TWI645010B - Resin film with adhesive and optical laminate using the same - Google Patents

Abstract

An object of the present invention is to provide an adhesive-attached resin film which is excellent in durability under severe environments even if an optical film which is easily deformed is used as a resin film, and the adhesive-attached resin film is bonded to a liquid crystal. Optical laminated body made of glass substrates such as cells.

The solution of the present invention is a resin film with an adhesive provided with an adhesive layer formed of an adhesive composition containing a first acrylic resin on the surface of the resin film. The weight ratio of the carbonyl group present in the acrylic resin calculated from the compounding ratio of the monomer and the weight of the carbonyl group per molecule of the monomer is 24% or more. The above-mentioned adhesive layer system may be formed of an adhesive composition containing (A) 100 parts by weight of a first acrylic resin, (B) 0.1 to 1 part by weight of an isocyanate-based crosslinking agent, and (C) 0.05 to 5 parts by weight of a silane compound. .

Description

Adhesive-attached resin film and optical laminated body using the same

The present invention relates to an adhesive-attached resin film having an adhesive layer formed on a film surface. Examples of the resin film include an optical film including a polarizing plate and a retardation film. Moreover, this invention relates to the optical laminated body for liquid crystal displays which laminated | stacked the resin film with the resin film with an adhesive agent which consists of an optical film on a glass substrate.

A polarizing plate is mounted on a liquid crystal display device and is widely used. This polarizing plate is generally formed by laminating a transparent resin film as a protective film on at least one side of the polarizing film. In addition, a transparent resin film (a retardation film) that imparts a retardation is also formed by laminating a polarizing plate. (Ellipsoidal polarizer). These polarizing plates are provided with an adhesive layer on the surface of the protective film or the retardation film, and circulate in a state where a release film is adhered to the adhesive layer. In this specification, the above-mentioned polarizing plate, elliptically polarizing plate, retardation film, and the like are collectively referred to as an optical film. An optical film provided with an adhesive layer is used to serve as a liquid crystal display device after the release film is peeled off from the adhesive layer and then bonded to the liquid crystal cell via the exposed adhesive layer.

When the above liquid crystal display device is exposed to high temperature or high humidity Under thermal conditions or repeated heating and cooling conditions, dimensional changes occur in the optical film as the constituent member, and sometimes foaming of the adhesive layer occurs, or between the optical film and the adhesive layer or the adhesive. Floating or peeling occurs between the layer and the liquid crystal cell. Therefore, there is a demand for a liquid crystal display device that does not cause such a defect and has excellent durability.

As one of the countermeasures, the development of an adhesive layer was performed. For example, in Japanese Patent No. 3997270 (Patent Document 1), it is described that the following acrylic adhesive composition is used as an adhesive for an optical film, and the acrylic adhesive composition uses an aromatic-containing monomer as a copolymer. By polymerizing a specific (meth) acrylic polymer, when an optical film (optical member) having the adhesive layer formed thereon is adhered to a glass substrate, the size change due to the optical member can be alleviated. The stress caused, or to prevent peeling or foaming under high humidity and heat conditions. However, although such an adhesive composition exhibits sufficient durability in a test in a general temperature range, in a test in which a severe use environment such as a vehicle-mounted application is assumed, there is a problem between the adhesive layer and the liquid crystal cell. Floating or peeling occurs. In particular, the floating or peeling is more prominently observed when the moisture permeability of the optical film to which the adhesive layer is bonded is low.

As an adhesive agent for improving durability under the severe use environment described above, for example, in Japanese Patent No. 4134350 (Patent Document 2), a monomer using (meth) acrylate and having a hydroxyl group in the molecule is described. The monomer and the monomer having a specific functional group in the molecule are used as monomer components of the acrylic polymer contained in the adhesive composition. In addition, Japanese Patent Application Laid-Open No. 2012-196953 (Patent Document 3) describes that A specific acrylic resin adhesive composition, and this example shows that the adhesive composition has sufficient durability even when used in an optical film with low moisture permeability.

On the other hand, liquid crystal display devices have been gradually applied to portable devices such as mobile phones and in-vehicle navigation systems in recent years, and they have been required to be thinner, lighter, and lower in cost. Therefore, the protective film used for the liquid crystal display device is also required to be converted into a thin film or a cheap resin film that can achieve a film, and a thinner film or a resin film with lower rigidity than the conventional protective film is sometimes used. However, with such a protective film, the shrinkage suppressing power of the polarizing film is insufficient, and the resulting polarizing plate tends to be easily deformed. In addition, when the polarizing plate is applied to a liquid crystal display device of a liquid crystal cell, there is still a problem that the durability is insufficient in a severe environment.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 3997270 (Japanese Patent Laid-Open No. 2007-138056)

[Patent Document 2] Japanese Patent No. 4134350 (Japanese Patent Laid-Open No. 2004-91500)

[Patent Document 3] Japanese Patent Laid-Open No. 2012-196953

The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide an optical film that is easily deformed as a resin, for example. A film, an adhesive-attached resin film which is also excellent in durability under severe environments, and an optical laminated body formed by bonding the adhesive-attached resin film to a glass substrate typified by a liquid crystal cell.

That is, the present invention provides an adhesive-attached resin film. An adhesive layer formed of an adhesive composition containing a first acrylic resin is provided on a surface of the resin film, and is characterized in that: The weight ratio of the carbonyl groups present in the acrylic resin obtained from the blending ratio of the monomers used and the weight of the carbonyl groups per molecule of the monomers is 24% or more.

The adhesive layer in the above-mentioned adhesive-attached resin film may be formed of an adhesive composition containing the following (A), (B), and (C): (A) is composed of a unit including the following (a1) to (a4) 100% by weight of the first acrylic resin having a weight average molecular weight of 500,000 to 1.7 million: (a1) alkyl (meth) acrylate 60 to 96.99% by weight, (a2) having 1 in the molecule 2 to 30% by weight of unsaturated monomers having an olefinic double bond and at least one aromatic ring, (a3) 0.01 to 2% by weight of unsaturated monomers having a carboxyl group, and (a4) selected from unsaturated monomers having a hydroxyl group 1 to 8% by weight of at least one monomer in the group consisting of a polymer, an unsaturated monomer having an amidine bond, and an unsaturated monomer having an amine group; (B) an isocyanate-based crosslinking agent 0.1 to 1% by weight And (C) a silane compound of 0.05 to 5 parts by weight.

The alkyl (meth) acrylate (a1) preferably contains at least an alkyl acrylate having an alkyl group having 1 to 3 carbon atoms, and a carbon number of 4 to 4 having an alkoxy group which may be substituted with 1 to 10 carbon atoms. 14 alkyl (methyl) A mixture of alkyl acrylates.

The resin film of the present invention may be an optical film selected from a polarizing plate and a retardation film. This polarizing plate may be one in which a protective film, a polarizing film, and a retardation film are sequentially laminated. The protective film is made of a transparent resin film made of a second acrylic resin. The retardation film is selected from a cycloolefin resin and a fiber. A resin film composed of a resin composed of a plain resin, a polyester resin, and a polycarbonate resin. In addition, the above-mentioned optical film can be used: a warpage amount after being held at 85 ° C. for 24 hours in a state of being adhered to a glass having a thickness of 0.5 mm through a commercially available adhesive layer, and the absolute value is 1400 μm or more .

In the present invention, the tensile elastic modulus of the adhesive layer at a temperature of 23 ° C. is preferably 0.22 MPa or more. In addition, the adhesive-attached resin film of the present invention is a surface-attachable release film on the surface of the adhesive layer.

When the resin film is an optical film, an optical laminate for liquid crystal display can be formed by laminating a liquid crystal cell on the side of the adhesive layer. The present invention also provides such an optical laminate.

According to the present invention, for example, a resin film composed of an optical film and laminated on a glass substrate of a liquid crystal cell can obtain an optical laminated body for a liquid crystal display. Even if this optical laminate constitutes an optical film that is liable to undergo deformation such as dimensional change or curling under severe environments such as assumed in-vehicle applications, the adhesive layer can suppress deformation, and because of this, The adhesive layer strongly bonds the optical film and the liquid crystal cell, so it can be suppressed at the interface between the optical film and the adhesive layer, or the interface between the adhesive layer and the liquid crystal cell. Floating, peeling, etc. occur, and it is excellent in this durability.

1‧‧‧ polarizing film

2‧‧‧ surface treatment layer

3‧‧‧ (first) protective film

4‧‧‧Second protective film

5‧‧‧ polarizing plate

7‧‧‧ retardation film

8‧‧‧ interlayer adhesive

10‧‧‧ Optical Film

20‧‧‧ Adhesive layer attached to liquid crystal cell (glass substrate)

25‧‧‧Resin film with adhesive

30‧‧‧LCD cell (glass substrate)

40‧‧‧ Optical Laminate

Figs. 1 (A) to (D) are schematic cross-sectional views showing examples of preferred layer configurations of the optical multilayer body of the present invention.

Hereinafter, the present invention will be described in detail. The adhesive-attached resin film of the present invention is provided on the resin film with an adhesive layer formed of an adhesive composition containing a first acrylic resin as a main component. The first acrylic resin is characterized by the following characteristics: The weight ratio of the carbonyl group present in the acrylic resin obtained from the blending ratio of the monomer used and the weight of the carbonyl group per molecule of the monomer is 24% or more. As the resin film of the present invention, an optical film including a polarizing plate and a retardation film can be used. Thus, in this specification, the resin film with an adhesive agent which comprises a resin film with an optical film may be called "an optical film with an adhesive agent." First, an adhesive layer provided on a resin film will be described.

[Adhesive layer (adhesive composition)]

In the present invention, the adhesive layer provided on the resin film is formed of an adhesive composition containing the following first acrylic resin. The first acrylic resin is prepared from a monomer blending ratio used for copolymerization and the monomer. The weight ratio of the carbonyl group present in the acrylic resin per one molecular weight of the carbonyl group is 24% or more. This adhesive composition is mainly composed of a first acrylic resin, and may contain, for example, a first acrylic resin (A), isocyanide, etc. An acid ester-based crosslinking agent (B) and a silane compound (C).

<First acrylic resin (A)>

In the present invention, it is important to form an adhesive layer from an adhesive composition containing a first acrylic resin having a weight ratio of 24% or more of the carbonyl groups present in the acrylic resin. The weight ratio of the carbonyl group existing in the acrylic resin can be obtained from the blending ratio of the monomer used in the copolymerization of the first acrylic resin and the weight of the carbonyl group per molecule of the monomer. The weight ratio of the carbonyl group is obtained by calculating the molecular weight (Mw) per molecule of the monomer and the number of carbonyl groups (N) and the molecular weight of the carbonyl group (28) for all the monomers used in the copolymerization. Calculate the weight ratio of the carbonyl group per molecule of the monomer, then multiply the blending ratio (X) of the monomer based on the total amount of the monomer used in the copolymerization of the first acrylic resin by the weight ratio, and The sum of the values obtained for each monomer is expressed as a percentage, and is then obtained by the following formula.

The carbonyl group of the monomer is a carbon-oxygen double bond existing in the molecule. Examples of the atomic group having a carbonyl group include acetamyl (CH ₃ CO-), acetamyloxy (CH ₃ COO-), aldehyde (-CHO), isocyanate (-NCO), and carbamate (-CONH ₂ ), carboxyl (-COOH), allyloxy (CH ₂ = CH-COO-), methacryloxy (CH ₂ = C (CH ₃ ) -COO-), keto ( -CO-), ester group (-COO-), amido group (-CONH-), and the like. Weight ratio of carbonyl group. When there is one carbonyl group based on 1 molecule of the monomer, the N in the above formula (I) is 1, and when there are 2 molecules in the molecule, the N in the above formula (I) is Calculate for 2.

The weight ratio of the carbonyl groups present in the acrylic resin obtained according to the above formula (I). When the value is higher, the polarity of the acrylic resin increases, so the cohesion of the adhesive can be improved. The cohesive force of the adhesive can generally be improved by adding a common cross-linking agent. However, according to this method, the adhesive layer tends to harden, and it is difficult to relax the stress generated at the interface with the adherend. The adhesive force of the adhesive layer decreases. On the other hand, if the weight ratio of the carbonyl group existing in the acrylic resin as the main component of the adhesive satisfies the above conditions, an adhesive having cohesive force and adhesiveness can be formed. In the present invention, by using this first acrylic resin as the main component of the adhesive, even when the resin film of the adhesive is bonded to a glass substrate such as a liquid crystal cell, the resin film of the optical laminate is at a high temperature or It is composed of an optical film that produces large deformation under severe conditions such as high humidity and heat environment. Since the adhesive layer can suppress the deformation of the optical film, and the optical film and the glass substrate are strongly adhered, it can be suppressed between the glass substrate and the adhesive. Floating or peeling at the interface of the layer.

