  Further, the acrylic polymer must have a weight average molecular weight to number average molecular weight (Mn) ratio (Mw / Mn) of 10 to 50, a broad molecular weight distribution, and a low tensile elastic modulus. It is. This low tensile elastic modulus provides good stress relaxation properties and effectively prevents display unevenness. From this viewpoint, the ratio (Mw / Mn) is preferably 20 to 50. In the present invention, when the molecular weight distribution is in an appropriate range, and an appropriate amount of the aromatic ring-containing monomer is copolymerized, the light leakage prevention property is remarkably improved by a synergistic effect. The reason for this is that, in addition to the broadening of the molecular weight distribution and the copolymerization of the aromatic ring-containing monomer, the stress relaxation to the film during heat shrinkage is improved. It is considered that the light leakage prevention property is remarkably improved by reducing the birefringence. However, if the ratio (Mw / Mn) becomes too large, the amount of low molecular weight polymer increases and foaming is likely to occur. If the ratio (Mw / Mn) becomes too small, the stress relaxation property decreases, and affixing Light leakage is likely to occur when the area is large.

  The pressure-sensitive adhesive composition for an optical film of the present invention comprises 100 parts by weight of the acrylic polymer of component (A), 0.005 to 5 parts by weight of the isocyanate compound of component (B), and a silane coupling agent of 0. It consists of 05 to 1.0 part by weight and a component (D) crosslinking accelerator.

  Examples of isocyanate compounds that can be used in the optical film pressure-sensitive adhesive composition of the present invention include tolylene diisocyanate, chlorophenylene diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, diphenylmethane. Isocyanate monomers such as diisocyanate, hydrogenated diphenylmethane diisocyanate, and isocyanate compounds obtained by adding these isocyanate monomers with trimethylolpropane, isocyanurates, burette-type compounds, polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, Urethane prepolymer type such as polyisoprene polyol Or the like can be mentioned isocyanate.

  Examples of silane coupling agents that can be used in the optical film pressure-sensitive adhesive composition of the present invention include polymerizable unsaturated group-containing silicon compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane, and 3-glycol. Silicon compounds having an epoxy structure such as sidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- Examples include amino group-containing silicon compounds such as (2-aminoethyl) 3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3aminopropylmethyldimethoxysilane, and 3-chloropropyltrimethoxysilane.

  As the component (C), those having an isocyanate group, a carboxyl group or an amino group are particularly preferred.

  When using a component (C), it is 0.05-1.0 weight part with respect to 100 weight part of component (A), Preferably it is set as the range of 0.05-0.6 weight part. If the content of these silane coupling agents is too small, the effect of preventing peeling cannot be exhibited. If the content is too large, bleeding may occur, causing peeling or milling.

  The component (D) will be described. Generally, the crosslinking reaction between the hydroxyl group and the isocyanate compound may not require a catalyst. However, the aromatic ring-containing monomer copolymerized as an essential component in the present invention is bulky. When a crosslinking reaction promoting catalyst such as an amino group is not present in the polymer, a long time is required for the crosslinking reaction to proceed. In order to solve this, a crosslinking accelerator is used in the present invention.

  Examples of this crosslinking accelerator include amino compounds such as N, N, N ′, N′-tetramethylhexanediamine, triethylamine, imidazole; cobalt naphthenate, dibutyltin diacetate, dibutyltin diacetylacetonate, tetra- There may be mentioned organometallic compounds such as n-butyltin, trimethyltin hydroxide, dibutyltin dilaurate and the like. When such a crosslinking accelerator is used, the crosslinking accelerator is usually 0.001 to 0.5 parts by weight, preferably 0.001 to 0.3 parts by weight with respect to 100 parts by weight of the acrylic polymer. Used in quantity.

  If the amount of crosslinking accelerator deviates and is small, a long aging time may be required, or peeling or foaming may occur under high temperature or high humidity heat conditions. When it is large, the light leakage prevention property may not be sufficient. In addition, contamination may remain at the time of bleed-out and re-peeling.

  When the acrylic polymer is prepared by solution polymerization, the isocyanate compound and the silane coupling agent are added to the acrylic polymer solution after the polymerization is completed. In the case where the acrylic polymer is prepared by bulk polymerization, it is difficult to uniformly mix after completion of the polymerization.

  The pressure-sensitive adhesive composition for optical films of the present invention may contain an antioxidant, an ultraviolet absorber, a tackifier, a plasticizer, and the like as long as the effects of the present invention are not impaired.

The pressure-sensitive adhesive sheet for optical members of the present invention is a sheet in which a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition for optical films is provided on one side or both sides of a support. What is necessary is just to provide an adhesive layer by a conventionally well-known method.

