TW201728722A - Adhesive composition for optical film, adhesive layer for optical film, optical film having adhesive layer and picture display unit - Google Patents

Abstract

To provide an adhesive composition for an optical film capable of forming an adhesive layer satisfying durability to glass and a transparent conductive layer, the durability with which foaming, detachment, nor humidification white turbidness can be prevented, while suppressing display unevenness due to leak light. An adhesive composition for an optical film includes a (meth)acrylic polymer (A) containing alkyl (meth)acrylate (a1) of 33 wt.% or more, aromatic ring-containing (meth)acrylate (a2) of 3 to 25 wt.%, N-vinyl group-containing lactam-based monomer (a3) of 5 to 35 wt.% and hydroxyl group-containing monomer (a4) of 0.01 to 7 wt.% as monomer units, and a crosslinking agent (B) of 0.01 to 3 pts.wt. based on 100 pts.wt. of the (meth)acryl polymer (A).

Description

Adhesive composition for optical film, adhesive layer for optical film, optical film with adhesive layer, and image display device

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical film for an optical film and an optical film with an adhesive layer, wherein the optical film with the adhesive layer is formed with an adhesive on at least one side of the optical film. Layer. Further, the present invention relates to a liquid crystal display device, an organic EL display device, and an image display device such as a PDP using the optical film with the above-mentioned adhesive layer. As the optical film, a polarizing film, a retardation film, an optical compensation film, and a brightness enhancement film can be used, and a laminate thereof can be further used.

BACKGROUND OF THE INVENTION A liquid crystal display device or the like is indispensable for arranging a polarizing element on both sides of a liquid crystal element from the viewpoint of image formation, and generally a polarizing film is attached. Further, in addition to the polarizing film on the liquid crystal panel, various optical elements have been gradually used in order to improve the display quality of the display. For example, a retardation film used for anti-coloring, a viewing angle expanding film for improving the viewing angle of the liquid crystal display, and a brightness enhancing film for improving the contrast of the display, and the like are used. These films are collectively referred to as optical films.

When an optical member such as the optical film is attached to a liquid crystal element, an adhesive is usually used. Further, in order to reduce the loss of light, the optical film and the liquid crystal element or the optical film are usually adhered to each other by an adhesive. In this case, an optical film with an adhesive layer, that is, an optical film in which an adhesive is provided in advance in the form of an adhesive layer on one side of the optical film, is generally used because it has an optical film that can be fixed but does not need to be used. The advantages of drying steps and the like. A release film is usually adhered to the adhesive layer of the optical film with the adhesive layer.

The required properties of the adhesive layer are required to be durable when the optical film with the adhesive layer is bonded to the glass substrate of the liquid crystal panel. For example, it is required to use heating and humidification as an environment-promoting test. In the endurance test, defects such as peeling and floating caused by the adhesive layer were not generated.

Further, an optical film (for example, a polarizing plate) tends to shrink due to heat treatment. Due to the shrinkage of the polarizing plate, the base polymer forming the adhesive layer is aligned to cause a phase difference, which may become a problem of display unevenness due to light leakage. Therefore, it is required to suppress display unevenness to the aforementioned adhesive layer.

Various adhesive compositions capable of forming the above-mentioned adhesive layer of the optical film with the adhesive layer have been proposed (for example, Patent Documents 1 to 3).

On the other hand, when the liquid crystal display device is manufactured, when the polarizing film with the adhesive layer is adhered to the liquid crystal element, the release film is peeled off from the adhesive layer of the polarizing film with the adhesive layer, but The peeling of the film is caused by static electricity. The static electricity thus generated affects the alignment of the liquid crystal inside the liquid crystal display device, resulting in defective defects. Further, when the liquid crystal display device is used, display unevenness due to static electricity may occur. The generation of static electricity can be suppressed by, for example, forming an antistatic layer on the outer surface of the polarizing film. However, in order to suppress the occurrence of the static electricity at the fundamental position, it is effective to impart an antistatic function to the adhesive layer.

As means for imparting an antistatic function to the adhesive layer, for example, an ionic compound is blended in an adhesive forming an adhesive layer (Patent Documents 4 to 5). It is described that an organic molten salt which is liquid at normal temperature is blended in an acrylic adhesive used for a polarizing film, and an ionic solid containing an imidazole cation and an inorganic anion is disclosed in Patent Document 4, and Patent Document 5 It is an onium salt composed of a cation having 6 to 50 carbon atoms and a fluorine atom-containing anion having a nitrogen atom of 4 stages. Advanced technical literature

Patent Document 1: Japanese Patent Publication No. 2012-158702 Patent Document 2: Japanese Patent Publication No. 2009-215528 Patent Document 3: Japanese Patent Publication No. 2009-242767 Patent Document 4: Japanese Patent Publication No. Patent Publication No. 2009-251281 Patent Document 5: International Publication No. 2007/034533

SUMMARY OF THE INVENTION Problems to be Solved by the Invention When a liquid crystal display device is used, display unevenness may occur due to static electricity. Therefore, a transparent conductive layer (for example, indium oxide containing tin oxide may be formed on a glass substrate of a liquid crystal panel: ITO layer). Further, in addition to the countermeasure against display unevenness due to static electricity, the transparent conductive layer can also function to separate the driving electric field in the liquid crystal element from the touch panel when the liquid crystal display device is used in the touch panel. The function of the shielding electrode. In the liquid crystal display device of the above configuration, the adhesive layer of the optical film with the adhesive layer is directly bonded to the ITO layer. Therefore, the adhesive layer is required to have not only adhesion to the glass substrate but also adhesion to the ITO layer. In general, compared with the glass plate, the adhesion between the ITO layer and the adhesive layer is poor and the durability is a problem. It is known that after the optical film with the adhesive layer is placed on a glass substrate in a state of high temperature and high humidity such as 60° C. and 95% RH, the adhesive layer may become cloudy after returning to normal temperature ( Humidification and white turbidity). If humidification is turbid, it will cause the visibility of the display to be low.

Further, the pressure-sensitive adhesive layer is a metal such as copper which directly contacts the ITO layer of the liquid crystal panel and the wiring wires. Therefore, it is feared that the ITO layer and the metal are corroded by the composition of the aforementioned adhesive layer. Moreover, if corrosion occurs, there is a problem that the resistance of the ITO layer and the wiring wires rises.

Patent Document 1 proposes an adhesive composition in which 4 to 20 parts by weight of an isocyanate crosslinking agent is blended with respect to 100 parts by weight of an acrylic polymer containing an aromatic ring-containing monomer and a guanamine-containing monomer. However, in Patent Document 1, since the monomer forming the acrylic polymer does not contain the hydroxyl group-containing monomer, the acrylic polymer and the isocyanate crosslinking agent are not directly reacted and phase separated, and the adhesive is likely to be generated. The tendency to be turbid is not appropriate. Further, since the adhesive composition of Patent Document 1 has a high ratio of the crosslinking agent, it tends to peel off easily in the durability test.

Further, Patent Documents 2 and 3 propose a (meth)acrylic polymer containing an aromatic ring (meth) acrylate and an amine group-containing (meth) acrylate; and a binder containing a crosslinking agent Agent composition. However, the adhesive layer formed of the adhesive compositions of Patent Documents 2 and 3 has poor adhesion to the ITO layer and cannot satisfy durability. Further, in the comparative example of Patent Document 2, it is disclosed that the amine group-containing (meth) acrylate is replaced with a guanamine-containing monomer, but as shown in the results of Table 2 of each of Patent Documents 2 and 3, Durability cannot be satisfied when a guanamine-containing monomer is used.

On the other hand, as described in Patent Documents 4 and 5, the antistatic function can be imparted by blending an ionic compound in an adhesive for forming an adhesive layer. Further, since the liquid crystal display device is preset to be used in various temperature and humidity environments, the required adhesive agent does not change even if the temperature and humidity change, and the surface resistance is not changed, and can be imparted with stable resistance over a long period of time. Electrostatic function. In recent years, a so-called on-cell touch panel type liquid crystal display device in which a liquid crystal display device laminated with a touch panel and an induction electrode such as an ITO layer are directly formed on a glass substrate of a liquid crystal panel has been gradually increased. In this case, it has been found that if the surface resistance of the adhesive layer is too low, the sensitivity of the touch panel is lowered. In order to avoid static unevenness and the sensitivity of the touch panel at the same time, it is necessary to control the surface resistance to a narrower range than before, so that it is required to have a more stable antistatic function than before.

Patent Document 4 proposes to form an adhesive layer capable of imparting long-term stable antistatic performance by an acrylic adhesive containing an imidazole cation, an inorganic anion, and an ionic solid. However, the adhesive layer of Patent Document 4 is insufficient in adhesion to the ITO layer under humidified conditions. Further, Patent Document 5 proposes an acrylic pressure-sensitive adhesive containing an organic molten salt which is liquid at normal temperature. However, the acrylic pressure-sensitive adhesive described in Patent Document 5 has poor dispersibility of the organic molten salt, and the antistatic performance stability of the adhesive layer formed of the adhesive is not sufficient.

SUMMARY OF THE INVENTION An object of the present invention is to provide an adhesive composition for an optical film which can form an adhesive layer, which can satisfy foaming and flaking or humidification and white turbidity regardless of either the glass or the transparent conductive layer. Durability and can suppress uneven display caused by light leakage.

It is an object of the present invention to provide an adhesive composition for an optical film which can form an adhesive layer, which can satisfy any non-foaming and peeling or humidification white turbidity for either the glass or the transparent conductive layer. It is durable and can suppress the display unevenness caused by light leakage, and it can impart metal corrosion resistance and stable antistatic function.

Still another object of the present invention is to provide an optical film having an adhesive layer having an adhesive layer formed using the above-described adhesive composition for an optical film; and further providing an image display device using the above-mentioned adhesive layer Optical film. Means to solve the problem

The present inventors have intensively studied in order to solve the above problems, and as a result, the following adhesive composition for an optical film has been found, and the present invention has been completed.

That is, the present invention relates to an adhesive composition for an optical film, which comprises a (meth)acrylic polymer (A) and 0.01 with respect to 100 parts by weight of the above (meth)acrylic polymer (A). ~3 parts by weight of the crosslinking agent (B), the (meth)acrylic polymer (A) contains 33% by weight or more of the alkyl (meth)acrylate (a1), and 3 to 25% by weight of the aromatic ring-containing ring (meth) acrylate (a2), 5 to 35% by weight of an N-vinyl containing decylamine monomer (a3), and 0.01 to 7% by weight of a hydroxyl group-containing monomer (a4) as a monomer unit .

In the adhesive composition for an optical film, the (meth)acrylic polymer (A) may further contain 2% by weight or less of a carboxyl group-containing monomer (a5) as a monomer unit.