When the weight ratio of the carbonyl group existing in the acrylic resin is 24% or more, even if an optical film having a large deformation is used, the durability is good. On the other hand, if the weight ratio of the carbonyl group is too high, durability can be improved, but the reworkability of the adhesive tends to decrease. Therefore, the weight ratio of carbonyl group, Practically, it is preferably 30% or less, and particularly preferably 28% or less.

This first acrylic resin may be a copolymer of monomers, and the preferred example may include an alkyl (meth) acrylate (a1) as a main component and contained in the molecule having an olefinic double bond and A copolymer obtained by a monomer mixture of an unsaturated monomer (a2) having at least one aromatic ring, an unsaturated monomer (a3) having a carboxyl group, and an unsaturated monomer (a4) having a polar group. The unsaturated monomer (a4) having a polar group is other than the unsaturated monomer (a3) having a carboxyl group, and examples thereof include unsaturated monomers having a hydroxyl group, unsaturated monomers having a amide bond, and Unsaturated monomers such as amines.

Here, the term "(meth) acrylic" refers to any of acrylic acid and methacrylic acid, and "(meth)" when referred to as (meth) acrylate has the same meaning. In addition, in this specification, the (meth) acrylic acid alkyl ester (a1) may only be referred to as a "monomer (a1)", and only one olefinic double bond and at least one aromatic ring in the molecule will Saturated monomer (a2) is called "monomer (a2)", unsaturated monomer (a3) having a carboxyl group is called "monomer (a3)", and unsaturated monomer (a4) having a polar group is only ) Is called "monomer (a4)".

The alkyl (meth) acrylate (a1) is represented by the following formula (II). Here, R ₁ is a hydrogen atom or a methyl group, and R ₂ is an alkyl group having 1 to 14 carbon atoms. In the alkyl group represented by R ₂ , a hydrogen atom in each group may be substituted by an alkoxy group having 1 to 10 carbon atoms.

Specific examples of the alkyl (meth) acrylate represented by the formula (II) include linear chains of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-octyl acrylate, and lauryl acrylate. Alkyl acrylate; Isopropyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, etc. branched alkyl acrylate; methyl methacrylate, ethyl methacrylate, methacrylic acid Linear alkyl methacrylates such as propyl ester, n-butyl methacrylate, n-octyl methacrylate, and lauryl methacrylate; isobutyl methacrylate, 2-ethylhexyl methacrylate, and Branched alkyl methacrylate and the like, such as isooctyl methacrylate and the like.

When R _{2 is} an alkyl group substituted by an alkoxy group, that is, when R ₂ is an alkoxyalkyl group, an alkyl (meth) acrylate represented by the formula (II) may be specifically illustrated as 2-methyl acrylate Ethoxyethyl, ethoxymethyl acrylate, 3-methoxybutyl acrylate, 4-methoxypentyl acrylate, 8-octyl acrylate, 2-methoxyethyl methacrylate, methacrylic acid Ethoxymethyl and so on.

The alkyl (meth) acrylate (a1) may be composed of one type of monomer or a mixture of two or more types. In the present invention, a mixture of two or more types of monomers is preferred. This preferred example includes at least an alkyl acrylate having an alkyl group having 1 to 3 carbon atoms and an alkyl group having 4 to 14 carbon atoms which may be substituted by an alkoxy group having 1 to 10 carbon atoms ( A mixture of alkyl (meth) acrylates.

In the alkyl acrylate having an alkyl group having 1 to 3 carbon atoms, R _{2 in} the formula (II) is an alkyl acrylate equivalent to an alkyl group having 1 to 3 carbon atoms. Among them, methyl acrylate and ethyl acrylate are preferably used, and methyl acrylate is more preferably used.

In an alkyl (meth) acrylate having an alkyl group having 4 to 14 carbon atoms which may be substituted by an alkoxy group having 1 to 10 carbon atoms, R ₂ of the above formula (II) is equivalent to having a carbon number of 1 to 10 Alkyl (meth) acrylates having 4 to 14 carbons substituted by alkoxy. Among them, n-butyl acrylate is preferably used.

Alkyl (meth) acrylate (a1), in addition to the above-mentioned alkyl acrylate having an alkyl group having 1 to 3 carbon atoms, and an alkyl group having 4 to 14 carbon atoms which may be substituted by an alkoxy group having 1 to 10 carbon atoms In addition to the (meth) acrylic acid alkyl ester, it may contain at least one (1-methyl) alkyl group having 1 to 3 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms. ) Alkyl acrylate. When formulating this compound, it is only necessary to add an appropriate amount within a range satisfying the weight ratio of the carbonyl group existing in the acrylic resin.

The monomer (a1) is an alkyl acrylate having an alkyl group having 1 to 3 carbon atoms, and a (methyl) group having an alkyl group having 4 to 14 carbon atoms which may be substituted by an alkoxy group having 1 to 10 carbon atoms. In the case of a mixture of alkyl acrylates, specifically, the blending ratio is such that the alkyl acrylate having an alkyl group having 1 to 3 carbon atoms is 25% by weight or more in all the monomers constituting the first acrylic resin (A). , Particularly preferably in a manner of 30% by weight or more, more preferably 35% by weight or more. In addition, the alkyl (meth) acrylate having an alkyl group having 4 to 14 carbon atoms which may be substituted by an alkoxy group having 1 to 10 carbon atoms is 25% by weight or more, more preferably 35% by weight or more, and more preferably 45% by weight or more To deploy. When a monomer (a1) is used as a mixture, it is preferable to use it at such a compounding ratio and satisfying the compounding quantity of the said monomer (a1). In the present invention, the alkyl (meth) acrylate (a1) is preferably a mixture containing methyl acrylate and n-butyl acrylate in the above ratio.

The monomer (a1) is preferably the above-mentioned mixture, but in addition, it may further contain: at least one of the above-mentioned carbons constituting an alkyl group having 1 to 3 carbon atoms substituted by an alkoxy group having 1 to 10 carbon atoms Alkyl (meth) acrylate is equivalent to other alkyl (meth) acrylates of formula (II). One of the preferable compositions of the monomer (a1) at this time includes, among all the monomers constituting the acrylic resin (A), 25% by weight or more, particularly preferably 30% by weight or more, more preferably 35% by weight or more of methyl acrylate, and 25% by weight or more, more preferably 35% by weight or more, more preferably 45% by weight or more, and 65% by weight or less, and most preferably 60% by weight or less Come to deploy n-butyl acrylate. When the compounding ratio of n-butyl acrylate to methyl acrylate increases, the weight ratio of the carbonyl group represented by the formula (I) decreases, and the cohesive force of the adhesive layer decreases. Therefore, the deformation of the optical film cannot be sufficiently suppressed.

The unsaturated monomer (a2) having one olefinic double bond and at least one aromatic ring in the molecule preferably has a (meth) acrylfluorenyl group as a group containing an olefinic double bond. The unsaturated monomer also includes benzyl (meth) acrylate, neopentyl glycol (meth) acrylate, and the like, but is particularly preferably a phenoxyethyl group-containing ( (Meth) acrylic compounds.

In the aforementioned formula (III) representing the phenoxyethyl-containing (meth) acrylic compound, R ₃ is a hydrogen atom or a methyl group, n is an integer of 1 to 8, R ₄ is a hydrogen atom, an alkyl group, Aralkyl or aryl. When R ₄ in the formula (III) is an alkyl group, the carbon number may be about 1 to 9, and similarly, when it is an aralkyl group, the carbon number is about 7 to 11; The number is about 6 to 10.

Examples of the alkyl group having 1 to 9 carbon atoms constituting R ₄ in formula (III) include methyl, ethyl, butyl, nonyl, and the like, and aralkyl groups having 7 to 11 carbon atoms include benzyl , Phenethyl, naphthylmethyl, and the like, and aryl groups having 6 to 10 carbon atoms include phenyl, tolyl, and naphthyl.

Examples of the (meth) acrylic compound represented by the formula (III) include 2-phenoxyethyl (meth) acrylate and 2- (2-phenoxyethoxy) ethyl (meth) acrylate Esters, (meth) acrylates of nonylphenol modified with ethylene oxide, 2- (o-phenylphenoxy) ethyl (meth) acrylate, and the like. This is equivalent to an unsaturated monomer (a2) having one olefinic double bond and at least one aromatic ring in the molecule, and can be used alone or in combination of two or more kinds. Among these, it is particularly preferable to use 2-phenoxyethyl (meth) acrylate or 2- (2-phenoxyethoxy) ethyl (meth) acrylate as a constituent of the first acrylic resin (A). One of the unsaturated monomers (a2) of the aromatic ring.

Examples of the unsaturated monomer (a3) having a carboxyl group include acrylic acid, methacrylic acid, and those represented by formula (IV).

In the formula (IV), R ₅ is a hydrogen atom or a methyl group, and A is a divalent organic group having 2 to 4 carbon atoms. The divalent organic group represented by A is typically an alkylene group. This is also preferably a linear alkylene group. However, at the (meth) acrylic acid site [CH ₂ = C (R ₅ ) COO-] Assuming that at least two carbon chains in series with the carboxyl group (-COOH) at the terminal are connected in series, they may be branched as long as the carbon is 3 or more. In formula (IV), an acrylate is preferred, and specific examples thereof include 2-carboxyethyl acrylate, 3-carboxypropyl acrylate, 4-carboxybutyl acrylate, 2-succinyloxyethyl acrylate, and the like. Of course, a compound in which these acrylates are changed to methacrylates may also be monomers (a3).

2-carboxyethyl acrylate is usually produced by dimerization of acrylic acid. In this case, in addition to 2-carboxyethyl acrylate as a main component, acrylic acid itself or an oligomer with acrylic acid terpolymer or more is obtained. The mixture is often sold directly as a mixture. In this way, of course, the copolymerization of the carboxyl group-containing (meth) acrylate (a3) represented by formula (III) with other carboxyl group-containing (meth) acrylic monomers has no effect.

The unsaturated monomer (a4) having a polar functional group is preferably at least one selected from unsaturated monomers having a hydroxyl group, unsaturated monomers having an amine bond, and unsaturated monomers having an amine group. The unsaturated monomer having a hydroxyl group is a (meth) acrylic monomer having a hydroxyl group. Examples of the unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (methyl) base) 4-hydroxybutyl acrylate, 2- (2-hydroxyethoxy) ethyl (meth) acrylate, 2- or 3-chloro-2-hydroxypropyl (meth) acrylate, diethylene glycol mono (methyl Group) acrylate and the like. Among these, 2-hydroxyethyl acrylate is preferably used as one of the monomers (a4) constituting the first acrylic resin (A).

The unsaturated monomer having a amide bond is preferably a (meth) acrylamide or a (meth) acrylamide derivative. Examples of (meth) acrylamide derivatives include N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- (3 -Hydroxypropyl) (meth) acrylamide, N- (4-hydroxybutyl) (meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N- ( 6-hydroxyhexyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (methyl Propyl) acrylamide, N- (3-dimethylaminopropyl) (meth) acrylamine, N- (1,1-dimethyl-3-oxobutyl) (meth) acrylamine Amine, N- [2- (2-oxo-1-imidazolinyl) ethyl] (meth) acrylamidonium, 2-acrylamido-2-methyl-1-propanesulfonic acid, N- (Methoxymethyl) acrylamide, N- (ethoxymethyl) (meth) acrylamide, N- (propoxymethyl) (meth) acrylamide, N- (1-methylethyl) Oxymethyl) (meth) acrylamide, N- (1-methylpropoxymethyl) (meth) acrylamide, N- (2-methylpropoxymethyl) (meth) acrylamine Amine [alias N- (isobutoxymethyl) (meth) acrylamide], N- (butoxymethyl) (meth) acrylamide, N- (1,1-dimethylethoxymethyl) (Meth) acrylamide, N- (2-methoxyethyl) ( ) Acrylamide, N- (2-ethoxyethyl) (meth) acrylamide, N- (2-propoxyethyl) (meth) acrylamide, N- [2- (1- Methylethoxy) ethyl] (meth) acrylamide, N- [2- (1-methylpropoxy) ethyl] (meth) acrylamide, N- [2- (2- Methylpropoxy) ethyl] (meth) acrylamide [alias N- (2-isobutoxyethyl) (meth) acrylamine Amine], N- (2-butoxyethyl) (meth) acrylamide, N- [2- (1,1-dimethylethoxy) ethyl] (meth) acrylamide, and the like. Among these, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (butoxymethyl) Group) acrylamide, or N- (2-methylpropoxymethyl) acrylamide.

