KR20110037894A - A liquid crystal panel - Google Patents

Abstract

PURPOSE: A liquid crystal panel is provided to control adhesive layer from being split or taken off form a glass cell which is adhered to a pair of a polarized plate through an adhesive layer. CONSTITUTION: A liquid crystal panel includes a glass cell for rectangular liquid display. A first polarization plate has an absorption shaft which is adhered to long length of a glass cell through a first adhered layer to one surface of the glass cell. A second polarization plate has a absorption shaft which is vertical to the absorption shaft of the first polarization plate through a second adhesive layer on another surface of the glass cell.

Description

Liquid crystal panel {A LIQUID CRYSTAL PANEL}

This invention relates to the liquid crystal panel in which the polarizing plate adhered to the both surfaces of the glass cell for liquid crystal displays through an adhesive layer, respectively.

The polarizing plate is mounted on a liquid crystal display device and is widely used. A transparent protective film is laminated on both surfaces of a polarizing film, and an adhesive layer is formed on the surface of at least one protective film, and a release film is adhered on the adhesive layer. It is in circulation. Moreover, retardation film may be laminated | stacked on the polarizing plate of the state in which the protective film adhere | attached on both surfaces of a polarizing film, and an adhesive layer / peeling film may adhere to the retardation film side. Before sticking to a liquid crystal cell, a peeling film is peeled off from these polarizing plates, it adhere | attaches on the glass cell for liquid crystal displays through the exposed adhesive layer, it becomes a liquid crystal panel, and sets back light etc. and becomes a liquid crystal display device. When the liquid crystal panel in which the polarizing plate is adhered to the glass cell for liquid crystal display in this manner is exposed to high temperature, the distribution of residual stress acting on the polarizing plate becomes nonuniform, resulting in stress concentration on the outer peripheral portion of the polarizing plate, resulting in black display. In some cases, the outer periphery may cause a phenomenon called whiteout (also called a "light leak"), or cause color spots. Thus, suppression of such whiteout or color spots is required.

As one of the countermeasures, JP-2007-138056-A copolymerizes an aromatic ring-containing monomer with an alkyl acrylate ester, and the ratio (Mw / Mn) to the number average molecular weight (Mn) of the weight average molecular weight (Mw) of the resin obtained. The technique which suppresses light leakage by extending the molecular weight distribution shown by () to 10-50 is disclosed. Although light leakage is reduced by using such an adhesive, it cannot be said that it is necessarily enough, and because of the wide molecular weight distribution, foaming may occur under high temperature conditions.

On the other hand, when the liquid crystal panel is placed under high temperature or high temperature and high humidity conditions or when heating and cooling are repeated, foaming occurs in the pressure-sensitive adhesive layer according to the dimensional change of the polarizing plate, between the polarizing plate and the pressure-sensitive adhesive layer or between the pressure-sensitive adhesive layer and the liquid crystal cell. Floating, peeling, etc. may arise in the case. Therefore, it is required to be excellent in durability without causing such a problem. In addition, when a polarizing plate having an adhesive is attached to a glass cell for liquid crystal display to form a liquid crystal panel, when there is any problem, the polarizing plate is once detached and then a new film is fixed again. It is also required to be excellent in the so-called rework property that the film is pulled off along the polarizing plate, and no adhesive remains on the glass cell, and no dark part or the like is generated.

Moreover, JP-2010-66756-A has acrylic resin which copolymerized the (meth) acrylic-acid alkoxy alkyl ester which has 2-methoxyethyl as the representative example to the (meth) acrylic-acid alkylester which has butyl acrylate as a representative example. And an ionic compound, in particular, in combination with an ionic compound which is solid at room temperature, the pressure-sensitive adhesive layer is formed on an optical film, thereby providing the pressure-sensitive adhesive layer with antistatic properties, particularly antistatic properties excellent in stability over time. Is disclosed.