In the above-mentioned adhesive composition for an optical film, the hydroxyl group-containing monomer (a4) is preferably 4-hydroxybutyl (meth)acrylate.

The crosslinking agent (B) preferably contains at least one selected from the group consisting of an isocyanate compound and a peroxide. The isocyanate compound preferably contains an aliphatic polyisocyanate compound.

The above-mentioned adhesive composition for an optical film may further contain a decane coupling agent (C). The decane coupling agent (C) is preferably contained in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the above (meth)acryl-based polymer (A).

The above-mentioned adhesive composition for an optical film may further contain an ionic compound (D). The aforementioned ionic compound (D) is preferably an alkali metal salt and/or an organic cation-anion salt. Further, the ionic compound (D) preferably contains a fluorine-containing anion. The ionic compound (D) is preferably contained in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the (meth)acryl-based polymer (A).

Further, the present invention relates to an adhesive layer for an optical film, which is characterized in that it is formed using the above-mentioned adhesive composition for an optical film. The gel fraction of the adhesive layer for an optical film is preferably more than 70% by weight.

Further, the present invention relates to an optical film having an adhesive layer, characterized in that the adhesive layer for the optical film is formed on at least one side of the optical film.

Still further, the present invention relates to an image display apparatus characterized in that at least one layer of the above-mentioned optical film with an adhesive layer is used. Effect of the invention

The adhesive composition for an optical film of the present invention contains a (meth)acrylic polymer (A) as a base polymer, and the (meth)acrylic polymer (A) is contained in a predetermined unit ratio of monomer units. An aromatic ring (meth) acrylate (a2), an N-vinyl containing decylamine monomer (a3), and a hydroxyl group-containing monomer (a4). An adhesive layer obtained from an adhesive composition for an optical film containing the (meth)acrylic polymer (A) having the specific composition and a predetermined amount of a crosslinking agent (B), an adhesive layer having the adhesive layer Even in the high-temperature durability test of extremely high temperature conditions of a heating temperature of 95 ° C, the optical film does not cause humidification and white turbidity on any of the glass and the transparent conductive layer (ITO layer, etc.), and has excellent durability. It is possible to suppress peeling, floating, and the like from occurring in a state of being adhered to a liquid crystal element or the like. In particular, when the gel fraction of the pressure-sensitive adhesive layer exceeds 70% by weight, the high-temperature durability is good.

In general, the durability of a transparent conductive layer such as an ITO layer is also susceptible to the composition of the ITO layer, and a low tin ratio amorphous ITO layer can be seen compared to a high tin ratio crystalline ITO layer. Durability tends to deteriorate. The adhesive layer obtained from the adhesive composition for an optical film can achieve durability which is stable even for the amorphous ITO layer. Further, the optical film having the adhesive layer of the adhesive layer of the present invention is also excellent in metal corrosion resistance to the transparent conductive layer. When the carboxyl group-containing monomer (a5) is used, the metal corrosion resistance to the transparent conductive layer can also be satisfied by controlling the use ratio.

In addition, in a video display device such as a liquid crystal display device using an optical film with an adhesive layer such as a polarizing plate attached to an adhesive layer, when it is heated or humidified, the peripheral portion of the liquid crystal panel or the like may not be surrounded by the periphery. In the case where the average or the corner portion is uneven (whitening), display unevenness is caused, and the display defect is caused. However, since the adhesive layer of the optical film of the adhesive of the present invention is used as the adhesive composition for the optical film, the peripheral portion of the display screen can be suppressed. The display caused by the light leakage is uneven.

Further, by incorporating the ionic compound (D) into the adhesive composition for an optical film of the present invention, an antistatic function can be imparted. The adhesive composition for an optical film of the present invention contains an ionic compound (D) because it contains the (meth)acrylic polymer (A) having the specific composition described above and a predetermined amount of a crosslinking agent (B). In this case, an adhesive layer capable of imparting a stable antistatic function can be formed.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The adhesive composition for an optical film of the present invention contains a (meth)acrylic polymer (A) as a base polymer. The (meth)acrylic polymer (A) usually contains, as a main component, a (meth)acrylic acid alkyl ester of a monomer unit. Further, (meth) acrylate means acrylate and/or methacrylate, and (meth) of the present invention has the same meaning.

The alkyl (meth)acrylate constituting the main skeleton of the (meth)acrylic polymer (A) may, for example, be a linear or branched alkyl group having 1 to 18 carbon atoms. For example, as the alkyl group, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, cyclohexyl, heptyl, 2-ethylhexyl, isooctyl can be exemplified. , fluorenyl, fluorenyl, isodecyl, dodecyl, isotetradecyl, lauryl, thirteen, fifteen, sixteen, seventeen, eighteen, and the like. They can be used singly or in combination. The average carbon number of the alkyl groups is preferably from 3 to 9.

An aromatic ring-containing (meth) acrylate (a2) is used for the (meth)acrylic polymer (A). The (meth) acrylate (a2) containing an aromatic ring is a compound which contains an aromatic ring structure in its structure and contains a (meth) acryl fluorenyl group. The aromatic ring may, for example, be a benzene ring, a naphthalene ring or a biphenyl ring. The aromatic ring-containing (meth) acrylate (a2) satisfies durability (especially durability against a transparent conductive layer), and can improve display unevenness caused by whitening of the peripheral portion.

Specific examples of the aromatic ring-containing (meth) acrylate (a2) include benzyl (meth) acrylate, phenyl (meth) acrylate, and o-phenyl phenol (meth) acrylate phenoxy ( Methyl) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, phenoxy diethylene glycol (meth) acrylate, ethylene oxide modified nonyl phenol (methyl Acrylate, ethylene oxide modified cresol (meth) acrylate, phenol ethylene oxide modified (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, methoxy a benzene ring-like substance such as a benzyl benzyl (meth) acrylate, a chlorobenzyl (meth) acrylate, a cresyl (meth) acrylate or a polystyryl (meth) acrylate; a hydroxyethyl group; Β-naphthol acrylate, 2-naphthylethyl (meth) acrylate, 2-naphthyloxyethyl acrylate, 2-(4-methoxy-1-naphthalenyloxy)ethyl (A) A compound having a naphthalene ring such as an acrylate or a biphenyl ring such as biphenyl (meth)acrylate.

As the aromatic ring-containing (meth) acrylate (a2), benzyl (meth) acrylate or phenoxyethyl (meth) acrylate is preferred from the viewpoint of adhesion properties and durability. Phenyloxyethyl (meth)acrylate is preferred.

The N-vinyl-containing decylamine-based monomer (a3) is a compound containing a polymerizable unsaturated double bond such as a vinyl group on a nitrogen containing an indoleamine structure and having a structure in the indoleamine structure. Specific examples of the N-vinyl group-containing melamine-based monomer (a3) include N-ethylpyrrolidone and N-ethyl-ε-caprolactam. The N-vinyl-containing melamine-based monomer (a3) is preferable in that it satisfies high-temperature durability, and is particularly preferable in that it satisfies high-temperature durability to the transparent conductive layer.

The hydroxyl group-containing monomer (a4) is a compound which contains a hydroxyl group in its structure and contains a polymerizable unsaturated double bond such as a (meth)acrylonyl group or a vinyl group. Specific examples of the hydroxyl group-containing monomer (a4) include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. , (6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, -12-hydroxylauryl (meth)acrylate, etc. ( Hydroxyalkyl methacrylate, or (4-hydroxymethylcyclohexyl)methyl acrylate or the like. In the above hydroxyl group-containing monomer (a4), from the viewpoint of durability, 2-hydroxyethyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate is preferred, particularly ( Methyl)-4-hydroxybutyl acrylate is preferred.

The hydroxyl group-containing monomer (a4) becomes a reaction point with the crosslinking agent when the adhesive composition contains a crosslinking agent. The hydroxyl group-containing monomer (a4) is suitable for improving the aggregability and heat resistance of the obtained adhesive layer because of its high reactivity with the intermolecular crosslinking agent. Furthermore, it is desirable to have a hydroxyl group-containing monomer (a4) from the viewpoint of reworkability.

The (meth)acrylic polymer (A) contains a predetermined amount of each of the above monomers as a monomer unit in a weight ratio of the total constituent monomers (100% by weight). The weight ratio of the alkyl (meth)acrylate (a1) can be set to the remainder of the monomer other than the alkyl (meth)acrylate (a1), specifically, 33% by weight or more. The weight ratio of the alkyl (meth)acrylate (a1) can be adjusted within the range of 33 to 91.99% by weight. It is preferable to set the weight ratio of the alkyl (meth)acrylate (a1) within the above range to ensure adhesion.

The weight ratio of the aromatic ring-containing (meth) acrylate (a2) is 3 to 25% by weight, preferably 8 to 22% by weight, more preferably 12 to 18% by weight. When the weight ratio of the aromatic ring-containing (meth) acrylate (a2) is less than 3% by weight, display unevenness may not be sufficiently suppressed. On the other hand, when it exceeds 25% by weight, the display unevenness cannot be sufficiently suppressed, and the durability is also lowered.

The weight ratio of the N-vinyl-containing melamine-based monomer (a3) is 5 to 35% by weight. The weight ratio is preferably 8.5 wt% or more, more preferably 9% by weight or more, further preferably 10.5% by weight or more, and further preferably 13 wt% or more, from the viewpoint of high-temperature durability of the transparent conductive layer. It is better. On the other hand, when the weight ratio is too high, the anchoring property to the base film such as the polarizing film tends to be lowered. Therefore, the weight ratio is preferably 30% by weight or less, and more preferably 25% by weight or less.

The weight ratio of the hydroxyl group-containing monomer (a4) is 0.01 to 7% by weight, preferably 0.1 to 5% by weight, more preferably 0.5 to 5% by weight, still more preferably 0.5 to 3% by weight. When the weight ratio of the hydroxyl group-containing monomer (a4) is less than 0.01% by weight, the adhesive layer may become insufficiently crosslinked, and the high temperature durability and adhesion characteristics may not be satisfied. In particular, when the weight ratio of the fluorene-containing monomer (a3) containing the N-vinyl group is high, the gel fraction tends to decrease, and the heat foaming phenomenon tends to occur at the time of the high-temperature test. In terms of suppressing it, the weight ratio of the hydroxyl group-containing monomer (a4) is preferably set to 0.5% by weight or more. Further, in terms of the weight ratio of the hydroxyl group-containing monomer (a4) to the weight ratio of the N-vinyl group-containing melamine-based monomer (a3), the ratio of the aforementioned weight ratio {(a4)/(a3) )} is preferably 0.1 or more. On the other hand, when it exceeds 7% by weight, high-temperature durability cannot be satisfied.