The unsaturated monomer having an amine group is preferably a compound having an olefinic double bond and an amine group in the molecule. Examples thereof include amine ethyl (meth) acrylate and dimethyl amine ethyl (meth) acrylate. , Dimethylaminopropyl (meth) acrylate, vinylpyridine and the like.

The monomer (a4) can be prepared by selecting one monomer from an unsaturated monomer having a hydroxyl group, an unsaturated monomer having an amidine bond, and an unsaturated monomer having an amine group, or two or more types of monomers. Monomer to deploy. In addition, monomers (a4) having the same functional group and monomers having different structures may be used in combination.

When the four kinds of monomers are copolymerized, the blending amount of each monomer is based on the total amount of the monomer mixture, and is preferably an alkyl (meth) acrylate represented by formula (II), that is, a monomer ( a1) is an unsaturated monomer having 60 to 96.99% by weight and having an olefinic double bond and at least one aromatic ring in the molecule, that is, the monomer (a2) is 2 to 30% by weight and unsaturated with a carboxyl group The monomer, that is, the monomer (a3) is 0.01 to 2% by weight, and then, at least 1 is selected from unsaturated monomers having a hydroxyl group, unsaturated monomers having an amidine bond, or unsaturated monomers having an amine group. The monomer, that is, the monomer (a4) is 1 to 8% by weight. The monomer (a1) to the monomer (a4) are prepared at the ratio so defined, and the weight ratio of the carbonyl group existing in the acrylic resin is adjusted to 24% or more. Therefore, the optical laminated body to which the resin film with an adhesive of the present invention is applied does not easily float or peel off at the interface between the adhesive layer and the glass substrate, and becomes an excellent durability. In addition, in the blending amount of the monomer, the particularly preferred monomer (a1) is 96.99% by weight or less, the monomer (a2) is 10% by weight or less, the monomer (a3) is 1% by weight or less, and the monomer (a4) ) Is 5% by weight or less. Of course, the total amount of each blended amount of the monomers (a1) to (a4) will not exceed 100% by weight.

The first acrylic resin (A) used in the present invention may be copolymerized with monomers other than the monomers (a1) to (a4). Examples of monomers other than monomers (a1) to (a4) include unsaturated monomers having a heterocyclic group such as an epoxy ring, and (A) having an alicyclic structure in the molecule. Group) acrylic esters, styrene-based monomers, vinyl-based monomers, monomers having a plurality of (meth) acrylfluorene groups in the molecule, and the like.

Examples of unsaturated monomers having a heterocyclic group such as an epoxy ring include acrylamidomorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, (methyl ) Tetrahydrofuran acrylate, tetrahydrofuran acrylate modified by caprolactone, 3,4-epoxycyclohexyl methyl (meth) acrylate, glycidyl (meth) acrylate, 2,5-dihydrofuran, and the like.

Next, a (meth) acrylate having an alicyclic structure in the molecule will be described. The alicyclic structure is a cyclic paraffin structure having a carbon number of usually 5 or more, preferably 5 to 7. Examples of acrylates having an alicyclic structure include isoamyl acrylate, cyclohexyl acrylate, dicyclopentyl acrylate, cyclododecyl acrylate, methyl cyclohexyl acrylate, and trimethyl acrylate. Cyclohexyl, tertiary butyl cyclohexyl acrylate, α-epoxy cyclohexyl acrylate, cyclohexyl phenyl acrylate, and the like. In addition, alicyclic junctions are listed. Examples of structural acrylic esters are isoamyl methacrylate, cyclohexyl methacrylate, dicyclopentyl methacrylate, cyclododecyl methacrylate, methyl cyclohexyl methacrylate, and formazan. Trimethylcyclohexyl methacrylate, tertiary butyl cyclohexyl methacrylate, cyclohexyl phenyl methacrylate, and the like.

Examples of styrenic monomers are listed. In addition to styrene, there are methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, and triethylbenzene. Alkylstyrenes such as ethylene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodine Halogenated styrenes such as styrene; in addition, there are nitrostyrene, ethylacetostyrene, methoxystyrene, divinylbenzene, and the like.

Examples of vinyl monomers are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, and other fatty acid vinyl esters; vinyl chloride and vinyl bromide Vinyl halide, etc .; vinylidene halide, such as vinylidene chloride; vinyl pyridine, vinyl pyrrolidone, and vinyl carbazole; nitrogen-containing aromatic ethylene; butadiene, isoprene, and chloroprene Conjugated diene monomers such as alkenes; in addition, there are acrylonitrile and methacrylonitrile.

Examples of monomers having a plurality of (meth) acrylfluorenyl groups in the molecule include 1,4-butanediol di (meth) acrylate and 1,6-hexanedi (meth) acrylate. Alcohol esters, 1,9-nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene di (meth) acrylate Alcohol esters and tripropylene glycol di (meth) acrylate, etc. are monomers having 2 (meth) acrylfluorenyl groups in the molecule; tri (meth) propylene Acid trimethylolpropane is a monomer having three (meth) acrylfluorenyl groups in the molecule.

As the resin component constituting the adhesive composition, two or more kinds of the first acrylic resin (A) may be mixed, and the first acrylic resin (A) is the (meth) acrylic acid alkyl ester represented by the above formula (II), that is, Monomer (a1), an unsaturated monomer having one olefinic double bond and at least one aromatic ring in the molecule, that is, monomer (a2), an unsaturated monomer having a carboxyl group, that is, monomer (a3) ), And at least one monomer selected from unsaturated monomers having a hydroxyl group, unsaturated monomers having an amidine bond, and unsaturated monomers having an amine group, that is, a copolymer of the monomer (a4). Further, in the first acrylic resin (A) having a structural unit derived from the monomer (a1) to the monomer (a4) at a predetermined ratio, an acrylic acid ester different from this may be mixed. The different acrylates to be mixed at this time include, for example, those having a structural unit derived from the alkyl (meth) acrylate of the formula (II) and having no polar functional group. The first acrylic resin (A) that copolymerizes the monomers (a1) to (a4) at a predetermined ratio is preferably 80% by weight or more, and more preferably 90% by weight or more, in the entire acrylate.

The first acrylic resin (A) obtained by copolymerization of a monomer mixture containing monomers (a1) to (a4) is preferably a standard polystyrene according to gel permeation chromatography (GPC) The converted weight average molecular weight (Mw) is in the range of 500,000 to 1.7 million. When the weight-average molecular weight is 500,000 or more, the adhesiveness of the adhesive formed from the adhesive composition containing the first acrylic resin (A) under a high humidity and heat environment can be improved. Therefore, for example, the optical film with an adhesive provided on the optical film is suitable for an optical laminated body made of a liquid crystal cell or the like, and is interposed between the liquid crystal cell and the adhesive layer. The possibility of floating or peeling tends to decrease, and the reworkability also tends to improve, so it is preferable. In addition, when the weight average molecular weight is 1.7 million or less, even if the size of the resin film adhered to the adhesive layer changes, the adhesive layer can also change in accordance with the dimensional change. Therefore, even if the optical film provided with the adhesive layer changes in size, the adhesive layer also follows and changes, so no peeling or the like occurs. In the optical laminate, the brightness of the peripheral edge portion of the liquid crystal cell and the brightness of the central portion There is no difference between them, but there is a tendency to suppress whitening or color unevenness, so it is preferable. The molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is not particularly limited, but is preferably in the range of 3 to 7, for example.

The first acrylic resin (A) preferably has a glass transition temperature in the range of -10 ° C to -60 ° C in order to exhibit adhesion. The glass transition temperature of the resin can be measured by a differential scanning thermal analysis (DSC: Differential Scanning Calorimetry).

The first acrylic resin (A) constituting the adhesive composition can be, for example, various generally known methods such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method using a water-based polymerization method. Method to manufacture. In the production of this first acrylic resin, a polymerization initiator is usually used. The polymerization initiator is used in an amount of about 0.001 to 5 parts by weight based on 100 parts by weight of the total monomers used in the production of the first acrylic resin. In addition, the first acrylic resin may also be activated by, for example, ultraviolet rays. It is produced by a method of polymerization by irradiation.

As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator can be used. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) Phenyl (2-hydroxy-2-propyl) ketone and the like. Examples of the thermal polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), and 1,1'-azobis (cyclohexane). 1-Carbononitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxypentyl) Nitrile), dimethyl-2,2'-azobis (dimethylpropionate), and 2,2'-azobis (2-hydroxymethylpropionitrile), etc .; Lauryl oxide, tertiary butyl hydroperoxide, benzamidine peroxide, tertiary butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxy Organic peroxides such as oxydicarbonate, tert-butylperoxyneodecanoate, tert-butylperoxyvalerate, and peroxide (3,5,5-trimethylacetamido); Inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide. In addition, a redox-based initiator in which a peroxide and a reducing agent are used in combination can also be used as a polymerization initiator.

Of the methods for producing a first acrylic resin, among the methods described above, a solution polymerization method is preferred. The solution polymerization method is, for example, a method of mixing a desired monomer and an organic solvent, adding a thermal polymerization initiator under a nitrogen environment, and stirring at about 40 to 90 ° C, preferably about 60 to 80 ° C, for 3 to 10 hours. In addition, in order to control the reaction, a monomer or a thermal polymerization initiator may be added continuously or intermittently during the polymerization, or may be added in a state of being dissolved in an organic solvent. Here, as the organic solvent, for example, aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropanol; acetone and methyl ethyl ketone And ketones such as methyl isobutyl ketone.

<Crosslinking agent (B)>

The cross-linking agent (B) is a structural unit derived from the unsaturated monomer having a carboxyl group, the unsaturated monomer having a hydroxyl group, and the unsaturated monomer having an amine group in the first acrylic resin (A), and is present in A compound in which the unsaturated monomer having an epoxy ring in the first acrylic resin (A) reacts to crosslink the acrylic resin. Specific examples include isocyanate-based compounds, epoxy-based compounds, Aziridine-based compounds, and metal chelate-based compounds. Among these, the isocyanate-based compound, epoxy-based compound, and aziridine-based compound have at least two functional groups in the molecule that can react with the polar functional group in the first acrylic resin (A).

The isocyanate compound is a compound having at least two isocyanate groups (-NCO) in the molecule, and examples thereof include toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, and hydrogenated xylene diisocyanate. Isocyanates, diphenylmethane diisocyanates, hydrogenated diphenylmethane diisocyanates, naphthalene diisocyanates, triphenylmethane triisocyanates, and the like. In addition, an adduct obtained from a polyhydric alcohol such as glycerol or trimethylolpropane and an isocyanate compound or a dimerization or trimerization of an isocyanate compound can also be used as an adhesive agent. Crosslinker used. You may mix and use 2 or more types of isocyanate-type compounds.

The epoxy-based compound is a compound having at least two epoxy groups in the molecule, and examples thereof include bisphenol A epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and glycerol diglyceride. Glycidyl ether, glycerol triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N, N-diglycidyl aniline, N, N, N ', N'-tetraglycidyl-xylylenediamine, 1,3-bis (N, N'-diglycidylamine methyl) cyclohexane and the like. You may mix and use 2 or more types of epoxy compounds.

The aziridine-based compound is a compound having at least two skeletons of three-membered rings consisting of one nitrogen atom and two carbon atoms called ethyleneimine in the molecule, and examples thereof include diphenylmethane -4,4'-bis (1-aziridinecarboxamide), toluene-2,4-bis (1-aziridinecarboxamide), triethylene melamine, isobutylfluorenylbis-1- (2- (Methylaziridine), ginsane-1-aziridinephosphine oxide, hexamethylene-1,6-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridine Pyridine propionate, tetramethylol methane-tri-β-aziridine propionate and the like.