An object of the present invention is to provide a liquid crystal panel in which a pair of polarizing plates are adhered to both surfaces of a glass cell for liquid crystal display, respectively, through an adhesive layer, so that whiteout can be sufficiently suppressed even if it is enlarged.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve this problem, the present inventors adhere | attached the 1st polarizing plate and the 2nd polarizing plate through the adhesive layer, respectively, on both surfaces of the liquid crystal display glass cell with a rectangular display screen, In the liquid crystal panel used for the large sized liquid crystal display device whose absorption axis is parallel to the long side of the said glass cell, and whose absorption axis is orthogonal to the absorption axis of the said 1st polarizing plate, the said adhesive By adding an improvement to a layer, whiteout can be effectively suppressed, the liquid crystal panel excellent also in durability can be obtained, and this adhesive layer discovered that it was also excellent in the rework property of a polarizing plate, and reached this invention. Specifically, the pressure-sensitive adhesive layer contains (meth) acrylic acid alkyl ester as a main component, and includes a structural unit derived from an unsaturated monomer having a polar functional group and a structural unit derived from an unsaturated monomer having an aromatic ring in a molecule. It was found to be effective to comprise a predetermined amount including a predetermined amount, in which a predetermined amount of a crosslinking agent was added to an acrylic resin having a narrow molecular weight distribution.

[1] In other words, the liquid crystal panel according to the present invention has a rectangular liquid crystal display cell, and one side of the glass cell is attached so that the absorption axis is parallel to the long side of the glass cell through the first adhesive layer. A first polarizing plate and a second polarizing plate adhered such that an absorption axis is perpendicular to an absorption axis of the first polarizing plate through a second pressure sensitive adhesive layer on the other side of the glass cell, wherein the first pressure sensitive adhesive layer and the first agent One or more of 2 adhesive layers is formed from the adhesive composition containing the acrylic resin (A) and crosslinking agent (B) shown below, and this adhesive layer has a gel fraction of 60 to 99 weight%.

(A) (A-1) Formula I

(In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents an alkyl group having 1 to 14 carbon atoms, which may be substituted with an alkoxy group having 1 to 10 carbon atoms.)

80-96 weight% of (meth) acrylic-acid alkylester represented by

(A-2) 3 to 15% by weight of an unsaturated monomer having one olefinic double bond and at least one aromatic ring in the molecule (hereinafter sometimes referred to as an "aromatic ring-containing monomer"), and

(A-3) 0.1-5 weight% of unsaturated monomer which has polar functional group (Hereinafter, it may be called "polar functional group containing monomer.")

Molecular weight represented by Mw / Mn which is obtained by copolymerizing the monomer mixture containing and which has a weight average molecular weight (Mw) in the range of 1 million-2 million, and is a ratio with respect to the number average molecular weight (Mn) of a weight average molecular weight (Mw). 100 parts by weight of acrylic resin having a distribution in the range of 3 to 7, and

(B) 0.01-5 weight part of crosslinking agents.

As described above, in the present invention, at least one of the first pressure-sensitive adhesive layer and the second pressure-sensitive adhesive layer for adhering the first polarizing plate and the second polarizing plate disposed on both surfaces of the glass cell for liquid crystal display to the glass cell, respectively, the above formula I Acrylic resin (A) obtained by copolymerizing the monomer mixture containing the (meth) acrylic-acid alkylester (A-1), aromatic ring containing monomer (A-2), and polar functional group containing monomer (A-3) represented by And it forms in the adhesive composition containing a crosslinking agent (B), and makes it possible to suppress whiteout effectively by making the gel fraction into a predetermined range.

[2] The first pressure sensitive adhesive layer and the second pressure sensitive adhesive layer are both formed of an adhesive composition containing 100 parts by weight of the acrylic resin (A) and 0.01 to 5 parts by weight of the crosslinking agent (B), and the pressure sensitive adhesive layer is 60 to Liquid crystal panel as described in [1] which has a gel fraction of 99 weight%. This aspect is further more preferable in suppressing whiteout.

[3] The liquid crystal panel according to [1] or [2], wherein the aromatic ring-containing monomer (A-2) is an aromatic ring-containing (meth) acryl compound represented by the following Formula II. This aspect is preferred.