In the above (meth)acryl-based polymer (A), in addition to the above-mentioned monomer unit, it is not necessary to particularly contain other monomer units, but it is possible to improve the adhesion and heat resistance. One type or more of a copolymerizable monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acrylonitrile group or a vinyl group is introduced by copolymerization.

The aforementioned comonomer may, for example, be a carboxyl group-containing monomer (a5). The carboxyl group-containing monomer (a5) is a compound which contains a carboxyl group in its structure and contains a polymerizable unsaturated double bond such as a (meth)acryl fluorenyl group or a vinyl group. Specific examples of the carboxyl group-containing monomer (a5) include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, and fumaric acid. , Crotonic acid, etc. Among the carboxyl group-containing monomers (a5), acrylic acid is preferred from the viewpoints of copolymerizability, price, and adhesion characteristics.

In the case where the adhesive composition contains a crosslinking agent, the carboxyl group-containing monomer (a5) becomes a reaction point with the crosslinking agent together with the hydroxyl group-containing monomer (a4), and is suitable for improving the obtained adhesive layer. Aggregation and heat resistance. Further, the carboxyl group-containing monomer (a5) is preferable in terms of both high-temperature durability and reworkability.

The ratio of the carboxyl group-containing monomer (a5) in the (meth)acrylic polymer (A) is in the weight ratio of the total constituent monomer (100% by weight) of the (meth)acrylic polymer (A) It is preferably 2% by weight or less. When the weight ratio of the carboxyl group-containing monomer (a5) is more than 2% by weight, it is not suitable in terms of metal corrosion resistance. In addition, it is not suitable from the point of reworkability. The weight ratio of the carboxyl group-containing monomer (a5) is preferably from 0.01 to 2% by weight, more preferably from 0.05 to 1.5% by weight, still more preferably from 0.1 to 1% by weight, most preferably from 0.1 to 0.5% by weight.

Further, specific examples of the copolymerizable monomer other than the carboxyl group-containing monomer (a5) include an acid anhydride group-containing monomer such as maleic anhydride or itaconic acid anhydride; a caprolactone adduct of acrylic acid; a sulfonic acid group-containing monomer such as a sulfonic acid, 2-(meth)acrylamide, 2-methylpropanesulfonic acid, (meth)acrylamide, propionic acid, or sulfomethacrylate; a phosphate group-containing monomer or the like such as hydroxyethyl acrylonitrile phosphate.

Further, examples of the monomer for the purpose of modification include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and tert-butylamino B. An alkylaminoalkyl (meth) acrylate such as a (meth) acrylate; an alkoxyalkyl group such as methoxyethyl (meth) acrylate or ethoxyethyl (meth) acrylate ( Methyl) acrylate; N-(methyl) propylene oxymethylene succinimide or N-(methyl) propylene fluorenyl-6-oxyhexamethylene succinimide, N-( a succinimide monomer such as methyl)propenyl-8-oxyoctamethylene succinimide; N-cyclohexylmaleimide or N-isopropylmaleimide, N- a maleimide monomer such as lauryl maleimide or N-phenylmaleimine; N-methyl Ikonide, N-ethyl Ikonide, N-butyl Ikonium imine, N-octyl Icinoimine, N-2-ethylhexylkamponium imine, N-cyclohexylkkonium imine, N-lauryl Ikonide, etc. Kangimine monomer and the like.

Further, as the modifying monomer, a vinyl monomer such as vinyl acetate or vinyl propionate; a cyanoacrylate monomer such as acrylonitrile or methacrylonitrile; and a propylene propyl (meth)acrylate may be used. Epoxy group-containing (meth) acrylate; polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy ethylene glycol (meth) acrylate, methoxy group a diol-based (meth) acrylate such as polypropylene glycol (meth) acrylate; tetrahydrofuran methyl (meth) acrylate, fluorinated (meth) acrylate, poly methoxy (meth) acrylate or 2- A (meth) acrylate monomer such as methoxyethyl acrylate or the like. Further, isoprene, butadiene, isobutylene, vinyl ether or the like can be mentioned.

Further, examples of the copolymerizable monomer other than the above may be a decane-based monomer containing a ruthenium atom. Examples of the decane-based monomer include 3-propenyloxypropyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, 4-vinylbutyltrimethoxydecane, and 4 -vinylbutyltriethoxydecane, 8-vinyloctyltrimethoxydecane, 8-vinyloctyltriethoxydecane, 10-oxodecyltrimethoxydecane, 10-propenyloxime Trimethoxy decane, 10-methyl propylene fluorenyl methoxy decyl triethoxy decane, 10-propenyl fluorenyl decyl triethoxy decane, and the like.

Further, as the comonomer, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A may be used. Epoxypropyl ether di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol hexa a polyfunctional monomer having two or more unsaturated double bonds such as a (meth)acryl fluorenyl group or a vinyl group, such as an esterified product of a (meth)acrylic acid and a polyhydric alcohol such as a methyl acrylate, or a polyester, a polyester (meth)acrylic acid obtained by adding two or more unsaturated double bonds such as a (meth)acrylinyl group or a vinyl group having the same functional group as the monomer component to a skeleton such as an epoxy group or a urethane group. Ester, epoxy (meth) acrylate, urethane (meth) acrylate, and the like.

The ratio of the comonomer other than the carboxyl group-containing monomer (a5) in the (meth)acrylic polymer (A) to the total constituent monomer (100% by weight) of the (meth)acrylic polymer (A) The weight ratio is preferably about 0 to 10% by weight, more preferably about 0 to 7% by weight, and more preferably about 0 to 5% by weight.

The (meth)acrylic polymer (A) of the present invention usually has a weight average molecular weight of from 1,000,000 to 2,500,000. When durability, particularly heat resistance, is considered, the weight average molecular weight is preferably 1.2 million to 2,000,000. When the weight average molecular weight is less than 1,000,000, heat resistance is not suitable. Further, when the weight average molecular weight becomes larger than 2.5 million, the adhesive tends to be hard to be hardened, and peeling tends to occur. Further, the weight average molecular weight (Mw) / number average molecular weight (Mn) of the molecular weight distribution is 1.8 or more and 10 or less, and preferably 1.8 to 7, more preferably 1.8 to 5. When the molecular weight distribution (Mw/Mn) exceeds 10, it is not preferable in terms of durability. Further, the weight average molecular weight and the molecular weight distribution (Mw/Mn) were measured in accordance with GPC (gel permeation chromatography), and were obtained from values calculated by polystyrene conversion.

For the production of such a (meth)acrylic polymer (A), a known production method such as solution polymerization, bulk polymerization, emulsion polymerization, or various radical polymerization can be appropriately selected. Further, the obtained (meth)acryl-based polymer (A) may be any of a random copolymer, a block copolymer, and a graft copolymer.

Further, in the solution polymerization, as the polymerization solvent, for example, ethyl acetate, toluene or the like can be used. As a specific example of solution polymerization, the reaction is carried out by adding a polymerization initiator under an inert gas stream such as nitrogen, and reacting at a reaction temperature of usually about 50 to 70 ° C for about 5 to 30 hours.

The polymerization initiator, the chain transfer agent, the emulsifier, and the like used in the radical polymerization can be appropriately selected and used without particular limitation. Further, the weight average molecular weight of the (meth)acrylic polymer (A) can be controlled by the amount of the polymerization initiator, the chain transfer agent used, and the reaction conditions, and the amount thereof can be appropriately adjusted depending on the type thereof.

The polymerization initiator may, for example, be 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylamidinopropane) dihydrochloride or 2,2'-azobis [ 2-(5-methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine) disulfate, 2, 2'-couple Nitrogen (N, N'-dimethylene isobutyl hydrazine), 2, 2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine hydrate (Wako Pure Chemicals) Company-made, VA-057) azo initiator; potassium persulfate, ammonium persulfate, persulfate, di(2-ethylhexyl)peroxydicarbonate, di(4-tert-butyl Cyclohexyl)peroxydicarbonate, di-tert-butylperoxydicarbonate, tert-butylperoxy neodecanoate, third hexylperoxytrimethylacetate, tert-butylperoxy-3 Methyl acetate, dilauroyl peroxide, di-n-octyl peroxy, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, diperoxide (4- Methyl benzhydryl), benzhydryl peroxide, t-butylperoxy isobutyrate, 1,1-di(t-hexylperoxy)cyclohexane, tert-butyl hydrogen Peroxide, hydrogen peroxide, etc. a compound-based initiator; a combination of a persulfate and sodium hydrogen sulfite; a combination of a peroxide and sodium ascorbate; a redox-based initiator obtained by combining a peroxide with a reducing agent; .

The polymerization initiator may be used singly or in combination of two or more kinds. The total content is preferably from 0.005 to 1 part by weight, more preferably from 0.02 to 0.5 part by weight, per 100 parts by weight of the monomer.

In another example, when the (meth)acrylic polymer (A) having the above weight average molecular weight is produced by using, for example, 2,2'-azobisisobutyronitrile as a polymerization initiator, the amount of the polymerization initiator used is relative to The total amount of the monomer component of 100 parts by weight is preferably from about 0.06 to 0.2 parts by weight, more preferably from about 0.08 to about 0.175 parts by weight.

As the chain transfer agent, for example, lauryl mercaptan, propylene oxide thiol, hydrazine acetic acid, 2-hydrazine ethanol, thioglycolic acid, thioglycolic acid 2-ethylhexyl ester, 2,3-difluorene may be mentioned. -1-propanol and the like. The chain transfer agent may be used singly or in combination of two or more kinds, but the total content is about 0.1 part by weight or less based on 100 parts by weight of the total amount of the monomer components.

Further, examples of the emulsifier used in the emulsion polymerization include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, and polyoxyethylene alkylphenyl ether. Nonionic emulsifier such as an anionic emulsifier such as sodium sulfate, a polyoxyethylene alkyl ether, a polyoxyethylene alkylphenyl ether, a polyoxyethylene fatty acid ester, or a polyoxyethylene-polyoxypropylene block polymer Wait. These emulsifiers may be used alone or in combination of two or more.

Further, as the reactive emulsifier, an emulsifier to which a radical polymerizable functional group such as a propenyl group or an allyl ether group is introduced may, for example, be Aqualon HS-10, HS-20, KH-10, BC-05, or the like. BC-10, BC-20 (all of which are manufactured by First Industrial Pharmaceutical Co., Ltd.), Adeka Reasoap SE10N (made by Asahi Chemical Co., Ltd.), and the like. Since the reactive emulsifier is incorporated into the polymer chain after polymerization, the water resistance is improved and is ideal. The amount of the emulsifier used is 0.3 to 5 parts by weight based on 100 parts by weight of the total of the monomer components, and more preferably 0.5 to 1 part by weight from the viewpoint of polymerization stability and mechanical stability.