Examples of the metal chelate compound include a compound of polyvalent metal such as acetoacetone or acetoacetate in aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. Wait.

Among these crosslinking agents, it is preferable to use an isocyanate-based compound, especially xylene diisocyanate, toluene diisocyanate, or hexamethylene diisocyanate, or an isocyanate compound of these and a multicomponent of glycerol or trimethylolpropane, etc. The adduct obtained by the alcohol reaction is either a mixture of dimerization, trimerization, etc. of the isocyanate compound, or a mixture of these isocyanate compounds. Preferred isocyanate-based compounds include toluene diisocyanate, an adduct obtained by reacting toluene diisocyanate with a polyol, a dimer of toluene diisocyanate, and a terpolymer of toluene diisocyanate. In addition, examples include toluene diisocyanate. Hexamethylene diisocyanate, an adduct obtained by reacting hexamethylene diisocyanate with a polyol, a dimer of hexamethylene diisocyanate, and a terpolymer of hexamethylene diisocyanate.

The cross-linking agent (B) is usually formulated at a ratio of 0.1 to 1 part by weight based on 100 parts by weight of the first acrylic resin (A) (a total of two or more types are used), preferably 0.2 to 0.8. The ratio of parts by weight is more preferably formulated at a ratio of 0.3 to 0.7 parts by weight. If the amount of the cross-linking agent (B) is 0.1 part by weight or more with respect to 100 parts by weight of the first acrylic resin (A), the durability of the adhesive layer tends to be improved, so it is preferable, and if it is 1 part by weight or less, When an optical film with an adhesive is applied to a liquid crystal display device, whitening is not noticeable, so it is preferable.

<Silane Compound (C)>

The adhesive composition of the present invention preferably contains a silane compound (C). Thereby, when the resin film with an adhesive is bonded to a glass substrate such as a liquid crystal cell, the adhesion between the adhesive layer and the glass substrate can be improved. The silane compound (C) may contain the first acrylic resin (A) before the cross-linking agent is prepared.

The silane compound may be a hydrolyzable group such as an alkoxy group, which is bonded to a silicon atom, and a compound having a vinyl group, an amino group, an epoxy group, a haloalkyl group, a (meth) acryloxy group, or a mercapto group. Reactive functional organic compound. When each specific compound is exemplified, a silane compound having a vinyl group includes vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, and the like. Silane compounds with amine groups include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethyloxysilane and the like. Silane compounds with epoxy groups, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldioxane Methoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. The silane compounds having a haloalkyl group include 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, and the like. Examples of the silane compound having a (meth) acryloxy group include 3- (meth) acryloxypropyltrimethoxysilane and the like. Silane compounds having a mercapto group include 3-mercaptopropyltrimethoxysilane and the like. Two or more silane compounds can be used.

The silane compound (C) may be in the form of a polysiloxane oligomer. When a polysiloxane oligomer is represented as a (monomer)-(monomer) copolymer, the following is mentioned, for example.

3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxyoxide Mercaptopropyl-containing copolymers, such as methylmercaptosilane copolymers, 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymers; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymers, mercapto Contains methyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer, mercaptomethyltriethoxysilane-tetraethoxysilane copolymer, etc. Copolymer of mercaptomethyl; 3-glycidoxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer Polymer, 3-glycidoxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetraethoxysilane copolymer, 3- Glycidoxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3- Glycidoxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer, etc. Copolymer of 3-glycidoxypropyl; 3-methacryloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropyltrimethoxysilane -Tetraethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetramethoxysilane Ethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane -Tetraethoxy Silane copolymer, 3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropylmethyldiethoxysilane-tetraethyl Methacryloxypropyl-containing copolymers such as oxysilane copolymers; 3-acryloxypropyltrimethoxysilane-tetramethoxysilane, 3-acryloxypropyltrimethyl Ethoxysilane-tetraethoxysilane copolymer, 3-propenyloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-propenyloxypropyltriethoxysilane-tetraethyl Copolymer, 3-propenyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-propenyloxypropylmethyldimethoxysilane-tetraethoxysilane Copolymer, 3-propenyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-propenyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer And other copolymers containing propylene methoxypropyl; vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, Vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, Vinylmethyldiethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane-tetramethoxysilane copolymer, vinylmethyldiethoxysilane-tetraethoxy Vinyl-containing copolymers such as silane copolymers; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3- Aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane Methoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3 -Aminepropylmethyldiethoxysilane-tetraethoxysilane copolymers and other amine group-containing copolymers and the like.

These silane compounds are mostly liquid. The compounding amount of the silane compound in the adhesive is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight relative to 100 parts by weight of the solid content of the first acrylic resin (when two or more kinds are used). Parts, more preferably 0.1 to 2 parts by weight, and particularly preferably used in a ratio of 0.1 to 1 part by weight. When the amount of the silane compound is 0.01 part by weight or more with respect to 100 parts by weight of the solid content of the first acrylic resin (A), the adhesion between the adhesive layer and the glass substrate can be increased. Adhesiveness is preferred. In addition, when the amount is 10 parts by weight or less, it is preferable that the silane compound tends to be prevented from oozing out of the adhesive layer.

<Other ingredients constituting the adhesive composition>

In the adhesive composition described above, an antistatic agent, a cross-linking catalyst, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, and a first acrylic resin ( A) other than resin. In addition, it is also useful to formulate an ultraviolet curable compound to an adhesive composition and irradiate ultraviolet rays to harden the adhesive layer after forming the adhesive layer to form a harder adhesive layer. Among them, if the cross-linking agent and the cross-linking catalyst are formulated together in the adhesive composition, the adhesive layer can be prepared by curing in a short time, and the obtained resin film with the adhesive can be suppressed to the resin film and Floating or peeling occurs between the adhesive layers or foaming occurs in the adhesive layer. In addition, the reworkability sometimes becomes better. Examples of the crosslinking catalyst include hexamethylenediamine, ethylenediamine, polyethylenediamine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, and trimethylenediamine. , Amine compounds such as polyamine resin, melamine resin, etc. When an amine-based compound is formulated as a cross-linking catalyst in the adhesive composition, the cross-linking agent is preferably an isocyanate-based compound.

As the antistatic agent, generally known ones can be suitably used, and among them, an ionic compound can be preferably used. The cation component constituting the ionic compound is preferably an organic cation from the viewpoint of compatibility with an acrylic resin. The structure of the organic cation is not particularly limited, and examples thereof include a pyridine salt cation, an imidazole salt cation, an ammonium salt cation, a phosphonium salt cation, and a phosphonium salt cation. When an adhesive layer for an optical film is used, a pyridine salt cation or an imidazole salt cation is preferable from the viewpoint that it is not easy to be charged when the release film is peeled off. On the other hand, the anionic component constituting the ionic compound is not particularly limited, and may be an inorganic anion or an organic anion. From the viewpoint of imparting an ionic compound excellent in antistatic performance, an anionic component containing a fluorine atom is preferred. An anionic component comprising a fluorine atom, the anions include hexafluorophosphate [(PF ₆ ^-)], bis (trifluoromethane sulfonic acyl) acyl imide anion _{[(CF 3 SO 2) 2} N -] anion, bis (sulfo-fluoro-acyl) acyl imide anion ^{_{[(FSO 2) 2 N -}} ] anion. In addition, from the reason that the antistatic property of the adhesive is excellent in stability over time, the ionic compound is preferably an ionic solid that is solid at room temperature.

Each of these components constituting the adhesive is formed into an adhesive composition in a state of being dissolved in a solvent, and then coated on an appropriate substrate and dried to form an adhesive layer. The substrate used here is generally a plastic film. The typical example includes a release film after being subjected to a release treatment. The release film can be applied to, for example, an adhesive-formed surface of a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyarylate. Release processors such as polysiloxane treatment.

<Tensile Elasticity of Adhesive Layer>

In the present invention, the tensile elastic modulus of the adhesive layer formed of the adhesive composition is preferably 0.22 MPa or more. Hereinafter, a method for measuring the tensile elastic modulus will be described.

The tensile elastic modulus of the adhesive layer can be determined by the following method To measure. First, use a thin coater to apply a pressure-sensitive adhesive composition to the release-treated surface of a polyethylene terephthalate (PET) film after the release treatment is performed so that the thickness after drying becomes 20 μm. After drying at 100 ° C for 1 minute to form a sheet-like adhesive, it was aged at room temperature for 7 days. Next, after overlapping the adhesive surfaces of the two groups of PET films with adhesives, one PET film was peeled off, and the adhesive surfaces of the other PET films with adhesives were superimposed on the adhesive surface that appeared on the surface. This operation was repeated to produce an adhesive sheet having a thickness of 600 μm. A 15 mm × 50 mm slice was cut out from the adhesive sheet, and the sample was peeled from the PET film to produce a measurement sample. The tensile elastic modulus of the adhesive layer is determined by fixing the measurement sample to the upper and lower jigs of a tensile testing machine manufactured by Shimadzu Corporation to measure the tensile elastic modulus in the longitudinal direction of the measurement sample. The distance between the clamps is set at 30mm, and it is stretched under the condition of a tensile speed of 300mm / min in an environment of a temperature of 23 ° C and a relative humidity of 55%, a stress-strain curve is made, and a tensile elastic modulus (MPa) is obtained. After the value.

The tensile elastic modulus of the adhesive layer is preferably 0.22 MPa or more, particularly preferably 0.25 MPa or more, in order to prevent foaming or peeling of the adhesive layer in a high-temperature or high-humidity environment. The adhesive layer having this tensile elastic modulus can improve the reworkability of the polarizing plate because of its moderate cohesion. In addition, it can also suppress the deformation of the polarizing plate or the optical film with the adhesive during processing. The lack of glue, etc. On the other hand, if the tensile elasticity is too high, the relaxation of the stress caused by the difference in the dimensional change between the optical film and the glass substrate of the liquid crystal cell due to the adhesive layer tends to be insufficient, and it may be in the optical film. Interface with adhesive layer or adhesive layer The interface with the glass substrate is peeled off, or the display of the optical laminate is uneven. Therefore, the tensile elastic modulus is preferably 0.35 MPa or less, and particularly preferably 0.30 MPa or less.

[Resin film with adhesive]

The adhesive-attached resin film of the present invention is one in which an adhesive layer formed of the above-mentioned adhesive composition is provided on at least one side of the resin film. The resin film used herein may be an optical film including a film selected from a polarizing plate and a retardation film.

The polarizing film is a film having a function of converting natural light into linearly polarized light. Preferable examples of the polarizing film include those in which a dichroic dye such as iodine or a dichroic dye is adsorbed and aligned on a polyvinyl alcohol-based resin film after uniaxial stretching. The film thickness of the polarizing film is not particularly limited, and generally 0.5 to 35 μm is used. A protective film is laminated on one or both sides of the polarizing film to form a polarizing plate. Examples of the obtained polarizing plate include linear polarized light capable of absorbing linearly polarized light having a vibration surface incident on a certain direction of the film surface and transmitting linearly polarized light having a vibration surface orthogonal to the direction. A polarizing light separating plate capable of reflecting linearly polarized light having a vibrating surface incident on a film surface in a certain direction and transmitting linearly polarized light having a vibrating surface orthogonal to the direction; and a laminated polarizing plate and a later-described Elliptical polarizers such as retardation films.

In the present invention, when a protective film is bonded to both sides of a polarizing film to form a polarizing plate, an adhesive layer is formed on the surface of the protective film constituting the polarizing plate. Polarization is formed by bonding the protective film to only one side of the polarizing film In the case of a plate, an adhesive layer may be formed on the surface of the polarizing film (the surface on which the protective film is not attached). In the present invention, the protective film is bonded to a single-sided or double-sided polarizing film of the polarizing film, and can also be used as an optical film. When the protective film is bonded to both sides of the polarizing film, the protective film on both sides may be the same or different resin films.

As the protective film, a transparent resin film can be used. Examples of the transparent resin include cellulose resins, acrylic resins, polyester resins, polyolefin resins, polycarbonate resins, polyetheretherketone resins, and polyethers typified by triethyl cellulose and diethyl cellulose.碸 Resin and so on. In the resin constituting the protective film, it is also possible to formulate a salicylate-based compound, a diphenyl ketone-based compound, a benzotriazole-based compound, a triazine-based compound, a cyanoacrylate-based compound, a nickel complex compound, and the like. UV absorber. As the protective film, a cellulose-based resin film such as triethylammonium cellulose and an acrylic resin film can be preferably used. As the cellulose-based resin forming the protective film, the same resin as that described in the retardation film described later can be appropriately selected, and the film can be formed and stretched by a generally known method and used.