  Moreover, the optical member of this invention provides the adhesive layer obtained from the said adhesive composition on the at least single side | surface of an optical film. Examples of the optical film include a polarizing film, a retardation film, an elliptically polarizing film, an antireflection film, a brightness enhancement film, a light diffusion film, a glass scattering prevention and a surface protection film, and the like. When a phase difference film or an elliptically polarizing film is used, the stress relaxation property of the optical film adhesive can be more exhibited.

  EXAMPLES Next, although an Example is given and this invention is further demonstrated, this invention is not limited to these Examples.

Production Examples 1-3, 7-15, 19-20, 23
Copolymerizability of parts by weight shown in Table 1 (hereinafter sometimes abbreviated as “parts” in Examples or Tables) in a reactor equipped with a stirrer, reflux condenser, thermometer and nitrogen introduction tube Monomer and ethyl acetate were charged, 0.2 parts of azobisisobutyronitrile (Otsuka Chemical Co., Ltd.) (hereinafter abbreviated as “AIBN”) was added, and the air in the reaction vessel was replaced with nitrogen gas. Next, the mixture was heated to 60 ° C. with stirring in a nitrogen atmosphere, and then reacted for 1.5 hours. Thereafter, while 50 parts of ethyl acetate was added dropwise over 50 minutes, after 30 minutes from the start of addition, perhexyl PV (manufactured by NOF Corporation) (hereinafter abbreviated as “PHPV”) 0 .2 parts were added and the temperature was raised to 80 ° C. and reacted for 20 minutes. Next, 0.3 part of PHPV was added and reacted for 40 minutes, and 1.0 part of PHPV was further added and reacted for 3 hours. After completion of the reaction, the reaction mixture was diluted with ethyl acetate to obtain a (meth) acrylic polymer solution.

Production Example 4
In Production Example 1, a (meth) acrylic polymer solution was obtained in the same manner except that 50 parts of dripped ethyl acetate was changed to 65 parts.

Production Example 5
A (meth) acrylic polymer solution was obtained in the same manner as in Production Example 1 except that 50 parts of dripped ethyl acetate was changed to 80 parts.

Production Example 6
In Production Example 1, a (meth) acrylic polymer solution was obtained in the same manner except that 50 parts of dripped ethyl acetate was changed to 95 parts.

Production Example 16
In Production Example 1, a (meth) acrylic polymer solution was obtained in the same manner except that 50 parts of dripped ethyl acetate was changed to 110 parts.

Production Examples 17 and 18
In Production Example 1, a (meth) acrylic polymer solution was obtained in the same manner except that 50 parts of dripped ethyl acetate was changed to 20 parts.

Production Examples 21 and 25
A reactor equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube is charged with the copolymerizable monomer and ethyl acetate shown in Table 1, 0.1 part of AIBN is added, and the air in the reaction vessel is filled with nitrogen gas. Replaced. Next, the mixture was heated to 68 ° C. with stirring in a nitrogen atmosphere, and then reacted for 8 hours. After completion of the reaction, the reaction mixture was diluted with ethyl acetate to obtain a (meth) acrylic polymer solution.

Production Example 22
A reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube was charged with the parts by weight of the copolymerizable monomer shown in Table 1, ethyl acetate and toluene, and 0.2 parts of AIBN was added. Air was replaced with nitrogen gas. Next, the mixture was heated to 70 ° C. with stirring under a nitrogen atmosphere, and then reacted for 2 hours. Thereafter, 0.2 part of PHPV, which is a peroxide polymerization initiator, was added, the temperature was raised to 80 ° C., reacted for 20 minutes, then 0.3 part of PHPV was added and reacted for 40 minutes, and 1.0 part of PHPV was further added. Added and allowed to react for 3 hours. After completion of the reaction, the reaction mixture was diluted with ethyl acetate to obtain a (meth) acrylic polymer solution.

Production Example 24
A reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube was charged with the copolymerizable monomer and ethyl acetate in parts by weight shown in Table 1, 0.2 parts of AIBN was added, and the air in the reaction vessel was evacuated. Replaced with nitrogen gas. Next, the mixture was heated to 60 ° C. with stirring under a nitrogen atmosphere, and then reacted for 3 hours. Thereafter, while adding 20 parts of ethyl acetate dropwise over 50 minutes, 0.2 part of PHPV was added and reacted for 5 hours. After completion of the reaction, the reaction mixture was diluted with ethyl acetate to obtain a (meth) acrylic polymer solution.

  The weight average molecular weight (Mw) obtained from the GPC measurement of the (meth) acrylic polymer produced in Production Examples 1 to 25 and the value obtained by dividing the weight average molecular weight of the copolymer by the number average molecular weight (Mw / Mn) The numerical values are shown in Table 1.