The adhesive composition of the present invention contains a crosslinking agent (B). As the crosslinking agent (B), an organic crosslinking agent and a polyfunctional metal chelate compound can be used. The organic crosslinking agent may, for example, be an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, or an imide crosslinking agent. The polyfunctional metal chelate is a substance in which a polyvalent metal is covalently bonded or coordinately bonded to an organic compound. The polyvalent metal atom may, for example, be Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn or Ti. Examples of the atom to be covalently bonded or coordinately bonded to the organic compound include an oxygen atom, and the organic compound may, for example, be an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound or a ketone compound.

As the crosslinking agent (B), an isocyanate crosslinking agent and/or a peroxide crosslinking agent are preferred.

As the isocyanate crosslinking agent (B), a compound having at least two isocyanate groups can be used. For example, a known aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate or the like which is used for the urethanization reaction is generally used.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propyl propyl diisocyanate, and 1,3-. Butyl diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like.

Examples of the alicyclic isocyanate include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, and hydrogenated diphenylmethane. Diisocyanate, hydrogenated dimethyl diisocyanate, hydrogenated tolyl diisocyanate hydrogenated tetramethyl dimethyl diisocyanate, and the like.

Examples of the aromatic diisocyanate include phenyl diisocyanate, 2,4-tolyl diisocyanate, 2,6-tolyl diisocyanate, 2,2'-diphenylmethane diisocyanate, and 4,4. '-Diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, Benzyl diisocyanate or the like.

In addition, examples of the isocyanate-based crosslinking agent (B) include a reaction of a polyhydric alcohol (such as a dimer, a 3-mer or a 5-mer) and a trimethylolpropane with a polyhydric alcohol. A urethane modified product, a urea modified substance, a diurea modified substance, a urea formate modified substance, an isomeric cyanide modified substance, a carbodiimide modified substance, or the like.

Commercial products of the isocyanate-based crosslinking agent (B) include, for example, the trade name "Millionate MT", "Millionate MTL", "Millionate MR-200", "Millionate MR-400", "CORONATE L", "CORONATE HL", "CORONATE HX". [The above is made by Japan Polyurethane Industry Co., Ltd.]; trade name "Takenate D-110N" "Takenate D-120N" "Takenate D-140N" "Takenate D-160N" "Takenate D-165N" "Takenate D-170HN" "Takenate D-178N" "Takenate 500" "Takenate 600" [above is manufactured by Mitsui Chemicals Co., Ltd.]; These compounds may be used singly or in combination of two or more.

The isocyanate crosslinking agent (B) is preferably an aliphatic polyisocyanate compound of an aliphatic polyisocyanate and a modified product thereof. The aliphatic polyisocyanate compound is more flexible than the other isocyanate crosslinking agent, and the stress accompanying the expansion/contraction of the optical film is easily relaxed, and peeling is less likely to occur in the durability test. As the aliphatic polyisocyanate compound, hexamethylene diisocyanate and a modified product thereof are particularly preferable.

The peroxide may be suitably used as long as it generates a radical active species by heating or light irradiation, and the base polymer of the adhesive composition is crosslinked, but it is preferable to use for 1 minute in consideration of workability and stability. A peroxide having a half-life temperature of from 80 ° C to 160 ° C, and a peroxide of from 90 ° C to 140 ° C is preferably used.

Usable peroxides are bis(2-ethylhexyl)peroxydicarbonate (1 minute half-life temperature: 90.6 ° C), bis(4-t-butylcyclohexyl)peroxydicarbonate (1) Minute half-life temperature: 92.1 ° C), dibutyl peroxydicarbonate (1 minute half-life temperature: 92.4 ° C), peroxy neodecanoic acid tert-butyl ester (1 minute half-life temperature: 103.5 ° C), peroxyisobutyl Trihexyl acid ester (1 minute half-life temperature: 109.1 ° C), tert-butyl peroxyisobutyrate (1 minute half-life temperature: 110.3 ° C), dilauroyl peroxide (1 minute half-life temperature: 116.4 ° C) , di-n-octyl peroxide (1 minute half-life temperature: 117.4 ° C), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (1 minute half-life temperature: 124.3 ° C), Bis(4-methylbenzylidene) peroxide (1 minute half-life temperature: 128.2 ° C), benzotrifluoride peroxide (1 minute half-life temperature: 130.0 ° C), tert-butyl peroxyisobutyrate (1 minute half-life temperature: 136.1 ° C), 1,1-di(trihexylperoxy)cyclohexane (1 minute half-life temperature: 149.2 ° C), and the like. Among them, from the viewpoint of excellent cross-linking reaction efficiency, especially bis(4-t-butylcyclohexyl)peroxydicarbonate (1 minute half-life temperature: 92.1 ° C), dilauroyl peroxide (1 minute) Half-life temperature: 116.4 ° C), benzoyl peroxide base (1 minute half-life temperature: 130.0 ° C), etc. are suitable for use.

Further, the half-life of the peroxide is an index indicating the decomposition rate of the peroxide, and means the time until the residual amount of the peroxide becomes half. The decomposition temperature for achieving half-life at any time, and the half-life time at any temperature are described in the manufacturer's catalogue, etc., for example, in the "Organic peroxide catalogue" published by Nippon Oil & Fat Co., Ltd. (May 2003)" and so on.

The crosslinking agent (B) is preferably used in an amount of 0.01 to 3 parts by weight, more preferably 0.02 to 2 parts by weight, even more preferably 0.03 to 1 part, per 100 parts by weight of the (meth)acrylic polymer (A). Parts by weight. Further, when the crosslinking agent (B) is less than 0.01 part by weight, the adhesive layer may become insufficiently crosslinked, and the durability and the adhesive property may not be satisfied. On the other hand, if it is more than 3 parts by weight, the adhesion is adhered. The agent layer becomes too hard and the tendency to reduce durability can be seen.

The isocyanate-based crosslinking agent may be used singly or in combination of two or more kinds thereof. The total content is preferably 0.01% by weight based on 100 parts by weight of the (meth)acryl-based polymer (A). It is preferably contained in an amount of 0.02 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight. It can be appropriately contained in consideration of the cohesive force, the peeling in the durability test, and the like.

The peroxide may be used singly or in combination of two or more kinds, but the total content is 0.01 to 2 parts by weight based on 100 parts by weight of the (meth)acrylic polymer (A). The parts by weight are preferably contained in an amount of 0.04 to 1.5 parts by weight, more preferably 0.05 to 1 part by weight. In order to adjust workability, reworkability, crosslinking stability, peelability, and the like, it is preferred to appropriately select within this range.

Further, the method for measuring the amount of decomposition of the peroxide remaining after the reaction treatment can be measured by, for example, HPLC (High Speed Liquid Chromatography).

More specifically, for example, about 0.2 g of the post-reaction adhesive composition is taken out each time, immersed in 10 mL of ethyl acetate, and subjected to vibration extraction at 25 ° C, 120 rpm for 3 hours, at room temperature, at room temperature. Allow to stand for 3 days. Next, 10 mL of acetonitrile was added, and the mixture was shaken at 120 rpm for 30 minutes at 25 ° C, and about 10 μL of the extract obtained by filtration using a membrane filter (0.45 μm) was injected into HPLC for analysis, which can be regarded as the amount of peroxide after the reaction treatment.

In the adhesive composition of the present invention, a decane coupling agent (C) may be contained. Durability can be improved by using a decane coupling agent (C). Specific examples of the decane coupling agent include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-epoxypropoxypropane. Epoxy-containing decane coupling agent such as methyl-diethoxy decane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane; 3-aminopropyltrimethoxydecane, N-2 -(Aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-triethoxydecane-N-(1,3-dimethylbutylidene)propylamine, N-phenyl- An amine group-containing decane coupling agent such as γ-aminopropyltrimethoxydecane; 3-propenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, etc. (methyl An acryl-based decane coupling agent; an isocyanate group-containing decane coupling agent such as 3-isocyanate propyl triethoxy decane. As the decane coupling agent exemplified above, an epoxy group-containing decane coupling agent is preferred.

Further, as the decane coupling agent (C), a compound having a plurality of alkoxy fluorenyl groups in the molecule can be used. Specifically, for example, X-41-1053, X-41-1059A, X-41-1056, X-41-1805, X-41-1818, X-41-1810, X-40- manufactured by Shin-Etsu Chemical Co., Ltd. 2651 and so on. The decane coupling agent having a plurality of alkoxyfluorenyl groups in the molecule is highly effective in improving durability because it is less volatile and has a plurality of alkoxy fluorenyl groups. In particular, the adherend of the optical film with the adhesive layer is excellent in durability even when it is a transparent conductive layer (for example, ITO or the like) which is less reactive with the alkoxy fluorenyl group than the glass. Further, the decane coupling agent having a plurality of alkoxyfluorenyl groups in the molecule is preferably one having an epoxy group in the molecule, and the epoxy group is preferably contained in the molecule. A decane coupling agent having a plurality of alkoxyfluorenyl groups and an epoxy group in the molecule tends to have good durability even when the attached material is a transparent conductive layer (for example, ITO or the like). Specific examples of the decane coupling agent having a plurality of alkoxyfluorenyl groups and an epoxy group in the molecule include X-41-1053, X-41-1059A, and X-41-1056 manufactured by Shin-Etsu Chemical Co., Ltd. X-41-1056 manufactured by Shin-Etsu Chemical Co., Ltd. with high oxygen content is preferred.

The decane coupling agent (C) may be used singly or in combination of two or more kinds. However, the decane coupling agent is preferably used in an amount of 100 parts by weight of the (meth)acrylic polymer (A). The amount is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, more preferably 0.02 to 1 part by weight, still more preferably 0.05 to 0.6 part by weight. This is an amount that increases the durability and moderately maintains the adhesion to the glass and the transparent conductive layer.

The adhesive composition of the present invention may contain an ionic compound (D). The ionic compound (D) can be suitably used as an alkali metal salt and/or an organic cation-anion salt. As the alkali metal salt, an organic salt of an alkali metal and an inorganic salt can be used. Further, the term "organic cation-anion salt" as used in the present invention means an organic salt and a cationic portion thereof composed of an organic substance, and the anion portion may be an organic substance or an inorganic substance. "Organic cation-anion salts" are also known as ionic liquids and ionic solids.

<Alkali Metal Salt> The alkali metal ion constituting the cation portion of the alkali metal salt may, for example, be an ion such as lithium, sodium or potassium. Among these alkali metal ions, lithium ions are preferred.