In formula, R <_3> represents a hydrogen atom or a methyl group, n is an integer of 1-8, R <_4> represents a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group.

[4] The polar functional group-containing monomer (A-3) described in any one of [1] to [3], wherein the polar functional group-containing monomer (A-3) has at least one polar functional group selected from the group consisting of a free carboxyl group, a hydroxyl group, an amino group and an epoxy ring. Liquid crystal panel. This aspect is preferred.

[5] The liquid crystal panel according to any one of [1] to [4], wherein the crosslinking agent (B) contains an isocyanate compound. This aspect is preferred.

[6] The liquid crystal panel according to [4], wherein the crosslinking agent (B) contains at least an isocyanate compound. This aspect is preferred.

[7] The liquid crystal panel according to any one of [1] to [6], wherein the pressure sensitive adhesive composition further contains 0.03 to 1 part by weight of the (C) silane compound.

[8] The liquid crystal panel according to any one of [1] to [7], wherein the pressure sensitive adhesive composition further contains (D) an ionic compound. Antistatic property can also be provided by this aspect.

[9] The liquid crystal panel according to [8], wherein the aromatic ring-containing monomer (A-2) is an aromatic ring-containing (meth) acrylic compound represented by Formula II, wherein n in the formula is 2 or more. In this embodiment, when the ionic compound is blended into the pressure-sensitive adhesive composition containing an acrylic resin copolymerized with this monomer, the antistatic property is provided while maintaining a high whiteout suppression effect. I found out that I could do it.

[10] The liquid crystal panel according to any one of [1] to [9], wherein at least one of the first polarizing plate and the second polarizing plate is a protective film / polarizing film / protective film. This aspect is preferred.

[11] Of the two protective films having the polarizing film interposed thereon, the film located farther from the glass cell for liquid crystal display has an in-plane retardation value of 0 to 20 nm and a retardation value in the thickness direction of 20 to 80 nm. [10] The film containing the cellulose resin and positioned on the glass cell side for the liquid crystal display includes a cellulose acetate-based resin having an in-plane retardation value of 30 to 80 nm and a retardation value of 80 to 250 nm in the thickness direction. The liquid crystal panel described. This aspect is preferred.

[12] Of the two protective films having the polarizing film interposed therebetween, acetic acid having a phase difference value in the plane of 0 to 20 nm and a phase difference value in the thickness direction of 20 to 80 nm in a plane located farther from the glass cell for liquid crystal display. [10] A film containing cellulose resin and positioned on the glass cell side for liquid crystal display comprises cellulose acetate-based resin having an in-plane retardation value of 0 to 10 nm and a retardation value of -25 to 25 nm in the thickness direction. The liquid crystal panel described in. This aspect is also preferable.

[13] Of the two protective films having the polarizing film interposed therebetween, the film located farther from the glass cell for liquid crystal display includes cellulose acetate resin, and the film located on the glass cell side for liquid crystal display includes cycloolefin resin. The liquid crystal panel as described in [10] containing. This aspect is also preferable.

In the present invention, a pair of polarizing plates are adhered to both surfaces of the glass cell for liquid crystal display via an adhesive layer so as to cross orthogonal nicols, that is, each absorption axis is orthogonal, and one polarizing plate is absorbed. In the liquid crystal panel arrange | positioned so that an axis may become parallel to the long side of the said glass cell, WHEREIN: The acrylic resin (A) for forming an adhesive layer contains a predetermined amount the unit guide | induced from an aromatic ring containing monomer (A-2). By setting it as a copolymer and making the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) into a specific range, the optical defect resulting from nonuniform stress distribution is prevented and whiteout is suppressed.

Moreover, by making the gel fraction of an adhesive layer into the range of 60 to 99 weight%, the durability of an adhesive layer improves and this liquid crystal panel suppresses the external appearance change at the time of testing, such as heat resistance, heat and moisture resistance, and heat shock resistance. . In addition, after attaching a polarizing plate to the glass cell for liquid crystal display through the above-mentioned adhesive layer, this liquid crystal panel, even if there exists a problem, peels a polarizing plate from a glass cell with an adhesive layer, even if it peels from the glass cell after peeling. Adhesive debris and a dark part generate | occur | produce little, and it becomes the thing excellent in rework property.