<GPC measurement conditions>
Measuring device: HLC-8120GPC (manufactured by Tosoh Corporation)
GPC column configuration: The following five columns (all manufactured by Tosoh Corporation)
(1) TSK-GEL H _XL -H (guard column)
(2) TSK-GEL G7000H _XL
(3) TSK-GEL GMH _XL
(4) TSK-GEL GMH _XL
(5) TSK-GEL G2500H _XL
Diluted with tetrahydrofuran so that the sample concentration is 1.0 mg / cm ³ Mobile phase solvent: Tetrahydrofuran flow rate: 1.0 cm ³ / min
Column temperature: 40 ° C

Example 1
With respect to 100 parts of the (meth) acrylic polymer (solid content) in the (meth) acrylic polymer solution obtained in Production Example 1, the isocyanate crosslinking agent TD-75 (manufactured by Soken Chemical Co., Ltd.) 2 parts, 0.1 part of silane coupling agent KBE-9007 (manufactured by Shin-Etsu Chemical Co., Ltd.), and 0.003 part of dibutyltin dilaurate (hereinafter DBTDL, manufactured by Tokyo Chemical Industry Co., Ltd.) as a crosslinking accelerator A solution of the composition was obtained.

  The pressure-sensitive adhesive composition solution was applied to the surface of the peeled polyester film and dried to obtain a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer having a thickness of 25 μm. This pressure-sensitive adhesive sheet was affixed to one side of a polarizing film and aged for 7 days under conditions of a temperature of 23 ° C. and a humidity of 65% RH to obtain an optical member.

Examples 2-22, Comparative Examples 1-14
In the same manner as in Example 1, as shown in Table 2, with respect to 100 parts of the (meth) acrylic polymer (solid content) in the polymer solutions of Production Examples 2 to 25, an isocyanate crosslinking agent and a silane coupling An adhesive and a crosslinking accelerator were added to obtain a solution of the pressure-sensitive adhesive composition.

  Moreover, the optical member was obtained like Example 1 using the obtained adhesive composition.

  About the optical member obtained by the said Example and comparative example, the durability, rework property, and light leakage prevention property were evaluated with the following evaluation methods. The results are summarized in Table 2.

<Durability evaluation method>
Each of the optical members is cut into a predetermined size, adhered to one side of a non-alkali glass plate using a laminator roll, and then held in an autoclave adjusted to 50 ° C. and 5 atm for 20 minutes. It was created.
Two similar test plates were prepared and left for 500 hours under conditions of a temperature of 60 ° C. and a humidity of 95% RH and for 500 hours under a temperature of 85 ° C., respectively. The occurrence of cracks and the like were visually observed and evaluated.
○: Appearance defects such as foaming, peeling and cracking were not observed Δ: Appearance defects such as foaming, peeling and cracking were slightly observed ×: Appearance defects such as foaming, peeling and cracking were clearly recognized

<Cooling cycle durability evaluation method>
The optical member was attached to one side of an alkali-free glass plate using a laminator roll, and then held in an autoclave adjusted to 50 ° C. and 5 atm for 20 minutes to prepare a test plate. Using the thermal shock device TSA-71L-A manufactured by Espec Co., Ltd., the test plate thus prepared was repeated 200 times for a cooling cycle of -40 ° C. for 30 minutes and 80 ° C. for 30 minutes to foam the optical member. The presence or absence of floating or peeling was visually observed and evaluated according to the following criteria.
○: Appearance defects such as foaming, floating and peeling were not observed. Δ: Appearance defects such as foaming, floating and peeling were slightly observed. ×: Foaming, floating and peeling were confirmed.

<Reworkability test>
After the optical member was cut to a width of 25 mm, the polyester release film was peeled off and the polarizing film was adhered to the glass plate via the adhesive film. This was held in an autoclave adjusted to a temperature of 50 ° C. and a pressure of 5 atm for 20 minutes, and a polarizing film and a glass plate were bonded to obtain a test piece.

The test piece was allowed to stand at 70 ° C. for 6 hours and then allowed to cool to 23 ° C. Thereafter, the optical member was peeled 180 degrees from the glass plate, and the surface of the glass plate was visually observed.
○: No contamination or residual adhesive was observed on the glass plate surface.
Δ: Slight contamination or adhesive residue was observed on the glass plate surface.
X: Contamination and residual adhesive were clearly seen on the glass plate surface.