The anion portion of the alkali metal salt may be composed of an organic substance or an inorganic substance. As the anion portion constituting the organic salt, for example, CH ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₃ C ^- , C ₄ F ₉ SO ₃ ^- , C can be used. ₃ F ₇ COO ^- , (CF ₃ SO ₂ )(CF ₃ CO)N ^- , ^- O ₃ S(CF ₂ ) ₃ SO ₃ ^- , PF ₆ ^- , CO ₃ ^{2 -} and with the following general formula (1) (4) Representation and so on: (1): (C _n F _{2n +1} SO ₂ ) ₂ N ^- (only n is an integer from 1 to 10), (2): CF ₂ (C _m F _2m SO ₂ ) ₂ N ^- (only m is an integer from 1 to 10), (3): ^- O ₃ S(CF ₂ ) _l SO ₃ ^- (only l is an integer from 1 to 10), (4): (C _p F _{2p +1} SO ₂ )N ^- (C _q F _{2q +1} SO ₂ ), (only p and q are integers from 1 to 10). In particular, the anion portion of the fluorine-containing atom is suitably used because it can obtain an ionic compound having good ion dissociation properties. The anion portion constituting the inorganic salt may be Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , (CN) ₂ N ^- and the like. The anion moiety is preferably (CF ₃ SO ₂ ) ₂ N ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- or the like (perfluoroalkylsulfonyl)imide group represented by the above formula (1), especially CF ₃ SO ₂ ) ₂ N ^{- is} preferably a (trifluoromethanesulfonyl)imide group.

The organic salt of an alkali metal may specifically be exemplified by sodium acetate, sodium alginate, sodium lignosulfonate, sodium toluenesulfonate, LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) _{2 .} N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li(C ₄ F ₉ SO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₃ C, KO ₃ S(CF ₂ ) ₃ SO ₃ K, LiO ₃ S(CF ₂ ) ₃ SO ₃ K, etc., among which are LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li(C ₄ F ₉ SO ₂ ) ₂ N, Li(CF ₃ SO ₂ ) ₃ C, etc., and Li(CF ₃ SO ₂ ) ₂ N, Li(C ₂ F ₅ SO ₂ ) ₂ N, Li(C ₄ F ₉ SO ₂ ) ₂ N and other fluorine-containing lithium sulfoxide salts are preferred, and (perfluoroalkylsulfonyl) quinone imide lithium salts are particularly preferred.

Further, examples of the alkali metal inorganic salt include lithium perchlorate and lithium iodide.

<Organic cation-anion salt> The organic cation-anion salt used in the present invention is composed of a cationic component and an anionic component, and the cationic component is an organic compound. Specific examples of the cationic component include a pyridinium cation, a piperidine cation, a pyrrolidine cation, a cation having a dihydropyrrole skeleton, a cation having a pyrrole skeleton, an imidazolium cation, a tetrahydropyrimidine cation, a dihydropyrimidinium cation, and a pyrazole. a cation, a pyrazoline cation, a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, or the like.

As the anion component, for example, Cl ^- , Br ^- , I ^- , Al ^- Cl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , CH ₃ COO ^- , CF ₃ COO ^{- may be used.} , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₃ C ^- , AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , (CN) ₂ N ^- , C ₄ F ₉ SO ₃ ^- , C ₃ F ₇ COO ^- , ((CF ₃ SO ₂ )(CF ₃ CO)N ^- , ^- O ₃ S(CF ₂ ) ₃ SO ₃ ^- and the following general formulas (1) to (4) Those shown are: (1): (C _n F _{2n +1} SO ₂ ) ₂ N ^- (only n is an integer from 1 to 10), (2): CF ₂ (C _m F _2m SO ₂ ) ₂ N ^- ( Only m is an integer from 1 to 10), (3): ^- O ₃ S(CF ₂ ) _l SO ₃ ^- (only l is an integer from 1 to 10), (4): (C _p F _{2p +1} SO ₂ ) N ^- (C _q F _{2q +1} SO ₂ ), (p, q is an integer of 1 to 10). Among them, an anion component of a fluorine atom is particularly suitable for use because it can obtain an ionic compound having good ion dissociation property.

As a specific example of the organic cation-anion salt, a compound obtained by combining the above cationic component and anionic component can be appropriately selected and used. For example, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-3-methyl Pyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine, 1-butyl-3-methylpyridinium bis(pentafluoroethanesulfonate Mercapto) quinone imine, 1-hexylpyridinium tetrafluoroborate, 2-methyl-1-dihydropyrrole tetrafluoroborate, 1-ethyl-2-phenylindole tetrafluoroborate, 1, 2-dimethylindole tetrafluoroborate, 1-ethyloxazole tetrafluoroborate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazole Pyridinium acetate, 1-ethyl-3-methylimidazolidinium trifluoroacetate, 1-ethyl-3-methylimidazolidinium heptafluorobutyrate, 1-ethyl-3-methyl Isoimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolidinium perfluorobutanesulfonate, 1-ethyl-3-methylimidazolidinium dicyanoguanamine, 1-B 3-methylimidazolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-3-methylimidazolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-B 3-methylimidazolium tris(trifluoromethanesulfonyl) methide 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium trifluoroacetic acid Ester, 1-butyl-3-methylimidazolidinium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolidinium鎓Perfluorobutanesulfonate, 1-butyl-3-methylimidazolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-hexyl-3-methylimidazolium bromide, chlorination 1 -hexyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methyl Isoimidazolium trifluoromethanesulfonate, 1-octyl-3-methylimidazolium tetrafluoroborate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-2 , 3-dimethylimidazolium tetrafluoroborate, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1-methylpyrazolium tetra Fluoroborate, 3-methylpyrazolium tetrafluoroborate, tetrahexylammonium bis(trifluoromethanesulfonyl) quinone imine, diallyldimethylammonium tetrafluoroborate, diallyl Methylammonium triflate, diene Dimethylammonium bis(trifluoromethanesulfonyl) quinone imine, diallyldimethylammonium bis(pentafluoroethanesulfonyl) quinone imine, N,N-diethyl-N- --N-(2-methoxyethyl)ammonium tetrafluoroborate, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium triflate , N,N-Diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N- --N-(2-methoxyethyl)ammonium bis(pentafluoroethanesulfonyl) quinone imine, epoxypropyltrimethylammonium triflate, epoxypropyltrimethylammonium Bis(trifluoromethanesulfonyl) quinone imine, epoxypropyltrimethylammonium bis(pentafluoroethanesulfonyl) quinone imine, 1-butylpyridinium (trifluoromethanesulfonyl)trifluoro Acetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) Fluoroacetamide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium (trifluoromethanesulfonyl)trifluoroacetamide, diallyldimethyl Alkyl ammonium (trifluoromethanesulfonyl) trifluoroacetamide, epoxypropyltrimethylammonium (trifluoromethanesulfonyl) trifluoroacetamide, N,N-dimethyl-N-ethyl -N-propyl ammonium Bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-butylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl --N-ethyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-hexylammonium bis(trifluoromethanesulfonyl)醯imino, N,N-dimethyl-N-ethyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N - mercapto ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N,N-dipropylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N- Dimethyl-N-propyl-N-butylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-amyl ammonium bis(trifluoromethyl) Sulfhydryl) quinone imine, N,N-dimethyl-N-propyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl -N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-butyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N , N-dimethyl-N-butyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-pentyl-N-hexylammonium double (three Fluoromethanesulfonyl) quinone imine, N,N-dimethyl-N,N-dihexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, trimethyl Heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-propylammonium bis(trifluoromethanesulfonyl) quinone imine, N, N -Diethyl-N-methyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-heptyl ammonium bis(trifluoro Methanesulfonyl) quinone imine, N,N-diethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, triethyl propyl ammonium bis (trifluoro Methanesulfonyl) quinone imine, triethyl amyl ammonium bis(trifluoromethanesulfonyl) quinone imine, triethylheptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N, N -dipropyl-N-methyl-N-ethylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N-methyl-N-pentyl ammonium bis(trifluoro Methanesulfonyl) quinone imine, N,N-dipropyl-N-butyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N,N - Dihexyl ammonium bis(trifluoromethanesulfonyl) sulfinium imine, N,N-dibutyl-N-methyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N, N-dibutyl-N-methyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, trioctylmethylammonium bis(trifluoromethanesulfonyl) quinone imine, N-A --N-ethyl-N-propyl-N-amyl ammonium bis(trifluoromethanesulfonate Yl) (PEI), 1-butyl-3-methyl-pyridin-1-ium triflate and the like. For the above-mentioned commercial products, for example, "CIL-314" (manufactured by Japan Carlit Co., Ltd.), "ILA2-1" (manufactured by Kyoei Chemical Co., Ltd.), or the like can be used. Further, for example, tetramethylammonium bis(trifluoromethanesulfonyl) quinone imine, trimethylethylammonium bis(trifluoromethanesulfonyl) quinone imine, and trimethylbutylammonium bis ( Trifluoromethanesulfonyl) quinone imine, trimethylammonium bis(trifluoromethanesulfonyl) quinone imine, trimethylheptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, three Methyl octyl ammonium bis(trifluoromethanesulfonyl) quinone imine, tetraethylammonium bis(trifluoromethanesulfonyl) quinone imine, triethyl butyl ammonium bis(trifluoromethanesulfonyl) Yttrium imine, tetrabutylammonium bis(trifluoromethanesulfonyl) ruthenium imine, tetrahexylammonium bis(trifluoromethanesulfonyl) ruthenium, and the like. Further, for example, 1-dimethylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1 -Methyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1 -ethyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1 -ethyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1, 1-dipropylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-propyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1- Dibutyl pyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-propylpiperidinium bis(trifluoromethanesulfonyl)醯imino, 1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dimethylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1- Methyl-1-ethylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1 propyl piperidinium bis(trifluoromethanesulfonyl) quinone imine, 1- Methyl-1-butylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1- Methyl-1-hexylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-heptylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-B 1-propylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-butylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-B -1-pentylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-hexylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl 1-heptylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dipropyl piperidinium bis(trifluoromethanesulfonyl) quinone imine, 1-propyl-1 -butylpiperidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dibutylpiperidinium bis(trifluoromethanesulfonyl) ruthenium, 1,1-dimethylpyrrole Bismuth (pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-propylpyrrolidinium double (pentafluoroethanesulfonyl) quinone imine, 1-methyl-1 butyl pyrrolidine bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-pentylpyrrolidinium double (pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1 -heptylpyrrolidinium bis ( Pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-propylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-butylpyrrolidinium bis ( Pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-pentylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-hexylpyrrolidinium bis (five Fluoroethinyl) quinone imine, 1-ethyl-1-heptylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dipropylpyrrolidinium bis(pentafluoroethyl) Sulfhydryl) quinone imine, 1-propyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dibutylpyrrolidinium bis(pentafluoroethanesulfonate)醯imino, 1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-pentylpiperidinium bis ( Fluoroethinyl) quinone imine, 1,1-dimethylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-ethylpiperidinium bis(pentafluoroethyl) Sulfhydryl) quinone imine, 1-methyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-butylpiperidinium bis(pentafluoroethyl) Sulfhydryl) quinone imine, 1-methyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-hexylpiperidinium bis(pentafluoroethanesulfonate Indole, hydrazinimide, 1-methyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-propylpiperidinium bis(pentafluoroethanesulfonate) Indole, hydrazide, 1-ethyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-pentylpiperidinium bis(pentafluoroethanesulfonate Indole, hydrazinium, 1-ethyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-heptylpiperidinium bis(pentafluoroethanesulfonate) Iridium imine, 1-propyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dipropyl piperidinium bis(pentafluoroethanesulfonyl) Yttrium imide, 1,1-dibutyl piperidinium bis(pentafluoroethanesulfonyl) ruthenium, and the like. Further, a compound obtained by substituting a cation for the cationic component of the above compound: trimethyl phosphonium cation, triethyl phosphonium cation, tributyl phosphonium cation, trihexyl phosphonium cation, diethyl methyl group a compound of a phosphonium cation, a dibutylethyl phosphonium cation, a dimethyl sulfonium cation, a tetramethyl phosphonium cation, a tetraethyl phosphonium cation, a tetrabutyl phosphonium cation, a tetrahexyl phosphonium cation, or the like. Further, a compound obtained by substituting the following anion instead of the above bis(trifluoromethanesulfonyl) quinone imide: bis(pentafluorosulfonyl) quinone imine or bis(heptafluoropropylsulfonyl) Anthraquinone, bis(nonafluorobutylsulfonyl) quinone imine, trifluoromethanesulfonyl nonafluorobutylsulfonyl quinone imine, heptafluoropropanesulfonyltrifluoromethanesulfonyl quinone imine, Pentafluoroethanesulfonyl hexafluorobutanesulfonyl quinone imine, cyclohexafluoropropane-1,3-bis(sulfonyl) quinone imine anion, and the like.