In this liquid crystal panel, since the pressure-sensitive adhesive layer absorbs and relaxes the stress caused by the dimensional change of the polarizing plate and the glass cell under moist heat conditions, local stress concentration is reduced, and the pressure-sensitive adhesive layer is suppressed from being lifted or peeled off from the glass cell. do.

1 is an exploded perspective view showing the relationship between the layer configuration and the axial angle of a liquid crystal panel according to the present invention.
It is a cross-sectional schematic diagram which shows the example of the laminated constitution of the polarizing plate in which the adhesive layer for sticking to the glass cell for liquid crystal displays was formed.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings as appropriate. The relationship between the layer structure and the axial angle of the liquid crystal panel according to the present invention is shown in exploded perspective view in FIG. Referring to FIG. 1, the liquid crystal panel to which the present invention is applied may sometimes be referred to as a glass cell 10 for liquid crystal display (hereinafter, simply referred to as a "liquid crystal cell" or a "glass cell") having a rectangular display surface. ), The first polarizing plate 21 is adhered to the first adhesive layer 31 via the first adhesive layer 31, and the second polarizing plate 22 is attached to the other surface of the liquid crystal cell 10 via the second adhesive layer 32. This is sticky. These pairs of polarizing plates 21 and 22 are arranged to be orthogonal Nicole, that is, so that their absorption axes 21A and 22A are orthogonal, and the first polarizing plate 21 has its absorption axis 21A as its liquid crystal cell ( It is arrange | positioned so that it may become parallel with the long side 10A of 10). Therefore, the 2nd polarizing plate 22 is arrange | positioned so that the absorption axis 22A may be perpendicular to the long side 10A of the liquid crystal cell 10 (parallel with the short side of the liquid crystal cell 10).

At least one of the first pressure sensitive adhesive layer 31 for adhering the first polarizing plate 21 to the liquid crystal cell 10 and the second pressure sensitive adhesive layer 32 for adhering the second polarizing plate 22 to the liquid crystal cell 10. The side is formed from an adhesive composition containing 0.01 to 5 parts by weight of the crosslinking agent (B) based on 100 parts by weight of the specific acrylic resin (A), and the gel fraction of the adhesive layer is 60 to 99% by weight.

The first polarizing plate 21 is arranged such that its absorption axis 21A is parallel to (0 °) the long side 10A of the liquid crystal cell 10, and the second polarizing plate 22 has its absorption axis 22A. It was found that it is particularly effective to apply the pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition defined in the present invention to the liquid crystal panel arranged so as to be perpendicular to the long side 10A of the liquid crystal cell 10 (90 °). Although at least one of the adhesive layers 31 and 32 arrange | positioned on both surfaces of the liquid crystal cell 10 is formed by the above-mentioned specific adhesive composition, and the gel fraction becomes a specific range, the desired effect is expressed, but also before As mentioned above, it is preferable to comprise both of the adhesive layers 31 and 32 arrange | positioned at both surfaces of the liquid crystal cell 10 from a viewpoint of whiteout suppression.

Hereinafter, each member which comprises the liquid crystal panel of this invention advances description sequentially from the glass cell 10 for liquid crystal displays.

[Glass Cells for Liquid Crystal Display]

The glass cell 10 for liquid crystal displays is comprised from two transparent glass substrates 11 and 12, and sandwiches a liquid crystal (not shown) between them. The liquid crystal encapsulated between the two glass substrates 11 and 12 has a twisted nematic (TN), vertical alignment (VA), and in-plane switching (IPS) according to its alignment method. Etc. There are various systems. The present invention can be applied to any type of liquid crystal cell as long as the pair of polarizing plates are arranged at orthogonal nicols above and below the liquid crystal cell, and the absorption axis of one polarizing plate is arranged parallel to the long side of the glass cell. have. Although not shown, on the liquid crystal layer side of the transparent glass substrates 11 and 12, an alignment film for orienting the liquid crystal, a transparent electrode for turning the voltage on and off in order to control the alignment thereof, and a color filter for color display are also arranged.