As the acrylic resin forming the resin film, generally known ones can be suitably used. In the present invention, it is preferable to use a second acrylic resin as the acrylic resin. The second acrylic resin may be the same polymer as the first acrylic resin, but it is generally preferred to use a methacrylic acid ester as the main monomer and a copolymer in which a small amount of other copolymer components are copolymerized. . The copolymer is usually obtained by polymerizing a monofunctional monomer including methyl methacrylate and methyl acrylate in the coexistence of a radical polymerization initiator and a chain transfer agent. In addition, the second acrylic resin can copolymerize a second monofunctional monomer.

Examples of the second monofunctional monomer copolymerizable with methyl methacrylate and methyl acrylate include, for example, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, Methacrylates other than methyl methacrylate, such as benzyl methacrylate, 2-ethylhexyl methacrylate, and 2-hydroxyethyl methacrylate; ethyl acrylate, butyl acrylate, and cyclohexyl acrylate Esters, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate and 2-hydroxyethyl acrylate, etc .; 2- (hydroxymethyl) acrylate, 2- (1-hydroxyethyl) Hydroxyalkyl acrylates such as methyl acrylate, ethyl 2- (hydroxymethyl) acrylate and butyl 2- (hydroxymethyl) acrylate; unsaturated acids such as methacrylic acid and acrylic acid; chlorostyrene and bromine Halogenated styrenes such as styrene; Substituted styrenes such as vinyl toluene and α-methylstyrene; Unsaturated nitriles such as acrylonitrile and methacrylic; phenylcis butylene diimide and cyclic Unsaturated fluorene imines such as hexyl cis butene difluorene and the like. These can be used individually or in combination of a different plural number.

When polyfunctional monomers are copolymerized, polyfunctional monomers that can be copolymerized with methyl methacrylate and methyl acrylate include, for example, ethylene glycol di (meth) acrylate and di (meth) acrylic acid. Diethylene glycol ester, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, and fourteen di (meth) acrylate Ethylene glycol such as ethylene glycol ester or the two terminal hydroxyl groups of the oligomer are esterified with acrylic acid or methacrylic acid; propylene glycol or the two terminal hydroxyl groups of the oligomer are acrylic acid or methacrylic acid Esterified; neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, and butylene glycol di (meth) acrylate Ester of diol such as acrylic acid or methacrylic acid; bisphenol A, alkylene oxide adduct of bisphenol A, or halogen substituted products of the two terminal hydroxyl groups of acrylic acid or methacrylic acid Acrylic acid esterified; polyhydric alcohols such as trimethylolpropane and neopentyl alcohol are esterified with acrylic acid or methacrylic acid, and these terminal hydroxyl groups make glycidyl acrylate or glycidyl methacrylate Epoxy ring-opening adducts of esters; diprotic acids such as succinic acid, adipic acid, terephthalic acid, phthalic acid, halogenated substitutes thereof, and the like, and alkylene oxide adducts thereof Such as epoxy ring-opening addition of glycidyl acrylate or glycidyl methacrylate; aryl (meth) acrylate; aromatic divinyl compounds such as divinylbenzene and the like. Among them, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and neopentyl glycol dimethacrylate can be preferably used.

The second acrylic resin composed of such a composition can further undergo a reaction between functional groups of the copolymer and be modified. This reaction includes, for example, a de-methanol condensation reaction within a polymer chain of a methyl group of methyl acrylate and a hydroxyl group of methyl 2- (hydroxymethyl) acrylate, a carboxyl group of acrylic acid, and methyl 2- (hydroxymethyl) acrylate. Dehydration condensation reaction of the hydroxyl polymer chain.

In addition, the second acrylic resin may have any of a glutaridine imine derivative, a glutaric anhydride derivative, or a lactone ring structure.

The glass transition temperature of the second acrylic resin is preferably in a range of 90 ° C to 160 ° C. When the glass transition temperature of the second acrylic resin is adjusted to the above range, the polymerization ratio of the methacrylate-based monomer to the acrylate-based monomer and the carbon of each ester group can be generally appropriately selected. The chain length, the type of functional group it has, and the method of the polymerization ratio of the polyfunctional acrylic monomer to the entire monomer. The glass transition temperature of the second acrylic resin is more preferably 110 to 160 ° C, and particularly preferably 120 to 150 ° C.

The second acrylic resin may contain generally known additives as necessary. Commonly known additives include, for example, lubricants, anticaking agents, thermal stabilizers, antioxidants, antistatic agents, lightfasteners, impact resistance improvers, and surfactants. However, since the resin film formed of the second acrylic resin is required to be used as a protective film laminated on the polarizing film, the amount of these additives is preferably kept to a minimum.

As a method for producing a resin film (acrylic resin film) formed of the second acrylic resin, any method such as a melt vertical method, a T-die method, a melt extrusion method such as a blow molding method, and a calender method can be used. Among them, for example, a method in which a raw resin is melt-extruded from the T-die method, and at least one side of the obtained film-like material is brought into contact with a roller or a steel strip to form a film, from the viewpoint of obtaining a film with good surface properties. Better. The film-forming acrylic resin film can be stretched and used by a generally known method.

The second acrylic resin may contain acrylic rubber particles as an impact modifier from the viewpoints of film-forming properties of the film and impact resistance of the film. Here, the so-called acrylic rubber particles are particles having an elastic polymer mainly composed of acrylate as an essential component, and examples thereof include those having a single-layer structure consisting essentially of the elastic polymer or polymerized by the elasticity. Object as a multi-layered structurer. Examples of the elastic polymer include a crosslinkable elastomer having an alkyl acrylate as a main component and copolymerizing other vinyl monomers and crosslinkable monomers that can be copolymerized with the alkyl acrylate. Sexual copolymer. Examples of the alkyl acrylate as a main component of the elastic polymer include those having an alkyl group having a carbon number of about 1 to 8 such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Preferably, acrylic acid having an alkyl group having 4 or more carbon atoms can be used. Other vinyl monomers that can be copolymerized with the alkyl acrylate include compounds having one polymerizable carbon-carbon double bond in the molecule. Specific examples include methacrylates such as methyl methacrylate, Aromatic vinyl compounds such as styrene and vinyl cyanide compounds such as acrylonitrile. Examples of the crosslinkable monomer include compounds having crosslinkability of at least two polymerizable carbon-carbon double bonds in the molecule, and specific examples include ethylene glycol di (meth) acrylate and bis (methyl) ) (Meth) acrylates of polyhydric alcohols such as butanediol acrylate, (meth) acrylic alkenes such as allyl (meth) acrylate, divinylbenzene, and the like.

Further, a laminate of a film made of an acrylic resin not containing rubber particles and a film made of an acrylic resin containing rubber particles may be used as the protective film or retardation film. Acrylic resins are easily available on the market, and examples thereof include "Sumipex" (manufactured by Sumitomo Chemical Co., Ltd.) manufactured by Sumitomo Chemical Co., Ltd., "Acrypet" manufactured by Mitsubishi Rayon Co., Ltd., and "manufactured by Asahi Kasei Corporation" "Delpet", "Parapet" manufactured by Kuraray Co., Ltd., and "Acryviewa" manufactured by Japan Catalyst Co., Ltd. (the above are all trade names).

Among the polarizing plates described above, linear polarizing plates are often used in a state where a protective film is adhered on one or both sides of a polarizing film made of, for example, a polyvinyl alcohol resin. In addition, the above-mentioned elliptical polarizing plate is a laminated linear polarizing plate and a retardation film, but many of these polarizing plates are also used in One or both sides of the polarizing film are used with a protective film attached. When the adhesive layer of the present invention is formed on the elliptically polarizing plate, an adhesive layer is usually formed on the retardation film side.

The retardation film is an optical film exhibiting optical anisotropy, and examples thereof include a polyvinyl alcohol resin, a polycarbonate resin, a polyester resin, a polyacrylic resin, a polyimide resin, and an olefin. Based resins, cycloolefin based resins, styrene based resins, polyfluorene and polyether fluorene resins, polyvinylidene fluoride / polymethyl methacrylate, liquid crystal polyester resins, and fibers containing triethyl cellulose A resin film composed of a plain resin, an ethylene-vinyl acetate copolymer saponified product, a polyvinyl chloride resin, an acrylic resin, etc., is a stretched film obtained by stretching to about 1.01 to 6 times. Among them, a resin film obtained by uniaxially stretching or biaxially stretching a cycloolefin resin film, a cellulose resin film, a polyester resin film, and a polycarbonate resin film is preferred. In addition, in this specification, although it is an optical film which does not show optical anisotropy, a zero retardation film is also included in a retardation film. In addition, a film called a uniaxial retardation film, a low photoelasticity retardation film, a wide viewing angle retardation film, or the like can also be applied as a retardation film.

Cycloolefin-based resins are, for example, thermoplastic resins having monomer units of cycloolefins typified by norbornene or tetracyclododecene (alias dimethyl octahydronaphthalene) or derivatives thereof, except for the ring-opening of cycloolefins. The polymer or a hydrogenated product of a ring-opening copolymer using two or more cycloolefins may be an addition copolymer of a cycloolefin and a chain olefin or an aromatic compound having a vinyl group. Alternatively, a polar group may be introduced.

Commercially available thermoplastic cycloolefin-based resins, such as Germany "Topas" manufactured by TOPAS ADVANCED POLYMERS GmbH and sold by Polyplastics Co., Ltd. in Japan, "Arton" (ARTON) by JSR Co., Ltd., and sold by Nippon Zeon Co., Ltd. "ZEONEX" (ZEONEX) and "ZEONOR" (ZEONOR), "Apel" (both trade names) sold by Mitsui Chemicals Co., Ltd., etc.

When the cycloolefin resin is formed into a film to form a film, a generally known film-forming method such as a solvent casting method or a melt extrusion method can be used for the film formation. There are also commercially available cycloolefin resin films after film formation, or cycloolefin resin films that are further stretched to give a retardation. For example, there are "Arton Film" sold by JSR Corporation, "ZEONOR Film" sold by Nippon Zeon Corporation, "S-SINA" and "SCA40" sold by Sekisui Chemical Industry Co., Ltd. "(Both are trade names) and the like, all of which are preferably used.

The cellulose-based resin film is generally composed of a partially or completely esterified cellulose. Examples of the film include cellulose acetate, propionate, butyrate, and mixed esters thereof. Among them, a triethylammonium cellulose film, a diethylammonium cellulose film, a cellulose acetate propionate film, a cellulose acetate butyrate film, and the like can be preferably used.

Commercial products such as "Fujitac TD" sold by Fujifilm Co., Ltd., and "Konica MInolta TAC Film KC" sold by Konica Minolta Opto Co., Ltd. can be easily obtained.

Polyester resins are made by the condensation of diprotic acid and diol. Examples of the polymer obtained by polymerization include polyethylene terephthalate. In addition, the polycarbonate-based resin is a polymer having a carbonate bond (-O-CO-O-) in the main chain, and representative compounds include those obtained by the condensation polymerization of bisphenol A and carbonyl dichloride.

In the present invention, a zero retardation film of a liquid crystal display device in an IPS mode can be preferably used, and it can also be used as a retardation film. The so-called zero retardation film is a front retardation value R _e and a thickness direction retardation value R _th are both as small as -15 to +15 nm, and is called an optical isotropic film.

For the zero retardation film, for example, a resin film composed of a cellulose-based resin, a polyolefin-based resin containing a chain polyolefin-based resin and a polycycloolefin-based resin, and a polyethylene terephthalate-based resin can be used. In particular, a cellulose resin, a polyolefin resin containing a chain polyolefin resin, and a polycycloolefin resin can be preferably used from the viewpoint of easy control of the retardation value and easy availability.

As the zero retardation film, the same resin as that used in the film formation of the retardation film having the optical anisotropy can be appropriately used. The zero retardation film can be used not only as a retardation film, but also as a protective film.