Further, the ionic compound (D) may be, for example, ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, iron chloride or ammonium sulfate in addition to the above-mentioned alkali metal salt or organic cation-anion salt. Inorganic salt. The plasma compound (D) may be used singly or in combination of two or more.

The ratio of the ionic compound (D) in the adhesive composition of the present invention is preferably 0.05 to 10 parts by weight based on 100 parts by weight of the (meth)acrylic polymer (A). When the ionic compound (D) is less than 0.05 part by weight, the effect of improving the antistatic property may be insufficient. The ionic compound (D) is preferably 0.1 part by weight or more, more preferably 0.5 part by weight or more. On the other hand, when the ionic compound (D) is more than 10 parts by weight, the durability may be insufficient. The ionic compound (D) is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, still more preferably 1 part by weight or less. The ratio of the ionic compound (D) can be set to a desired range by using the above upper limit value or lower limit value.

In the adhesive composition of the present invention, a polyether compound (E) having a reactive mercapto group may be blended. The polyether compound (E) is preferred because it can improve reworkability. As the polyether compound (E), those disclosed in, for example, Japanese Patent Laid-Open Publication No. 2010-275522 can be used.

The polyether compound (E) having a reactive mercapto group has a polyether skeleton and has a reactive mercapto group represented by the following formula (1) at least at one end: -SiR _a M _{3 -a} (wherein R is a monovalent organic group having 1 to 20 carbon atoms which may have a substituent, M is a hydroxyl group or a hydrolyzable group, and a is an integer of 0 to 2. When R is plural, a plurality of R may be the same or different, M When there are a plurality of times, a plurality of Ms may be the same or different from each other.).

As the polyether compound (E) having the aforementioned reactive sulfhydryl group, a compound shown below can be given: Formula (2): R _a M _3-a Si-XY-(AO) _n -Z (wherein R A monovalent organic group having 1 to 20 carbon atoms which may have a substituent, M is a hydroxyl group or a hydrolyzable group, and a is an integer of 0 to 2. However, when R is plural, a plurality of R may be the same or different. When M is present plural, a plurality of M's may be the same or different from each other. AO represents a linear or branched carbon number of 1 to 10, and n is 1 to 1700, which represents an average addition of an oxygen-extended alkyl group. Molar number. X represents a linear or branched alkyl group having a carbon number of 1 to 20. Y represents an ether bond, an ester bond, a urethane bond, or a carbonate bond. Z is a hydrogen atom, a monovalent carbon a hydrocarbon group of 1 to 10 and a group represented by the following formula (2A) or formula (2B): General formula (2A): -Y ¹ -X-SiR _a M _3-a (wherein R, M, X Same as the above. Y ¹ represents a single bond, a -CO- bond, a -CONH- bond or a -COO- bond.), or, general formula (2B): -Q{-(OA) _n -YX-SiR _a M _{3 -a} } _m (wherein R, M, X, and Y are the same as described above. OA is the same as AO described above, and n is the same as above. Q is a hydrocarbon group having a carbon number of 1 to 10 or more, m and the hydrocarbon group Price Same.).)

Specific examples of the polyether compound (E) having a reactive sulfhydryl group include MS polymers S203, S303, and S810 manufactured by Kanek Co., Ltd.; SILYL EST250 and EST280; SAT10, SAT200, SAT220, SAT350, SAT400, and Asahi Glass Co., Ltd. EXCESTAR S2410, S2420 or S3430, etc.

The ratio of the polyether compound (E) in the adhesive composition of the present invention is preferably 0.001 to 10 parts by weight based on 100 parts by weight of the (meth)acryl-based polymer (A). When the polyether compound (E) is less than 0.001 part by weight, the effect of improving the reworkability may be insufficient. The polyether compound (E) is preferably 0.01 parts by weight or more, and more preferably 0.1 part by weight or more. On the other hand, when the polyether compound (E) is more than 10 parts by weight, the durability is poor. The polyether compound (E) is preferably 5 parts by weight or less, more preferably 2 parts by weight or less. The ratio of the above polyether compound (E) can be set to a desired range by using the above-mentioned upper limit 値 or lower limit 値.

Further, the adhesive composition of the present invention may contain other known additives. For example, a polyether compound such as a polyalkylene glycol such as polypropylene glycol, a colorant, a pigment, or the like may be appropriately added depending on the intended use. , surfactant, plasticizer, tackifier, surface lubricant, leveling agent, softener, antioxidant, anti-aging agent, light stabilizer, ultraviolet absorber, polymerization inhibitor, inorganic or organic filler, Metal powder, particles, foil, and the like. Further, a redox system to which a reducing agent is added may also be employed within a controllable range. The amount of the additive is preferably 5 parts by weight or less based on 100 parts by weight of the (meth)acryl-based polymer (A), and further preferably 3 parts by weight or less, and further preferably 1 part by weight or less.

The adhesive layer is formed by the above-mentioned adhesive composition, and when the adhesive layer is formed, the addition amount of the entire crosslinking agent should be adjusted, and the influence of the crosslinking treatment temperature and the crosslinking treatment time should be fully considered.

The crosslinking treatment temperature and the crosslinking treatment time can be adjusted by using the crosslinking agent used. The crosslinking treatment temperature is preferably 170 ° C or less.

Further, the crosslinking treatment may be carried out at a temperature at the drying step of the adhesive layer, or may be carried out by additionally providing a crosslinking treatment step after the drying step.

Further, the cross-linking treatment time can be set in consideration of productivity and workability, but it is usually about 0.2 to 20 minutes, and preferably about 0.5 to 10 minutes.

The above-mentioned cross-linking is controlled such that the gel fraction of the above-mentioned adhesive layer is usually 50% by weight or more, but from the viewpoint of high-temperature durability, the gel fraction of the above-mentioned adhesive layer is preferably controlled to exceed 70% by weight. The gel fraction is preferably 75% by weight, more preferably 80% by weight or more. On the other hand, when the gel fraction is too high, peeling tends to occur in the durability test. Therefore, the gel fraction is preferably 98% by weight or less, and more preferably 95% by weight or less.

In the optical member with an adhesive layer such as an adhesive layer optical film of the present invention, an adhesive layer is formed on at least one side of the optical film by using the above-described adhesive composition.

The method of forming the pressure-sensitive adhesive layer can be produced, for example, by applying the above-mentioned pressure-sensitive adhesive composition to a release-treated separator or the like, drying and removing a polymerization solvent or the like to form an adhesive layer. A method of transferring to an optical film; or a method of applying the above-described adhesive composition to an optical film, drying a polymerization solvent or the like to form an adhesive layer on an optical film, or the like. Further, when the adhesive is applied, one or more solvents other than the polymerization solvent may be appropriately added.

For the release-treated separator, it is preferred to use a polyoxynitride strip. In the step of applying the adhesive composition of the present invention to the lining material and drying it to form an adhesive layer, a suitable and appropriate method can be employed as a method of drying the adhesive. It is desirable to use a method of heating and drying the above coating film. The heating and drying temperature is preferably from 40 ° C to 200 ° C, more preferably from 50 ° C to 180 ° C, and particularly preferably from 70 ° C to 170 ° C. An adhesive having excellent adhesive properties can be obtained by setting the heating temperature to the above range.

The drying time can be suitably and suitably used. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.

Further, an anchor layer may be formed on the surface of the optical film, or an adhesive layer may be formed after various easy-to-treat treatments such as corona treatment and plasma treatment. Further, it is also possible to carry out an easy subsequent treatment on the surface of the adhesive layer.

Various methods can be used to form the adhesive layer. Specific examples thereof include roll coating, contact roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roller coating, bar coating, blade coating, air knife coating, and curtain. Coating, lip coating, a method such as a die coating method using a die coater or the like.

The thickness of the adhesive layer is not particularly limited, and is, for example, about 1 to 100 μm. It is preferably 2 to 50 μm, preferably 2 to 40 μm, more preferably 5 to 35 μm.

When the adhesive layer is exposed, the adhesive layer may be protected by a release-treated sheet (separator) before being used for practical use.

The constituent material of the separator may, for example, be a plastic film such as polyethylene, polypropylene, polyethylene terephthalate or polyester film, a porous material such as paper, cloth or non-woven fabric, a net, a foamed sheet, or the like. A suitable thin film or the like such as a metal foil and a laminate thereof, but a plastic film is suitable from the viewpoint of excellent surface smoothness.

The plastic film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer, and examples thereof include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, and a polymethylpentene film. A polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, or the like.

The thickness of the separator is generally 5 to 200 μm, preferably about 5 to 100 μm. In the separator, it is also possible to use a release agent such as an oxygen-based, fluorine-based, long-chain alkyl or fatty acid amide-based release agent, a vermiculite powder, or the like for release and antifouling treatment, or a coating type or kneading. Antistatic treatment such as type and evaporation. In particular, by appropriately performing a release treatment such as polyfluorination treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the separator, the peeling property from the pressure-sensitive adhesive layer can be further improved.