Soda-lime glass, low alkali glass, an alkali free glass, etc. can be used for the glass substrates 11 and 12 which comprise the liquid crystal cell 10, Especially an alkali free glass or a low alkali glass is used suitably.

[Adhesive Layer (Adhesive Composition)]

Next, the adhesive composition for forming the adhesive layers 31 and 32 is demonstrated. This pressure-sensitive adhesive composition basically comprises an acrylic resin and a crosslinking agent. In the present invention, at least one of the first pressure sensitive adhesive layer 31 for adhering the first polarizing plate and the second pressure sensitive adhesive layer 32 for adhering the second polarizing plate to both surfaces of the liquid crystal cell 10 is described above. It is a specific copolymer, It forms in the adhesive composition which the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) are in the predetermined range, and mix | blended the adhesive composition by which the crosslinking agent (B) was mix | blended in predetermined amount, The gel fraction is 60 to 99% by weight. Each component which comprises this adhesive composition is demonstrated.

<Acrylic resin (A)>

In the liquid crystal panel of the present invention, the acrylic resin (A) used in the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layers 31 and 32 includes a structural unit derived from the (meth) acrylic acid alkyl ester represented by the formula (I). In addition to the structural unit derived from such (meth) acrylic-acid alkylester, the structural unit derived from an aromatic ring containing monomer and the structural unit derived from a polar functional group containing monomer are included. Here, (meth) acrylic acid means that any of acrylic acid or methacrylic acid is good, and "(meth)" when referring to (meth) acrylate, (meth) acryloyl, etc. is also the same meaning. .

In said Formula I used as a main structural unit of an acrylic resin (A), R <_1> is a hydrogen atom or a methyl group, and R <_2> is a C1-C14 alkyl group. The hydrogen group in each group may be substituted by the C1-C10 alkoxy group in the alkyl group represented by R <_2> .

In the (meth) acrylic-acid alkylester (A-1) represented by Formula I, R <_2> is an unsubstituted alkyl group, Specifically, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-octyl acrylate, and acrylic acid Linear alkyl acrylates such as lauryl; Branched alkyl acrylate esters such as isobutyl acrylate, 2-ethylhexyl acrylate and isooctyl acrylate; Linear alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate and lauryl methacrylate; Branched methacrylic acid alkyl esters, such as isobutyl methacrylate, 2-ethylhexyl methacrylate, and isooctyl methacrylate, etc. are illustrated.

Among these, n-butyl acrylate is preferable, and the above-mentioned (meth) acrylic-acid alkylester (A-1) specifically, so that n-butyl acrylate may be 50 weight% or more among all the monomers which comprise an acrylic resin (A). It is desirable to satisfy the requirements of).

As (meth) acrylic-acid alkylester represented by Formula I, when R <_2> is an alkyl group substituted by the alkoxy group, ie, an alkoxyalkyl group, Specifically, 2-acrylate ethyl, ethoxy methyl acrylate, 2-methacrylate Oxyethyl, ethoxymethyl methacrylate, and the like are exemplified.

These (meth) acrylic-acid alkylesters may be used independently, and may copolymerize using several other things.

The unsaturated monomer (aromatic ring-containing monomer) (A-2) having one olefinic double bond and at least one aromatic ring in the molecule preferably has a (meth) acryloyl group as a group containing an olefinic double bond. Do. Examples thereof include benzyl (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, and the like, and preferred are aromatic ring-containing (meth) acryl compounds represented by the above formula (II).

In Formula II which represents an aromatic ring containing (meth) acryl compound, when R <_4> is an alkyl group, its carbon number may be about 1-9, and likewise, when it is an aralkyl group, its carbon number is about 7-11, and it is an aryl group In this case, the carbon number may be about 6-10. Methyl, butyl, nonyl and the like as the alkyl group having 1 to 9 carbon atoms; benzyl, phenethyl, naphthylmethyl and the like as the aralkyl group having 7 to 11 carbon atoms; and phenyl, tolyl, naphthyl and the like as the aryl group having 6 to 10 carbon atoms. Each can be mentioned.