A method for forming a film from a cellulose resin, a polyolefin resin, or the like may be appropriately selected in accordance with a method of various resins. For example, a solvent casting method in which a resin dissolved in a solvent is melt-flowed on a metal steel belt or a drum and dried to remove the solvent to obtain a film; or the resin is heated to a temperature above the melting temperature, kneaded and removed from a mold The head is extruded, and then cooled by a cooling drum to obtain a film by a melt extrusion method or the like. among them, For the polyolefin-based resin, from the viewpoint of productivity, a melt extrusion method is preferably used. On the other hand, cellulose resin is generally formed into a film by a solvent casting method.

The retardation value R _th in the thickness direction is a value obtained by multiplying the thickness of the film by the value obtained by subtracting the refractive index in the thickness direction from the average refractive index in the plane, and is expressed by the following formula (1). In addition, in-plane retardation value R _e, lines represented by the following formula (2) is a value obtained by multiplying the thickness of the film obtained from the difference between the refractive index in the above order.

R _th = [(n _x + n _y ) / 2-n _z ] × d (1)

R _e = (n _x -n _y ) × d (2)

In the formula, n _x is the refractive index of the in-plane late phase axis direction (x-axis direction) of the film, and n _y is the refractive index of the in-plane phase axis direction (y-axis direction orthogonal to the x-axis) of the film. Rate, n _z is the refractive index in the thickness direction of the film (the z-axis direction perpendicular to the film surface), and d is the thickness of the film.

Here, the retardation value may be a value of an arbitrary wavelength in the range of 500 to 650 nm near the center of visible light, but in this specification, a retardation value at a wavelength of 590 nm is used as a standard. The retardation value R _{th in the} thickness direction and the retardation value R _{e in the} plane can be measured using various commercially available retarders.

The in-plane retardation value R _e resin film and the thickness direction retardation value R _th in the process control range -15 to + 15nm include a method for the production of films, tried to reduce the residual strain in the thickness direction. For example, in the above-mentioned solvent casting method, a method of reducing the residual shrinkage strain in the thickness direction generated when the molten resin solution is dried by a heat treatment, or the like can be adopted. On the other hand, in the melt extrusion method, in order to prevent the resin film from being stretched from being extruded from the die until it is cooled, it is adopted to shorten the distance from the die to the roller as much as possible, and the film will not The method of stretching is to control the amount of extrusion and the speed of the cooling drum. In addition, as with the solvent casting method, a method of reducing the strain remaining in the obtained film by heat treatment may be used.

Zero-retardation films, such as "Z-TAC" sold by Fujifilm Co., Ltd., "Zerotac" sold by Konica Minolta Opto Co., Ltd., and "ZF-14" sold by Nippon Zeon Co., Ltd. "(Both are trade names) and the like can be preferably used.

When the adhesive layer is formed on an optical film including a retardation film, and is bonded to a glass substrate through the adhesive layer, if the moisture permeability of the retardation film is small, the moisture in the adhesive layer cannot be easily removed. This moisture causes foaming and the like, and is particularly disadvantageous in durability under high temperature conditions. In contrast, in the resin film with an adhesive of the present invention, when an optical film including a retardation film is used as the resin film, even if the retardation film is tested by the moisture-permeable cup test method specified in JIS Z 0208, When the measured moisture permeability at a temperature of ℃ and a relative humidity of 90% is less than 300 g / (m ² ‧24hr), it also shows excellent durability.

Examples of the retardation film having a low water vapor transmission rate include a film made of a cycloolefin-based resin described above. These retardation films have a water vapor transmission rate of approximately 300 g / (m ² ‧24hr) at a temperature of 40 ° C and a relative humidity of 90%.

In addition, a film exhibiting optical anisotropy by coating and alignment of a liquid crystalline compound, or coating by an inorganic layered compound A film exhibiting optical anisotropy can also be used as a retardation film. This retardation film is called a temperature-compensated retardation film. In addition, there is an obliquely aligned film of a rod-shaped liquid crystal sold by JX Nippon Oil & Energy Co., Ltd. under the trade name "NH Film", A disc oriented liquid crystal film sold by Fuji Film Co., Ltd. under the trade name of "WV Film", and a complete biaxial alignment sold by Sumitomo Chemical Co., Ltd. under the trade name of "VAC Film" And other biaxially oriented films sold by Sumitomo Chemical Co., Ltd. under the trade name "new VAC Film".

The adhesive-attached resin film of the present invention using the optical film described above as the resin film is an optical laminate that can be laminated on a glass substrate such as a liquid crystal cell with the adhesive layer side. The optical multilayer body of the present invention is excellent in durability even if it has an optical film with a large amount of warpage when the film is heated.

The amount of warpage of the film can be measured in the following manner. First, a commercially available acrylic adhesive sheet having a thickness of 25 μm (storage elasticity at a temperature of 23 ° C. of 0.05 MPa) was laminated on one side of an optical film by a laminator to form an optical film with an adhesive. . This adhesive-attached optical film was cut into 150 mm (stretching direction of the film) × 40 mm (direction perpendicular to the stretching direction of the film) slices, and bonded to a size of 51 mm × 156 mm and a thickness of 0.5 mm. Glass [trade name "Eagle XG" manufactured by Corning]. Next, the laminated body was stored in a dry condition at a temperature of 85 ° C. for 24 hours, and then left at room temperature for 30 minutes. The amount of warpage of the laminated body was measured and determined. The amount of warpage of the laminated body is the one in which the curved laminated body faces downward and is convex. It is placed on the measuring table in the same manner, and the longest one is expressed in absolute value at the four corners of the optical film constituting the laminated body based on the position of the center of gravity.

The greater the amount of warpage of the optical film, the greater the stress applied to the adhesive layer interposed between the glass substrate with small deformation and the optical film with large warpage during endurance tests such as heating tests. For an optical film with a large warpage, in particular, an optical film with a warpage of 1400 μm or more and further 1600 μm or more, when a commonly known acrylic adhesive is applied, it is caused by the stress caused by the deformation of the optical film. As a result, appearance defects such as floating, peeling, and foaming occurred between the optical film and the adhesive layer or between the glass substrate and the adhesive layer. As described above, the adhesive layer of the present invention has high cohesive force and high adhesion to the glass substrate. Even if the optical film is greatly deformed, the deformation can be suppressed, and the adhesion to the glass substrate can be firmly maintained. Therefore, even if the optical laminate of the present invention uses such an optical film with a large warpage as the resin film constituting it, the durability is excellent under severe conditions.

In addition to the optical film described above, the resin film used in the adhesive-attached resin film of the present invention may be an optical film attached to the object to be protected to prevent damage or dirt on the surface. Surface protective film etc. used for the purpose. The surface protection film is a film used for the purpose of protecting the surface of an optical film or the like of a protected object from damage or dirt. For example, in general, a polarizing film or a polarizing film used in the production of liquid crystal display Various optical films such as plates, retardation films, light-diffusing sheets, reflective sheets, etc. When an adhesive layer is present, it circulates in the state of the surface on the opposite side to the adhesive layer), and after being bonded to a liquid crystal cell or the like, the surface protective film is peeled off and removed. Examples of the substrate of the surface protective film include polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; and fluorinated polyolefin resins such as polyvinyl fluoride, polyvinylidene fluoride, and polyvinyl fluoride. ; Polyester resins such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, and polyethylene terephthalate / isophthalate copolymers Polyamides such as nylon 6 and nylon 6,6; polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, polyvinyl alcohol, and Vinylon ) And other vinyl polymers; cellulose resins such as triethyl cellulose, diethyl cellulose and Cellophane; polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate Acrylic resins such as esters and polybutyl acrylate; others include polystyrene, polycarbonate, polyarylate, and polyimide.

When the adhesive-attached resin film of the present invention is used as a surface protective film, the above-mentioned substrate film may be provided with the adhesive layer described above.

In addition, in the adhesive-attached resin film of the present invention, it is preferable to stick a release film on the surface of the adhesive layer, and temporarily protect it before use. The release film used here includes, for example, a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyarylate as the substrate. A release treatment such as a polysiloxane treatment is applied to the bonding surface of the substrate with the adhesive layer.

Adhesive-coated resin film can be obtained by, for example, The method of coating the adhesive composition described above on the release film to form an adhesive layer, and then laminating the resin film on the obtained adhesive layer; or coating the adhesive composition on the resin film to form an adhesive layer , And a release film is bonded to the surface of the adhesive to protect it, and a method of forming a resin film with an adhesive is produced.

The thickness of the adhesive layer is not particularly limited, but is usually preferably 30 μm or less, more preferably 10 μm or more, and more preferably 10 to 20 μm. When the thickness of the adhesive layer is 30 μm or less, the adhesiveness in a high humidity and heat environment can be improved, the possibility of floating or peeling between the glass substrate and the adhesive layer tends to decrease, and the tendency to improve reworkability tends to be reduced. Therefore, it is preferable. In addition, when the thickness is 10 μm or more, even if the size of the optical film attached thereto changes, the adhesive layer will change in accordance with the size change, and the brightness and the central portion of the peripheral portion of the liquid crystal cell There is no difference between the brightness, but there is a tendency to suppress whitening or color unevenness, so it is preferable. In general, the thickness of an adhesive layer pasted to a liquid crystal cell was 25 μm as a standard, but in the present invention, even if the thickness is set to 20 μm or less, sufficient performance as an adhesive layer can be exhibited.

After the resin film with an adhesive of the present invention is bonded to a glass substrate such as a liquid crystal cell to form an optical laminate, there are always some defects, and it is sometimes necessary to peel the optical film from the glass substrate and re-attach it. The so-called rework operation of the adhesive-attached resin film. In the adhesive-attached resin film of the present invention, when the rework operation is performed, the adhesive layer is peeled off along with the optical film, and there is almost no blur or residue on the surface of the glass substrate that is in contact with the adhesive layer. Easy to re-launch on the released glass substrate Attach a resin film with an adhesive. That is, the reworkability is excellent.

[Optical laminated body]

The resin film with an adhesive of the present invention can be constituted by an optical film, and laminated on a glass substrate with the adhesive layer side to constitute an optical laminate. When the resin film with an adhesive is laminated on a glass substrate to form an optical laminate, for example, the release film can be peeled from the resin film with an adhesive obtained as described above, and the exposed adhesive layer can be bonded to the glass substrate. Just the surface. Here, the glass substrate includes, for example, a glass substrate of a liquid crystal cell, an anti-glare glass, a glass for sunglasses, and the like. Among them, a resin film (an upper polarizing plate) with an adhesive layer provided with an adhesive layer on a polarizing plate is laminated on a glass substrate on the front side (viewing side) of a liquid crystal cell, and an adhesive layer is provided on the polarizing plate. Another optical laminated body in which a resin film (lower polarizing plate) with an adhesive is laminated on a glass substrate on the rear side of the liquid crystal cell can be used as a liquid crystal display device, so it is preferable. Examples of the material of the glass substrate include soda-lime glass, low-alkali glass, and alkali-free glass.

Regarding the optical multilayer body of the present invention, examples of several preferred layer configurations are shown in the schematic sectional view of FIG. 1. In the example shown in FIG. 1 (A), the protective film 3 having the surface treatment layer 2 is adhered to one surface of the polarizing plate 1 with a surface opposite to the surface treatment layer 2 to constitute a polarizing plate. 5. In this example, the polarizing plate 5 also becomes the so-called optical film 10 of the present invention. An adhesive layer 20 is provided on a surface of the polarizing plate 1 opposite to the protective film 3 to constitute a resin film 25 with an adhesive. Then, the surface of the adhesive layer 20 opposite to the polarizing plate 5 is bonded to a liquid crystal as a glass substrate. The unit 30 constitutes an optical laminated body 40.

In the example shown in FIG. 1 (B), the first protective film 3 having the surface treatment layer 2 is adhered to one side of the polarizing plate 1 with a surface opposite to the surface treatment layer 2, and The second protective film 4 is adhered to the other surface of the polarizing plate 1 to form a polarizing plate 5. In this example, the polarizing plate 5 also becomes the so-called optical film 10 of the present invention. An adhesive layer 20 is provided on the outer side of the second protective film 4 constituting the polarizing plate 5 to constitute a resin film 25 with an adhesive. Then, the surface of the adhesive layer 20 on the side opposite to the polarizing plate 5 is bonded to a liquid crystal cell 30 as a glass substrate to form an optical laminated body 40.