<Evaluation method for light leakage prevention>
Two optical members are attached to the front and back surfaces of an alkali-free glass plate using a laminator roll so that they are mutually orthogonal Nicols, and then held in an autoclave adjusted to 50 ° C. and 5 atm for 20 minutes. A test plate was prepared.
The prepared test plate was allowed to stand at 85 ° C. for 500 hours, visually observed for light leakage prevention properties, and evaluated according to the following criteria.
◎: No light leakage was observed ○: Light leakage was hardly observed △: Light leakage was slightly observed ×: Clear light leakage was observed

表１中の略号は、以下の通りである。
ＢＡ ： ブチルアクリレート
２ＥＨＡ ： ２−エチルヘキシルアクリレート
ＭＥＡ ： ２−メトキシエチルアクリレート
ＢＺＡ ： ベンジルアクリレート
ＰＨＥＡ ： ２−フェノキシエチルアクリレート
ＰＨＤＥＧＡ： フェノキシジエチレングリコールアクリレート
ＰＨＡ ： フェニルアクリレート
２ＨＥＡ ： ２−ヒドロキシエチルアクリレート
４ＨＢＡ ： ４−ヒドロキシブチルアクリレート

Abbreviations in Table 1 are as follows.
BA: butyl acrylate 2EHA: 2-ethylhexyl acrylate MEA: 2-methoxyethyl acrylate BZA: benzyl acrylate PHEA: 2-phenoxyethyl acrylate PHDEGA: phenoxydiethylene glycol acrylate PHA: phenyl acrylate 2HEA: 2-hydroxyethyl acrylate
4HBA: 4-hydroxybutyl acrylate

表２中、成分（Ｂ）、成分（Ｃ）および成分（Ｄ）の名称は以下の通りである。
ＴＤ−７５ ：綜研化学社製、イソシアネート系架橋剤
Ｄ−９４ ：綜研化学社製、イソシアネート系架橋剤
ＫＢＥ−９００７ ：信越化学工業社製、イソシアネート型シランカップリング剤
ＫＢＭ−５７３ ：信越化学工業社製、アミノ型シランカップリング剤
ＤＢＴＤＬ ：東京化成工業社製、ジブチルすずジラウレート
カオーライザーＮｏ．１：花王社製、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルヘキサンジアミン
Ｕ−ＣＡＴ ＳＡ １ ：サンアプロ社製、ＤＢＵ（Ｒ）−フェノール塩

In Table 2, the names of component (B), component (C) and component (D) are as follows.
TD-75: manufactured by Soken Chemical Co., Ltd., isocyanate-based crosslinking agent D-94: manufactured by Soken Chemical Co., Ltd., isocyanate-based crosslinking agent KBE-9007: manufactured by Shin-Etsu Chemical Co., Ltd., isocyanate type silane coupling agent KBM-573: Shin-Etsu Chemical Co., Ltd. Manufactured by Amino-type silane coupling agent DBTDL: manufactured by Tokyo Chemical Industry Co., Ltd., dibutyltin dilaurate kaorizer No. 1: Kao Corporation, N, N, N ′, N′-tetramethylhexanediamine U-CAT SA 1: San Apro Corporation, DBU (R) -phenol salt

  As is clear from the evaluation results shown in Table 2, the pressure-sensitive adhesive sheet using the pressure-sensitive adhesive of the present invention was free from milling and peeling, and was excellent in durability and reworkability. Moreover, it was also shown that it is an adhesive with excellent light leakage prevention properties in each size. On the other hand, the adhesive sheet of the comparative example has a defect in any of durability, reworkability, and light leakage prevention.

According to the present invention, a pressure-sensitive adhesive that has both durability and light leakage properties, has no low molecular weight bleed, can suppress contamination during re-peeling, can be prevented from peeling under severe conditions, and has excellent reworkability Since the composition can be provided, it can be applied to various uses such as a pressure-sensitive adhesive sheet for optical films such as a polarizing film and a retardation film.

Claims (4)

Next component (A), component (B), component (C) and component (D)
(A) The weight average molecular weight obtained by copolymerizing at least the following components (a1), (a2) and (a3) is 800,000 to 1,600,000, and the weight average molecular weight of the copolymer is divided by the number average molecular weight. An acrylic polymer having a measured value (Mw / Mn) of 10-50;
(A1) (meth) acrylic acid alkyl ester and / or (meth) acrylic acid alkoxyalkyl ester 5-89.5 wt%, (a2) aromatic ring-containing monomer 10-85 wt%, (a3) hydroxyl group-containing monomer 5-10% by weight,
(B) 0.005 to 5 parts by weight of isocyanate-based crosslinking agent with respect to 100 parts by weight of acrylic polymer (C) 0.05 to 1.0 parts by weight of (C) silane coupling agent with respect to 100 parts by weight of acrylic polymer (D ) An optical film pressure-sensitive adhesive composition containing 0.001 to 0.5 parts by weight of a crosslinking accelerator per 100 parts by weight of an acrylic polymer. Component (a2) is phenyl acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, hydroxyethylated β-naphthol acrylate, biphenyl (meth) The pressure-sensitive adhesive composition for an optical film according to claim 1, which is at least one monomer selected from acrylate, styrene, vinyltoluene, and α-methylstyrene. A pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition according to claim 1 or 2 on at least one side of a support. An optical member comprising a pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition according to claim 1 or 2 on at least one surface of an optical film.