Specific examples of the aromatic ring-containing (meth) acrylic compound of formula II include (meth) acrylic acid 2-phenoxyethyl, (meth) acrylic acid 2- (2-phenoxyethoxy) ethyl, and (meth) acrylic acid of ethylene oxide-modified nonylphenol. Ester, (meth) acrylic acid 2- (o-phenylphenoxy) ethyl, and the like. These aromatic ring containing monomers may be used independently, respectively and may be used in combination of several other thing. Among these, a (meth) acrylate, 2-phenoxyethyl [In the formula II, R ₄ = H, the compound of n = 1], (meth) acrylate, 2- (o- phenyl phenoxy) acetate [the formula II Wherein R ₄ = o-phenyl, a compound of n = 1], or (meth) acrylic acid 2- (2-phenoxyethoxy) ethyl [compound of R ₄ = H, n = 2 in the formula II]] It is used suitably as one of the aromatic ring containing monomers (A-2) which comprise this acrylic resin (A).

In the polar functional group-containing monomer (A-3), the polar functional group may be a free carboxyl group, a hydroxyl group, an amino group, a heterocyclic group including an epoxy ring, or the like. The polar functional group-containing monomer is preferably a (meth) acrylic acid compound having a polar functional group. Examples thereof include unsaturated monomers having free carboxyl groups such as acrylic acid, methacrylic acid and β-carboxyethyl acrylate; Hydroxyl groups such as (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 2- or 3-chloro-2-hydroxypropyl and diethylene glycol mono (meth) acrylate Unsaturated monomer having: acryloyl morpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclo Unsaturated monomers having heterocyclic groups such as hexylmethyl (meth) acrylate, glycidyl (meth) acrylate and 2,5-dihydrofuran; And unsaturated monomers having an amino group different from the heterocycle, such as N, N-dimethylaminoethyl (meth) acrylate.

It is preferable that a polar functional group is a free carboxyl group, a hydroxyl group, an amino group, or an epoxy ring. These polar functional group containing monomers may be used independently, respectively and may use several other things.

Among these, it is preferable to use the unsaturated monomer which has a hydroxyl group as one of the polar functional group containing monomers (A-3) which comprise an acrylic resin (A). Moreover, in addition to the unsaturated monomer which has a hydroxyl group, it is also effective to use together the unsaturated monomer which has another polar functional group, for example, the unsaturated monomer which has a free carboxyl group.

In acrylic resin (A), although the structural unit derived from the (meth) acrylic-acid alkylester (A-1) represented by said Formula I is 80-96 weight%, Preferably it is 82 weight% or more, Furthermore, Preferably it is 94 weight% or less. Although the structural unit derived from an aromatic ring containing monomer (A-2) is 3-15 weight%, Preferably it is 5 weight% or more, Furthermore, 7 weight% or more, Especially 8 weight% or more, Preferably it is Up to 13% by weight, further up to 11% by weight, in particular up to 10% by weight. Although the structural unit derived from a polar functional group containing monomer (A-3) is 0.1 to 5 weight%, Preferably it is 0.5 weight% or more, Preferably it is 3 weight% or less.

The acrylic resin (A) used for this invention is a (meth) acrylic-acid alkylester (A-1) represented by the above-mentioned Formula I, an aromatic ring containing monomer (A-2), and a polar functional group containing monomer (A-3). The structural unit derived from the monomer different from may be included. As an example of these, the structural unit derived from the (meth) acrylic acid ester which has an alicyclic structure in a molecule | numerator, the structural unit derived from a styrene monomer, the structural unit derived from a vinylic monomer, and a some (meth) acryloyl group in a molecule | numerator Structural units derived from the monomer which has a etc. are mentioned.