In the example shown in FIG. 1 (C), the protective film 3 having the surface treatment layer 2 is adhered to one surface of the polarizing plate 1 with a surface opposite to the surface treatment layer 2 to constitute a polarizing plate. 5. The retardation film 7 is adhered to the surface of the polarizing plate 1 on the side opposite to the protective film 3 via an interlayer adhesive 8 to form an optical film 10. An adhesive layer 20 is provided on the outside of the retardation film 7 constituting the optical film 10, and a resin film 25 with an adhesive is formed. Then, the surface of the adhesive layer 20 on the side opposite to the optical film 10 is bonded to a liquid crystal cell 30 as a glass substrate to form an optical laminate 40.

In the example shown in FIG. 1 (D), the first protective film 3 having the surface treatment layer 2 is adhered to one surface of the polarizing plate 1 with a surface opposite to the surface treatment layer 2, and The second protective film 4 is adhered to the other surface of the polarizing plate 1 to form a polarizing plate 5. The retardation film 7 is pasted on the outer side of the second protective film 4 constituting the polarizing plate 5 through the interlayer adhesive 8 to form an optical film 10. Outside the retardation film 7 constituting the optical film 10 An adhesive layer 20 is provided to constitute a resin film 25 with an adhesive. Then, the surface of the adhesive layer 20 on the side opposite to the optical film 10 is bonded to a liquid crystal cell 30 as a glass substrate to form an optical laminate 40.

In these examples, the first protective film 3 and the second protective film 4 are generally composed of a triethyl cellulose cellulose film, but other than that, they can also be composed of various transparent resin films described above. In the present invention, as described above, the protective film 3 may be an acrylic resin film. In addition, the surface treatment layer formed on the surface of the first protective film 3 may be a hard coat layer, an anti-glare layer, an anti-reflection layer, an anti-static layer, or the like. A plurality of these layers may be provided. The method of adhering the first protective film 3, the second protective film 4 and the polarizing plate 1 is not particularly limited. For example, it can be used: it is composed of an aqueous solution or an aqueous dispersion, and the adhesive force is developed by evaporating water as a solvent. Water-based adhesives, or UV-curable adhesives that harden by ultraviolet irradiation to develop adhesiveness.

As the examples shown in (C) and (D) of FIG. 1, when the retardation film 7 is laminated on the polarizing plate 5, if the liquid crystal display device is a small-to-medium-sized liquid crystal display device, a preferable example of the retardation film 7 can be listed. 1/4 wavelength plate. At this time, the absorption axis of the polarizing plate 5 and the retardation film 7 of the retardation film 7 of the quarter-wave plate are generally arranged so as to intersect at almost 45 degrees. However, according to the characteristics of the liquid crystal cell 30, the The angle deviates somewhat from 45 degrees. On the other hand, in the case of a large liquid crystal display device such as a television, a phase difference film having various phase difference values is used in accordance with the characteristics of the liquid crystal cell 30 for the purpose of phase difference compensation or viewing angle compensation of the liquid crystal cell 30. At this time, it is generally arrange | positioned so that the absorption axis of the polarizing plate 5 and the retardation axis of the retardation film 7 may become almost orthogonal or almost parallel. When constructed with a 1/4 wavelength plate For the retardation film 7, a uniaxially or biaxially stretched film can be preferably used. In addition, when the retardation film 7 is provided for the purpose of phase difference compensation or viewing angle compensation of the liquid crystal cell 30, in addition to a uniaxial or biaxial stretching film, in addition to uniaxial or biaxial stretching, more A film called an optical compensation film, such as a film which is aligned in the thickness direction, or a film which is coated with a phase difference developing substance such as liquid crystal on a supporting film and whose orientation is fixed, is used as the retardation film 7.

Similarly, as in the examples shown in (C) and (D) of FIG. 1, when the polarizing plate 5 and the retardation film 7 are bonded via the interlayer adhesive 8, the interlayer adhesive 8 is generally acrylic-based. Agent, but of course, the adhesive layer specified in the present invention can also be formed here. As in the large-scale liquid crystal display device described above, when the absorption axis of the polarizing plate 5 and the retardation axis of the retardation film 7 are arranged so as to have an almost orthogonal or almost parallel relationship, the polarizing plate 5 and The retardation film is bonded by 7 rolls to 7 rolls. In applications that do not require re-release properties between the two, an adhesive that can be firmly bonded and cannot be peeled off after replacement can be used instead of (C ) And (D) interlayer adhesives 8. Examples of such an adhesive include a water-based adhesive that is composed of an aqueous solution or an aqueous dispersion and that exhibits adhesive force by evaporating water as a solvent, or that exhibits adhesive force by hardening by ultraviolet irradiation. UV-curable adhesive.

As shown in (C) and (D) of FIG. 1, the adhesive layer 20 itself is formed on the retardation film 7, and the adhesive layer 20 may be circulated to form a resin film with an adhesive in the present invention. A resin film with an adhesive formed by forming an adhesive layer on a retardation film, in addition to bonding the adhesive layer to a liquid crystal cell as a glass substrate to form an optical laminate, can also be a polarizing plate. The resin film is bonded to the retardation film side to form another adhesive agent.

FIG. 1 shows an example in which the adhesive-attached resin film 25 is arranged on the viewing side of the liquid crystal cell 30. However, the adhesive-attached resin film of the present invention may be arranged on the back side of the liquid crystal cell, that is, the backlight side. When the adhesive-attached resin film of the present invention is disposed on the back side of a liquid crystal cell, a protective film without a surface treatment layer may be used instead of the protective film 3 with a surface treatment layer 2 shown in FIG. 1 and others. It can be configured in the same manner as (A) to (D) in FIG. 1. In addition, at this time, various optical films that can be arranged on the back side of the liquid crystal cell, such as a brightness enhancement film, a light-condensing film, and a diffusion film, may be provided outside the protective film constituting the polarizing plate.

As described above, the optical laminate of the present invention can be preferably used in a liquid crystal display device. The liquid crystal display device formed of the optical laminated body of the present invention can be used, for example, in a personal computer liquid crystal display including a notebook type, a desktop type, a PDA (Personal Digital Assistant), a television, a vehicle-mounted display, and an electronic device. Dictionary, digital camera, digital video camera, electronic computer, clock, etc.

[Example]

The following series of examples illustrate the present invention in more detail, but the present invention is not limited to these examples. In the examples, parts and% indicating the amount and content are used as the basis of weight unless otherwise specified.

In the following example, the weight average molecular weight is used: "Shodex GPC KF-802" manufactured by Tosoh Co., Ltd. 4 "TSKge1 XL" and manufactured by Showa Denko Corporation and sold by Sokotsu Trading Co., Ltd. A total of 5 pieces are connected in series as a pipe string It is connected to a GPC device, and the eluent is tetrahydrofuran. The sample concentration is 5mg / mL, the sample introduction volume is 100μL, and the value is measured by standard polystyrene conversion at a temperature of 40 ° C and a flow rate of 1mL / min. .

In the following examples, the amount of warpage of a polarizing plate as an optical film during heating was measured in the following manner. First, a commercially available acrylic adhesive sheet having a storage elasticity of 0.05 MPa and a thickness of 25 μm at a temperature of 23 ° C. was laminated on one side of a polarizing plate by a laminator to form a polarizing plate with an adhesive. The polarizing plate with the adhesive was cut into slices having a size of 150 mm × 40 mm in a direction in which the polarizing film is stretched × a direction perpendicular to the direction in which the polarizing film is stretched. The exposed adhesive layer was bonded to a glass having a size of 51 mm × 156 mm and a thickness of 0.5 mm [trade name "Eagle XG" manufactured by Corning, Inc.] to obtain a polarizer plate / commercially available adhesive layer / glass. body. After the laminated body was stored under dry conditions at a temperature of 85 ° C. for 24 hours, the amount of warpage was measured after standing at room temperature for 30 minutes. The amount of warpage is placed on the measuring table with the curved laminated body facing downward and convex, and the position of the center of gravity is used as a reference, and the four corners of the polarizing plate constituting the laminated body float from the reference. The height is the longest in absolute value. The measured value was defined as the amount of warpage of the polarizing plate when heated.

First, polymerization examples of the first acrylic resins A to O and the acrylic resins P to W similar to the acrylic resins P to W specified in the present invention are shown. In the following polymerization examples, the (meth) acrylic acid alkyl ester of the monomer (a1) and the unsaturated monomer having the monomer (a2) having one olefinic double bond and at least one aromatic ring in the molecule Monomers, unsaturated monomers having a carboxyl group in the monomer (a3), unsaturated monomers having a hydroxyl group in the monomer (a4), unsaturated monomers having a amide bond, or unsaturated monomers having an amine group, Use the following.

<Monomer (a1)>

Butyl acrylate: abbreviated as "BA" in Table 1 described later.

2-ethylhexyl acrylate: abbreviated as "EHA" in Table 1 described later.

Methyl acrylate: abbreviated as "MA" in Table 1 described later.

<Monomer (a2)>

2-phenoxyethyl acrylate: abbreviated as "PEA" in Table 1 described later.

2- (2-phenoxyethoxy) ethyl acrylate: abbreviated as "PEA2" in Table 1 described later.

Benzyl acrylate: abbreviated as "BZA" in Table 1 described later.

<Monomer (a3)>

Acrylic acid: abbreviated as "AA" in Table 1 described later.

2-Succinyloxyethyl acrylate: abbreviated as "A-SA" in Table 1 described later.

<Monomer (a4)>

2-hydroxyethyl acrylate: abbreviated as "HEA" in Table 1 described later.

4-Hydroxybutyl acrylate: abbreviated as "4HBA" in Table 1 described later.

N, N-dimethylacrylamide: abbreviated as "DMAA" in Table 1 mentioned later.

2- (dimethylamino) ethyl acrylate: abbreviated as "DMAEA" in Table 1 described later.

N- (methoxymethyl) acrylamide: abbreviated as "MMAM" in Table 1 described later.

[Polymerization Example 1]

81.8 parts of ethyl acetate, 39.0 parts of butyl acrylate as monomer (a1) and 50.0 parts of methyl acrylate, 7.0 parts of 2-phenoxyethyl acrylate as monomer (a2), and monomer (a3) A mixed solution of 1.0 part of acrylic acid and 3.0 parts of 2-hydroxyethyl acrylate as a monomer (a4) was put into a reaction vessel including a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirrer, and the air in the apparatus was replaced with nitrogen. The composition does not contain oxygen and raises the internal temperature to 55 ° C. Then, a solution of 0.14 parts of azobisisobutyronitrile (polymerization initiator) dissolved in 10 parts of ethyl acetate was added in total. The temperature was maintained for 1 hour after the starter was added, and then while the internal temperature was maintained at 54 to 56 ° C, ethyl acetate was continuously added to the reaction container at an addition rate of 17.3 parts / hr, and the concentration of acrylic resin When it reached 35%, the addition of ethyl acetate was stopped, and the temperature was maintained at this temperature until 12 hours had passed since the start of the addition of ethyl acetate. Finally, ethyl acetate was added to adjust the concentration of the acrylic resin to 20%, and an ethyl acetate solution of the acrylic resin was prepared. The obtained acrylic resin had a weight average molecular weight Mw of 1.2 million based on polystyrene conversion of GPC and Mw / Mn of 4.94. This is called acrylic resin A. The weight ratio of the carbonyl group present in the acrylic resin A was 26.93%.

[Polymerization Example 2]

In addition to changing the composition of the copolymerized monomers, the monomer (a1) was 49.0 parts of butyl acrylate and 40.0 parts of methyl acrylate, the monomer (a2) was 7.0 parts of 2-phenoxyethyl acrylate, and the monomer (a3 ) Is 1.0 parts of acrylic acid, and monomer (a4) is 3.0 parts of 2-hydroxyethyl acrylate, and the rest are the same as in Polymerization Example 1 to produce an acrylic resin. The obtained acrylic resin had a weight-average molecular weight Mw based on GPC of polystyrene of 1.48 million and a Mw / Mn of 5.20. This is called acrylic resin B. The weight ratio of the carbonyl group present in the acrylic resin B was 25.86%.