Further, the release-treated sheet used in the production of the above-mentioned optical film with an adhesive layer can be directly used as a separator of an optical film with an adhesive layer, and the engineering surface can be simplified.

As the optical film, an image display device which can be used for forming a liquid crystal display device or the like is used, and the kind thereof is not particularly limited. For example, a polarizing film can be mentioned as an optical film. The polarizing film is generally used as a transparent protective film on one or both sides of the polarizing member.

The polarizer is not particularly limited, and various polarizers can be used. The polarizing material may be a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film or an ethylene-vinyl acetate copolymer-based partially saponified film, which adsorbs iodine or a dichroic dye. The coloring material is uniaxially stretched, and a polyene-based alignment film such as a dehydrated material of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride is used. Among them, a polarizing member composed of a polyvinyl alcohol-based film and a dichroic substance such as iodine is particularly preferable. The thickness of the polarizers is not particularly limited, but is generally about 80 μm or less.

A polarizing material obtained by dyeing a polyvinyl alcohol-based film with iodine and uniaxially stretching can be obtained by, for example, immersing a polyvinyl alcohol-based film in an aqueous iodine solution and dyeing it to a length of 3 to 7 times. to make. It may also be immersed in an aqueous solution containing potassium iodide or the like such as boric acid or zinc sulfate or zinc chloride as needed. Further, it is also possible to immerse the polyvinyl alcohol-based film in water for washing with water before dyeing. By washing the polyvinyl alcohol-based film with water, the dirt and the anti-caking agent on the surface of the polyvinyl alcohol-based film can be washed, and the polyvinyl alcohol-based film can be swollen to prevent unevenness such as uneven dyeing. The extension may be carried out after dyeing with iodine, or may be dyed while stretching, or may be dyed with iodine after stretching. It can also be extended in an aqueous solution of boric acid, potassium iodide or the like or in a water bath.

Further, as the polarizing material, a thin polarizing member having a thickness of 10 μm or less can be used. From the viewpoint of thinning, it is preferred that the thickness be 1 to 7 μm. Such a thin polarizer is preferred because it has less thickness unevenness and is excellent in visibility, and has a small dimensional change, so that durability is excellent, and the thickness of the polarizing plate is also reduced in thickness.

As a thin type of polarizing member, for example, Japanese Patent Laid-Open Publication No. Sho 51-069644, Japanese Patent Laid-Open Publication No. 2000-338329, No. WO2010/100917, and PCT/JP2010/001460 Or a thin polarizing film described in the specification of Japanese Patent Application No. 2010-269002 and the specification of No. 2010-263692. The thin polarizing film can be obtained by a method comprising the steps of: extending a polyvinyl alcohol-based resin (hereinafter also referred to as a PVA-based resin) layer and a resin substrate for stretching in a state of being laminated; The step of dyeing. According to this production method, even if the PVA-based resin layer is thinned, it can be extended by the resin substrate for stretching, and can be extended without defects such as cracking due to elongation.

As the thin polarizing film, in the method of including the step of stretching in the state of the laminated body and the dyeing step, it is possible to extend at a high magnification and enhance the polarizing performance, and it is preferably as described in WO2010/100917, PCT/JP2010/ The method of the method of performing the step of extending in an aqueous solution of boric acid as described in the specification of 001460, or the specification of Japanese Patent Application No. 2010-269002, and the specification of Japanese Patent Application No. 2010-263692, especially preferably by Japanese Patent Application The method described in the specification of the Japanese Patent Application No. 2010-263692, which is incorporated in the specification of the Japanese Patent Application No. 2010-263692, includes a process for performing an auxiliary aerial extension step before extending in an aqueous boric acid solution.

As the material constituting the transparent protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture resistance, and isotropic properties can be used. Specific examples of such a thermoplastic resin include cellulose resins such as cellulose triacetate, polyester resins, polyether oxime resins, polyfluorene resins, polycarbonate resins, polyamide resins, and polyimide resins. A mixture of a polyolefin resin, a (meth)acrylic resin, a cyclic polyolefin resin (northene-based resin), a polyarylate resin, a polystyrene resin, a polyvinyl alcohol resin, and the like. Further, a transparent protective film is bonded to one side of the polarizer by an adhesive layer, and on the other side, (meth)acrylic, urethane-based, urethane-based, epoxy-based, or the like can be used. A thermosetting resin such as polyoxymethylene or an ultraviolet curable resin is used as the transparent protective film. One or more optional additives may be contained in the transparent protective film. The additive may, for example, be an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a release agent, a coloring preventive agent, a flame retardant, a nucleating agent, an antistatic agent, a pigment, a colorant or the like. In the transparent protective film, the thermoplastic resin is preferably contained in an amount of from 50 to 100% by weight, preferably from 50 to 99% by weight, more preferably from 60 to 98% by weight, particularly preferably from 70 to 97% by weight. In the transparent protective film, when the content of the thermoplastic resin is 50% by weight or less, the thermoplastic resin may not sufficiently exhibit the high transparency and the like which it originally has.

The adhesive used for bonding the polarizer and the transparent protective film is not particularly limited as long as it is optically transparent, and various forms of water, solvent, hot melt, radical hardening, and cationic hardening can be used. The subsequent agent is preferably a water-based adhesive or a radical-curable adhesive.

Further, the optical film may be, for example, a reflecting plate or a reflection transmissive plate, a phase difference plate (including a 1/2 or 1/4 wavelength plate), an optical compensation film, a visual compensation film, a brightness enhancement film, or the like to form a liquid crystal display device. Used and can be an optical layer. In addition to being used as an optical film alone, it can be used by laminating one or more layers on the polarizing film in actual use.

The optical film in which the optical layer is laminated on the polarizing film may be formed by sequentially laminating in a process of manufacturing a liquid crystal display device or the like, but in order to form an optical film in advance, quality stability and assembly work are required. Excellent in terms of advantages, and has the advantage of being able to improve the process of a liquid crystal display device or the like. An appropriate bonding means such as an adhesive layer can be used for lamination. When the polarizing film is bonded to another optical layer, the optical axis of the polarizing film can be set to an appropriate arrangement angle in accordance with the target phase difference characteristic or the like.

The optical film with an adhesive layer of the present invention can be suitably used in various image display devices and the like for forming a liquid crystal display device or the like. The formation of the liquid crystal display device can be carried out in accordance with the conventional art. In other words, the liquid crystal display device is generally formed by appropriately assembling a display panel such as a liquid crystal element, an optical film with an adhesive layer, and an illumination system such as a required illumination device, and mounting a driver circuit or the like. The optical film with an adhesive layer of the present invention is not particularly limited as long as it is not limited thereto, and it is customary. For the liquid crystal element, for example, a TN type, an STN type, a π type, a VA type, an IPS type, or the like can be used.

A liquid crystal display device in which an optical film with an adhesive layer is disposed on one side or both sides of a display panel such as a liquid crystal element, or an appropriate liquid crystal display device such as a backlight or a reflector for an illumination system can be formed. In this case, the optical film of the adhesive layer of the present invention may be disposed on one side or both sides of the display panel such as a liquid crystal element. When the optical film is disposed on both sides, the same may be the same or different. Further, when forming a liquid crystal display device, suitable components such as a diffusion layer, an antiglare layer, an antireflection film, a protective plate, a ruthenium array, a lens array sheet, a light diffusion sheet, and a backlight can be disposed in a proper position at a suitable position. Or 2 or more layers. Example

The invention is specifically illustrated by the following examples, but the invention is not limited by the examples. In addition, parts and % in each case are based on weight. The room temperature conditions which are not specifically defined below are 23 ° C and 65% RH.

<Measurement of Weight Average Molecular Weight of (Meth)Acrylic Polymer (A)> The weight average molecular weight (Mw) of the (meth)acrylic polymer (A) is measured by GPC (gel permeation chromatography) . Mw/Mn was also measured in the same manner.・Analytical device: Tosoh (Tosoh) company, HLC-8120GPC ・Pipe column: Tosoh (Tosoh) company, G7000H _XL +GMH _XL +GMH _XL・Column size: each 7.8mmφ×30cm 90cm ・Tub column temperature: 40°C ・Flow rate: 0.8mL/min ・Injection amount: 100μL ・Solution solution: Tetrahydrofuran ・Detector: Differential refractometer (RI) ・Standard sample: Polystyrene

<Preparation of Polarized Film> A polyvinyl alcohol film having a thickness of 80 μm was stretched to 3 times while being dyed in a iodine solution at 30° C. and a 0.3% concentration for 1 minute between rolls having different speed ratios. Thereafter, the mixture was immersed in an aqueous solution containing 4% of boric acid and 10% of potassium iodide at 60 ° C for 0.5 minutes, and then extended to a total stretching ratio of 6 times. Subsequently, the mixture was immersed in an aqueous solution containing potassium iodide at a concentration of 1.5% at 30 ° C for 10 seconds to be washed, and then dried at 50 ° C for 4 minutes to obtain a polarizing member having a thickness of 30 μm. The saponified cellulose triacetate film having a thickness of 80 μm was bonded to both surfaces of the polarizer via a polyvinyl alcohol-based adhesive to form a polarizing film.

Example 1 (Preparation of Acrylic Polymer (A1)) A monomer mixture was charged into a 4-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a cooler, and contained 77 parts of butyl acrylate and phenoxy acrylate. 16 parts of ester, 6 parts of N-vinyl-2-pyrrolidone and 1 part of 4-hydroxybutyl acrylate. Next, 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator and 100 parts of ethyl acetate were put together with 100 parts of the above-mentioned monomer mixture (solid content), and nitrogen gas was introduced while stirring slowly. After the nitrogen substitution, the liquid temperature in the flask was maintained at around 55 ° C, and polymerization was carried out for 8 hours to prepare a solution of an acrylic polymer (A1) having a weight average molecular weight (Mw) of 1.8 million and Mw/Mn = 4.1.

(Preparation of Adhesive Composition) The isocyanate crosslinking agent was blended with 100 parts of the solid content of the acrylic polymer (A1) solution obtained in Production Example 1 (Takenate D160N, Trimethylolpropane hexamethine manufactured by Mitsui Chemicals, Inc.) 0.2 parts of bis-isocyanate), 0.2 parts of benzoyl peroxide (NYPER BMT manufactured by Nippon Oil & Fats Co., Ltd.) and γ-glycidoxypropyl methoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403) 0.2 parts A solution of the acrylic adhesive composition is prepared.

<Preparation of Polarizing Film Attached to Adhesive Layer> Next, a solution of the above acrylic adhesive composition is subjected to a polyethylene terephthalate film treated with a polyoxynitride-based release agent (separation film: Mitsubishi Chemical Polymerization) On one side of the ester film (MRF38), the thickness of the adhesive layer after drying was applied to a thickness of 23 μm, and dried at 155 ° C for 1 minute to form an adhesive layer on the surface of the separation film. . Next, the adhesive layer formed on the separation film was transferred onto the polarizing film prepared above to form a polarizing film with an adhesive layer.