The alicyclic structure is a cycloparaffin structure having usually 5 or more, preferably 5 to 7, carbon atoms forming a ring. Specific examples of the acrylate ester having an alicyclic structure include isobornyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, cyclododecyl acrylate, methylcyclohexyl acrylate, trimethylcyclohexyl acrylate, tert-butylcyclohexyl acrylate, and α-E. Cyclohexyl oxyacrylate, cyclohexyl acrylate, etc. are mentioned, As a specific example of the methacrylic acid ester which has an alicyclic structure, isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, and methacrylic acid Cyclododecyl, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, cyclohexyl methacrylate, and the like.

Specific examples of the styrene monomers include, in addition to styrene, alkyl styrene such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene and octyl styrene; Halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene and iodine styrene; Moreover, nitro styrene, acetyl styrene, methoxy styrene, divinyl benzene, etc. are mentioned.

Specific examples of the vinyl monomers include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate and vinyl laurate; Vinyl halides such as vinyl chloride and vinyl bromide; Vinylidene halides such as vinylidene chloride; Nitrogen-containing aromatic vinyls such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; Conjugated diene monomers such as butadiene, isoprene and chloroprene; Furthermore, acrylonitrile, methacrylonitrile, etc. are mentioned.

As a specific example of the monomer which has a some (meth) acryloyl group in a molecule | numerator, 1, 4- butanediol di (meth) acrylate and 1, 6- hexanediol di (meth) acrylate. 1,9-nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate and tripropylene glycol di (meth) acrylic Monomers having two (meth) acryloyl groups in the same molecule as the rate; The monomer etc. which have three (meth) acryloyl groups in the same molecule as a trimethylol propane tri (meth) acrylate are mentioned.

Monomers different from the (meth) acrylic-acid alkylester (A-1), an aromatic ring containing monomer (A-2), and a polar functional group containing monomer (A-3) represented by the above Formula I are each independently or two types The above combination can be used. In acrylic resin (A) used for an adhesive, the structure derived from a monomer different from a (meth) acrylic-acid alkylester (A-1), an aromatic ring containing monomer (A-2), and a polar functional group containing monomer (A-3) A unit is contained in the ratio of 0-10 weight part normally with respect to 100 weight part of non volatile matters of this resin.

The resin component which comprises an adhesive composition originates in the (meth) acrylic-acid alkylester (A-1), aromatic ring containing monomer (A-2), and polar functional group containing monomer (A-3) represented by the above Formula I. You may contain two or more types of acrylic resin containing a structural unit. In addition, to the acrylic resin (A) defined in the present invention, an acrylic resin having a structural unit derived from a different acrylic resin, for example, a (meth) acrylic acid alkyl ester of formula I, and containing no polar functional group is mixed. May be used. The acrylic resin (A) containing the structural unit derived from the (meth) acrylic-acid alkylester (A-1) represented by Formula I, an aromatic ring containing monomer (A-2), and a polar functional group containing monomer (A-3) is It is preferable to set it as 80 weight% or more and also 90 weight% or more in the whole acrylic resin.

Acrylic resin (A) obtained by copolymerizing the monomer mixture containing the (meth) acrylic-acid alkylester (A-1) represented by Formula I, an aromatic ring containing monomer (A-2), and a polar functional group containing monomer (A-3). Employ | adopts that the weight average molecular weight (Mw) of standard polystyrene conversion by gel permeation chromatography (GPC) exists in the range of 1 million-2 million. If the weight average molecular weight in terms of standard polystyrene is 1 million or more, the adhesiveness under high temperature and high humidity tends to be improved, and the possibility of floating or peeling between the liquid crystal cell and the pressure-sensitive adhesive layer tends to be lowered, and the reworkability tends to be improved. It is so desirable. If the weight average molecular weight is 2 million or less, even if the size of the polarizing plate adhered to the pressure-sensitive adhesive layer changes, the pressure-sensitive adhesive layer follows the change in size, and thus the difference between the brightness of the periphery of the liquid crystal cell and the brightness of the center part is varied. It is preferable because it tends to be eliminated and whiteout and color staining are suppressed.

The molecular weight distribution shown by Mw / Mn which is ratio with respect to the number average molecular weight (Mn) of a weight average molecular weight (Mw) shall be 3-7. By making molecular weight distribution (Mw / Mn) into the range of 3-7, even if a liquid crystal panel thru | or a liquid crystal display device are exposed to high temperature, troubles, such as a whiteout, are prevented from occurring.