[Polymerization Example 3]

After 120 parts of ethyl acetate was put into a reaction vessel including a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, and nitrogen was used instead of the air in the device to make it oxygen-free, the internal temperature was raised to 75 ° C. A solution of 0.05 parts of azobisisobutyronitrile (polymerization initiator) dissolved in 5 parts of ethyl acetate was added in the entire amount, and the monomer was used as a monomer (a1) within 2 hours while maintaining the internal temperature at 74 to 76 ° C. ) 49.0 parts of butyl acrylate and 40.0 parts of methyl acrylate, 7.0 parts of 2-phenoxyethyl acrylate as monomer (a2), 1.0 part of acrylic acid as monomer (a3), and monomer (a4) A mixed solution of 3.0 parts of 2-hydroxyethyl acrylate was dropped into the reaction system. The reaction was then completed by holding at an internal temperature of 74 to 76 ° C for 5 hours. Finally, ethyl acetate was added to adjust the concentration of the acrylic resin to 40%, and an ethyl acetate solution of the acrylic resin was prepared. The obtained acrylic resin had a weight average molecular weight Mw of 580,000 based on GPC polystyrene conversion, and Mw / Mn of 4.49. Call this Acrylic resin C. The weight ratio of the carbonyl group present in the acrylic resin C was 25.86%.

[Polymerization Examples 4 to 23]

The acrylic resins D to W were produced in the same manner as in Polymerization Example 1 except that the composition of the copolymerized monomers was changed as shown in Table 1. The weight average molecular weight, molecular weight distribution, and weight ratio of the carbonyl groups present in the acrylic resin of the obtained acrylic resin in terms of polystyrene in terms of GPC are shown in Table 1.

The composition of the copolymerized monomers of Polymerization Examples 1 to 23, the weight-average molecular weight of the obtained acrylic resin in terms of polystyrene conversion based on GPC, the molecular weight distribution, and the weight ratio of carbonyl groups present in the acrylic resin are shown in Table 1. In the columns of "Composition of monomer used for copolymerization of acrylic resin", "Mw", "Mw / Mn", and "CO weight ratio", respectively.

Next, examples and comparative examples of using the acrylic resin produced above to prepare an adhesive and applying it to an optical film are shown. In the following examples, the following are used as the crosslinking agent and the silane compound.

<Crosslinking agent>

Coronate-L: ethyl acetate solution of trimethylolpropane adduct of toluene diisocyanate (solid content concentration 75%), obtained from Nippon Polyurethane Industry Co., Ltd. It is abbreviated as "Cor-L" in Table 2 described later.

Takenate D-204EA: ethyl acetate solution of isocyanurate of toluene diisocyanate (solid content concentration: 50%) was obtained from Mitsui Chemicals Co., Ltd. It is abbreviated as "D204EA" in the second table described later.

<Silane compound>

KBM-403: Glycidoxypropyltrimethoxysilane (liquid), obtained from Shin-Etsu Chemical Industry Co., Ltd. It is abbreviated as "KBM403" in Table 2 described later.

X-41-1053: polysiloxane oligomer (liquid), obtained from Shin-Etsu Chemical Industry Co., Ltd. It is abbreviated as "1053" in the second table described later.

[Examples 1 to 21 and Comparative Examples 1 to 8] (a) Manufacturing of adhesives

Using the ethyl acetate solution having a concentration of 20% of the acrylic resins obtained in Polymerization Examples 1, 2, and 4 to 23, the above-mentioned crosslinking agents were mixed in an amount shown in Table 2 with respect to 100 parts of the solid content, respectively, and The silane compounds were mixed in the amounts shown in Table 2 respectively, and then ethyl acetate was added so that the solid content concentration became 13% to form an adhesive composition. The cross-linking agent was obtained as an ethyl acetate solution, but the added amount shown in Table 2 is a solid Body composition amount.

In addition, using the ethyl acetate solution having a concentration of 40% of the acrylic resin obtained in Polymerization Example 3, each of the above-mentioned crosslinking agents was mixed in an amount shown in Table 2 with respect to 100 parts of the solid content, and as shown in Table 2 Each of the silane compounds was mixed in the amounts shown, and then ethyl acetate was added so that the solid content concentration became 28% to form an adhesive composition. The crosslinking agent was obtained as an ethyl acetate solution, but the amount of addition shown in Table 2 is the amount of solid content.

(b) Preparation of adhesive sheet

Using a thin coater, each adhesive composition prepared in (a) above was applied to a polyethylene terephthalate film subjected to a release treatment so that the thickness after drying was 20 μm [from The release treatment surface of the product name "PLR-382051" (referred to as a separator) obtained by Lintec Co., Ltd. was dried at 100 ° C for 1 minute to produce an adhesive sheet.

(c) Fabrication of polarizer with adhesive

A polyvinyl alcohol film [trade name "Kuraray Vinylon VF-PE # 6000" manufactured by Kuraray Co., Ltd.] having an average degree of polymerization of about 2400, a degree of saponification of 99.9 mol, and a thickness of 60 μm was immersed in pure water at 37 ° C, and then at 30 ° C. An aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.04 / 1.5 / 100 was immersed. Then, it was immersed in an aqueous solution having a weight ratio of potassium iodide / boric acid / water of 12 / 3.6 / 100 at 56.5 ° C. Next, it was washed with pure water at 10 ° C, and then dried at 85 ° C to obtain polarized light having an iodine adsorption alignment to the thickness of polyvinyl alcohol of about 23 μm. membrane. Stretching is mainly performed in the steps of iodine dyeing and boric acid treatment, and the total stretching ratio is 5.3 times.

A second acrylic resin containing a UV absorbing material with a thickness of 80 μm [trade name "Technolloy S001" manufactured by Sumitomo Chemical Co., Ltd.] was laminated on one side of the polarizing film produced above, and laminated on the other side A polarizing plate with a 3-layer structure consisting of a cycloolefin-based resin with a thickness of 52 μm [a moisture permeability of 42 g / (m ² ‧ 24 hr at a temperature of 40 ° C. and a relative humidity of 90%) of a polarizer The laminator applies the surface of the adhesive sheet (adhesive surface) on the opposite side of the separator sheet (adhesive surface) made in (b) above to a retardation film surface made of a cycloolefin resin, and the temperature is 23 ° C. After curing for 7 days under the conditions of ℃ and 65% relative humidity, a polarizing plate with an adhesive was produced. The amount of warpage of this polarizing plate when heated was 1650 μm.

(d) Determination of tensile elastic modulus of the adhesive layer

After the adhesive sheet prepared in (b) above was aged at room temperature for 7 days, the tensile elastic modulus was measured by the following method. First, after the adhesive sheet is matured, the operation of overlapping the adhesive surfaces of the two groups of adhesive sheets with each other and peeling off one of the separators, and the adhesive surface appearing on the surface further overlaps the adhesive surface of the other adhesive sheet is repeated. , And an adhesive sheet having a thickness of 600 μm was produced. A 15 mm × 50 mm slice was cut out from the adhesive sheet, and the sample was peeled from the separator to prepare a measurement sample. This measurement sample was fixed to the upper and lower jigs of a tensile tester [AUTOGRAPH AG-IS, manufactured by Shimadzu Corporation] to measure the length of the measurement sample. The method of tensile elasticity in the lateral direction is set with a distance of 30 mm between the clamps, and is stretched under a condition of a tensile speed of 300 mm / min in an environment of a temperature of 23 ° C and a relative humidity of 55% to produce a stress-strain And calculate the tensile elastic modulus (MPa). The results are shown in Table 2.

(e) Fabrication and evaluation of optical laminates

The optical laminated system peeled off the separator from the polarizer with the adhesive prepared in (c) above, and adhered the adhesive to the glass substrate for a liquid crystal cell in a cross-polarized manner [a product of Corning Corporation] The name "Eagle XG"] was made on both sides. The optical laminate was subjected to a durability test under the following three conditions. On the optical laminate after each test, the presence or absence of a change in appearance caused by the floating, peeling, or foaming of the adhesive layer was visually observed. . The endurance test is a heat resistance test stored for 1000 hours under dry conditions at a temperature of 100 ° C; a moist heat resistance test stored for 1000 hours at a temperature of 80 ° C and a relative humidity of 90%; and a temperature decrease from a heating state to 70 ° C to -40 ° C The process of heating up to 70 ° C for 1 cycle (30 minutes), and repeating the 500 cycle heat shock test. The results are classified according to the following criteria and summarized in Table 2.

<Evaluation Criteria for Heat Resistance Test, Humidity Resistance Test, and Thermal Shock Resistance Test>

：: No change in appearance such as lifting, peeling, or foaming was observed at all.

：: Almost no change in appearance such as floating, peeling, or foaming was observed.

△: Changes in appearance such as floating, peeling, or foaming are slightly noticeable.

×: Significant changes in appearance such as floating, peeling, or foaming were observed.

From Tables 1 and 2, it can be seen that Examples 1 to 2 using the adhesive composition specified in the present invention are compared with those using an adhesive composition composed of an acrylic resin outside the specified range of the present invention. Compared with Examples 1 to 5, in terms of heat resistance, damp heat resistance and thermal shock resistance, To excellent results.

[Industrial applicability]

When the adhesive-attached resin film of the present invention is bonded to a glass substrate with an adhesive layer interposed therebetween, even if the resin film is an optical film with a large amount of deformation in a durability test under a severe environment such as an assumed automotive use, It does not float or peel, and is excellent in durability. The resin film using an optical film as an adhesive with the resin film can be preferably used in a liquid crystal display device.

Claims (9)

A resin film with an adhesive is provided on the surface of the resin film with an adhesive layer formed of an adhesive composition containing a first acrylic resin, characterized in that the first acrylic resin is composed of the following (a1) (A2), (a3), and (a4) monomer copolymers, (a1) alkyl (meth) acrylate 60 to 96.99% by weight, (a2) has an olefinic double bond in the molecule 2 to 30% by weight of the unsaturated monomers with at least one aromatic ring, (a3) 0.01 to 2% by weight of the unsaturated monomers having a carboxyl group, and (a4) selected from unsaturated monomers having a hydroxyl group, and amidine 1 to 8% by weight of at least one monomer in a group consisting of an unsaturated monomer having a bond and an unsaturated monomer having an amine group, wherein the compounding ratio from the foregoing monomer and the carbonyl group per molecule of the monomer The weight ratio of the carbonyl group present in the acrylic resin is 24% or more. The adhesive-attached resin film according to item 1 of the scope of patent application, wherein the adhesive layer is formed of an adhesive composition containing the following (A), (B), and (C): (A) the foregoing 100 parts by weight of the first acrylic resin, which is a copolymer obtained from the monomer mixture containing the aforementioned (a1), (a2), (a3), and (a4), and has a weight average molecular weight of 500,000 to 1.7 million; (B ) 0.1 to 1 part by weight of an isocyanate-based crosslinking agent; and 0.05 to 5 parts by weight of a silane compound. The adhesive-attached resin film according to item 2 of the scope of patent application, wherein the (meth) acrylic acid alkyl ester (a1) is at least an alkyl acrylate having an alkyl group having 1 to 3 carbon atoms, and having A mixture of alkyl (meth) acrylates having 4 to 14 alkyl groups which may be substituted by alkoxy groups having 1 to 10 carbon atoms. The adhesive-attached resin film according to any one of claims 1 to 3, wherein the resin film is an optical film selected from a polarizing plate and a retardation film. According to the resin film with an adhesive as described in item 4 of the scope of the patent application, wherein the aforementioned polarizing plate is a laminated film having a protective film, a polarizing film, and a retardation film sequentially, the protective film is a transparent resin composed of a second acrylic resin The film and the retardation film are resin films composed of a resin selected from the group consisting of a cycloolefin resin, a cellulose resin, a polyester resin, and a polycarbonate resin. The resin film with an adhesive as described in item 4 of the scope of patent application, wherein the aforementioned optical film is an amount of warpage after being held at 85 ° C for 24 hours in a state of being adhered to a glass having a thickness of 0.5 mm, and the absolute value is It is 1400 μm or more. The adhesive-attached resin film according to any one of claims 1 to 3, wherein the adhesive layer has a tensile elasticity of at least 0.22 MPa at a temperature of 23 ° C. The adhesive-attached resin film according to any one of claims 1 to 3, wherein a release film is adhered to the surface of the aforementioned adhesive layer. An optical laminated body, characterized in that the resin film with an adhesive as described in any one of claims 4 to 7 of the scope of patent application is formed by laminating a glass substrate on the side of the adhesive layer.