Examples 2 to 15 and Comparative Examples 1 to 8 In Example 1, as shown in Table 1, the types of monomers used in preparing the acrylic polymer (A) and the ratios thereof were used, and the production conditions were controlled to prepare A solution of an acrylic polymer having a polymer property (weight average molecular weight, Mw/Mn) as described in Table 1.

Further, as shown in Table 1, the amount of the crosslinking agent (B) or the amount thereof and the amount of the decane coupling agent (C) were changed as shown in Table 1, except for the solution of each of the obtained acrylic polymers. A solution of the acrylic adhesive composition was prepared in the same manner as in Example 1. Further, a polarizing plate with an adhesive layer was produced by using a solution of the acrylic pressure-sensitive adhesive composition in the same manner as in Example 1. Further, in Examples 12 to 14 and Comparative Example 4, a solution of an acrylic polymer in which the ionic compound (D) was blended at a ratio shown in Table 1 was prepared.

The polarizing film with the adhesive layer obtained in the above Examples and Comparative Examples was subjected to the following evaluation. The evaluation results are shown in Tables 1 and 2. Further, the measurement of the surface resistance 値 was carried out only on the polarizing films of the adhesive layers obtained in Examples 12 to 14 and Comparative Example 4.

<Measurement of gel fraction> About 0.1 g of an adhesive layer was taken and wrapped in a pre-weighed fluororesin film (TEMISH NTF-1122, manufactured by Nitto Denko Co., Ltd.) (weight: Wa), and The test sample is prepared by not tying the adhesive to bleed out. The weight of the sample (weight: Wb) was measured, placed in a bottle, and 40 cc of ethyl acetate was added and allowed to stand for 7 days. Thereafter, the measurement sample was taken out, and the measurement sample was dried at 130 ° C for 2 hours. The weight (Wc) of the sample after drying was measured, and the gel fraction was determined by the following formula. [Number 1]

<Endurance Test on Glass> The polarizing film with the adhesive layer was cut into a size of 37 Å as a sample. This sample was attached to an alkali-free glass (manufactured by Corning Incorporated, EG-XG) having a thickness of 0.7 mm using a laminator. Subsequently, autoclaving was carried out for 15 minutes at 50 ° C and 0.5 MPa, and the above sample was completely adhered to the alkali-free glass. The sample subjected to the treatment is subjected to a treatment at 500 ° C for 500 hours (heating test), and then subjected to a treatment at 500 ° C / 95% RH for 500 hours (humidification test), and then After an environment of 85 ° C and -40 ° C was applied for 300 cycles in one cycle for one hour (thermal shock test), the appearance between the polarizing plate and the glass was visually evaluated by the following criteria. (Evaluation criteria) ◎: There was no change in appearance such as foaming or peeling. 〇: There is slight peeling or foaming at the end, but there is no problem in practical use. △: There was peeling or foaming at the end portion, but there was no problem in practical use in the range in which the outer frame was blocked. ×: There is a significant peeling at the end, which is practically problematic.

<Durability Test of ITO Glass> The alkali-free glass used as the object to be attached in the above-mentioned <Persistence Test for Glass>, the substance on which the crystalline ITO or the amorphous ITO layer is formed is referred to as < Durability test of ITO glass > attached. The durability test of the ITO glass was carried out in the same manner as in the above <Hardness Test for Glass> except that the adherend was changed as described above and the sample was bonded to the ITO layer. The ITO layer is formed by sputtering. In the composition of ITO, the Sn ratio of the crystalline ITO was 10% by weight, and the Sn ratio of the amorphous ITO was 3% by weight. The heating step of 140 ° C × 60 minutes was carried out before the bonding of the samples. Further, the Sn ratio of ITO is calculated from the weight of Sn atom / (weight of Sn atom + weight of In atom).

<metal corrosion resistance> A polarizing film with an adhesive layer was cut into a sample of 8 mm × 8 mm as a sample. A conductive film (trade name: ELECTRYSTA (P400L), manufactured by Nitto Denko Corporation) having an ITO layer formed on the surface of the film was cut into 15 mm × 15 mm, and the sample was bonded to the center of the conductive film. The part was then autoclaved at 50 ° C and 5 atm for 15 minutes, and then used as a measurement sample for corrosion resistance. The electric resistance 値 of the obtained measurement sample was measured using a measuring device described later, and this was referred to as "initial resistance 値". Then, the measurement sample was placed in an environment of 60 ° C / 90% RH for 500 hours, and then the resistance 値 was measured, and the measured value was referred to as "resistance enthalpy after moist heat". Further, the above resistance value was measured using HL5500PC manufactured by Accent Optical Technologies. The "resistance 値 change" was calculated from the "initial resistance 値" and the "resistance 湿 after wet heat" as measured above. [Number 2]

<Display unevenness> The polarizing film with the adhesive layer was cut into a size of 420 mm in length × 320 mm in width, and this was used as a sample to prepare two sheets. The sample was bonded to both sides of an alkali-free glass plate having a thickness of 0.07 mm by a bonding machine so as to be orthogonally polarized. Next, autoclaving treatment was carried out for 15 minutes at 50 ° C and 5 atm as a secondary sample (initial). Next, the secondary sample was treated at 90 ° C for 24 hours (after heating). The initial and heated secondary samples were placed on a 10,000-candle backlight, and the light leakage was visually evaluated according to the following criteria. (Evaluation criteria) ◎: No corner unevenness occurred, and there was no problem in practical use. 〇: Only corner unevenness occurs slightly, but since there is no display area, there is no practical problem. △: Corner unevenness occurred but only appeared in the display area a little, and there was no problem in practical use. ×: Corner unevenness occurred and appeared in the display area, which was practically problematic.

<Electrical conductivity: surface resistance 値 (Ω/□)> After the separation film of the polarizing film with the adhesive layer was peeled off, the surface resistance 値 (initial) of the surface of the adhesive was measured. The polarizing film with the adhesive layer was placed in an environment of 60 ° C / 95% RH for 500 hours, dried at 40 ° C for 1 hour, and the separation film was peeled off, and then the surface resistance of the surface of the adhesive was measured (after moist heat). . The measurement was carried out using MCP-HT450 manufactured by Mitsubishi Chemical Corporation ANALYTECH.

<Humidification and white turbidity> The polarizing film with the adhesive layer was cut into a size of 50 mm × 50 mm and attached to the glass. Further, a PET film (Diafoil T100-25B, manufactured by Mitsubishi Plastics Co., Ltd.) having a thickness of 25 μm was cut into a size of 50 mm × 50 mm, and bonded to the upper surface of the polarizing film to prepare a sample for measurement. The measurement sample was placed in an environment of 60 ° C / 95% RH for 250 hours, and then taken out at room temperature and the haze value after 10 minutes was measured. The haze value was measured using a haze meter HM150 manufactured by Murakami Color Research Co., Ltd.

【Table 1】

In Table 1, the monomer used in the preparation of the acrylic polymer (A) is represented by BA: butyl acrylate, PEA: phenoxyethyl acrylate, NVP: N-ethyl-pyrrolidone, NVC: N-ethyl - ε-caprolactam, HBA: 4-hydroxybutyl acrylate, HEA: 2-hydroxyethyl acrylate, AA: acrylic acid. "D160N" of the "isocyanate system" in the crosslinking agent (B) means Takenate D160N (trimethylolpropane hexamethylene diisocyanate adduct) manufactured by Mitsui Chemicals Co., Ltd., and "C/L" means Japan. Coronate L (trimethylolpropane toluene diisocyanate adduct) manufactured by Polyurethane Industry Co., Ltd.; "Peroxide system" means benzammonium peroxide (manufactured by Nippon Oil Co., Ltd., NYPER BMT); "Cetane coupling agent (C)" means KBM403, which is KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.; "Ionic compound (D)" means: Li-TFSI: bis(trifluoromethanesulfonate) manufactured by Mitsubishi Material Co., Ltd. Lithium quinone iodide; EMP-TFSI: 1-ethyl-1-methylpyrrolidinium bis(trifluoromethanesulfonate) imide produced by Mitsubishi Material Corporation.

【Table 2】

(no)

Claims (15)

An adhesive composition for an optical film, which comprises a (meth)acrylic polymer (A) and an amount of 0.01 to 3 parts by weight based on 100 parts by weight of the (meth)acrylic polymer (A). The crosslinking agent (B), the (meth)acrylic polymer (A) contains the following monomer as a monomer unit: 33% by weight or more of alkyl (meth)acrylate (a1), 3 to 25% by weight An aromatic ring (meth) acrylate (a2), 5 to 35% by weight of an N-vinyl containing decylamine monomer (a3), and 0.01 to 7% by weight of a hydroxyl group-containing monomer (a4) . The adhesive composition for an optical film according to claim 1, wherein the (meth)acrylic polymer (A) further contains 2% by weight or less of a carboxyl group-containing monomer (a5) as a monomer unit. The adhesive composition for an optical film according to claim 1 or 2, wherein the hydroxyl group-containing monomer (a4) is 4-hydroxybutyl (meth)acrylate. The adhesive composition for an optical film according to any one of claims 1 to 3, wherein the crosslinking agent (B) contains at least one selected from the group consisting of an isocyanate crosslinking agent and a peroxide crosslinking agent. The adhesive composition for an optical film according to claim 4, wherein the isocyanate crosslinking agent contains an aliphatic polyisocyanate compound. The adhesive composition for an optical film according to any one of claims 1 to 5, which further contains a decane coupling agent (C). The adhesive composition for an optical film according to claim 6, wherein the decane coupling agent (C) is contained in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the (meth)acryl-based polymer (A). The adhesive composition for an optical film according to any one of claims 1 to 7, which further contains an ionic compound (D). The adhesive composition for an optical film according to claim 8, wherein the ionic compound (D) is an alkali metal salt and/or an organic cation-anion salt. The adhesive composition for an optical film according to claim 8, wherein the ionic compound (D) contains a fluorine-containing anion. The adhesive composition for an optical film according to any one of claims 8 to 10, wherein the ionic compound (D) is 0.05 to 10 with respect to 100 parts by weight of the (meth)acrylic polymer (A). Parts by weight. An adhesive layer for an optical film, which is characterized in that it is formed of an adhesive composition for an optical film according to any one of claims 1 to 11. The adhesive layer for an optical film according to claim 12, which has a gel fraction of more than 70% by weight. An optical film with an adhesive layer, characterized in that at least one side of the optical film is formed with an adhesive layer for an optical film according to claim 12 or 13. An image display device characterized by the use of at least one layer of an optical film such as the adhesive layer of claim 14.