Moreover, it is preferable that the glass transition temperature of the said acrylic resin (A) exists in the range of -10-60 degreeC for adhesive expression. The glass transition temperature of the resin can generally be measured by a differential scanning calorimeter.

The acrylic resin (A) which comprises an adhesive composition can be manufactured by well-known various methods, such as a solution polymerization method, an emulsion polymerization method, a block polymerization method, and a suspension polymerization method, for example. In manufacturing this acrylic resin, a polymerization initiator is used normally. About 0.001-5 weight part of polymerization initiators are used with respect to a total of 100 weight part of all the monomers used for manufacture of an acrylic resin.

As a polymerization initiator, a thermal polymerization initiator, a photoinitiator, etc. are used. As a photoinitiator, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2- propyl) ketone etc. are mentioned, for example. As the thermal polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile) , 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2'-azo Azo compounds such as bis (2-methylpropionate) and 2,2'-azobis (2-hydroxymethylpropionitrile); Lauryl peroxide, tert-butylhydroperoxide, benzoyl peroxide, tert-butylperoxybenzoate, cumene hydroperoxide, diisopropylperoxydicarbonate, dipropylperoxydicarbonate, tert-butylperoxy Organic peroxides such as neodecanoate, tert-butylperoxypivalate and (3,5,5-trimethylhexanoyl) peroxide; Inorganic peroxides such as potassium persulfate, ammonium persulfate and hydrogen peroxide; and the like. Moreover, the redox type initiator etc. which used a peroxide and a reducing agent together can also be used as a polymerization initiator.

As a manufacturing method of an acrylic resin, the solution polymerization method is preferable among the methods shown above.

When the specific example of the solution polymerization method is given and demonstrated, a desired monomer and an organic solvent are mixed, and a thermal polymerization initiator is added in nitrogen atmosphere, about 40-90 degreeC, Preferably it is about 60-80 degreeC, about 3 to 10 hours. The method of stirring is mentioned. Moreover, in order to control reaction, you may add a monomer and a thermal polymerization initiator continuously or intermittently during superposition | polymerization, or may add in the state dissolved in an organic solvent. Here, as an organic solvent, For example, aromatic hydrocarbons, such as toluene and xylene; Esters such as ethyl acetate and butyl acetate; Aliphatic alcohols such as propyl alcohol and isopropyl alcohol; Ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, etc. can be used.

<Cross-linking system (B)>

A crosslinking agent (B) is mix | blended with the above acrylic resin (A), and it is set as an adhesive composition. A crosslinking agent (B) is a compound which reacts with the structural unit derived from especially polar functional group containing monomer (A-3) in an acrylic resin (A), and crosslinks an acrylic resin. Specifically, an isocyanate compound, an epoxy compound, an aziridine compound, a metal chelate compound, etc. are illustrated. Among these, an isocyanate type compound, an epoxy type compound, and an aziridine type compound have at least 2 functional groups which can react with the polar functional group in an acrylic resin (A) in a molecule | numerator.

An isocyanate type compound is a compound which has at least 2 isocyanate group (-NCO) in a molecule | numerator, For example, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, Diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc. are mentioned. Moreover, the adduct body which made these polyisocyanate compounds react with polyols, such as glycerol and a trimethylol propane, and also made the isocyanate compound into dimer, trimer, etc. can be a crosslinking agent used for an adhesive. You may use it in mixture of 2 or more types of isocyanate compounds.

The epoxy compound is a compound having at least two epoxy groups in a molecule, and for example, bisphenol A epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, and glycerin triglycis Dyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N, N- diglycidyl aniline, N, N, N ', N'- tetraglycidyl-m- Xylenediamine, 1, 3-bis (N, N'- diglycidyl aminomethyl) cyclohexane, etc. are mentioned. 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 a three-membered ring composed of one nitrogen atom and two carbon atoms, also called ethyleneimine, in a molecule, for example, diphenylmethane-4,4'-bis (1-aziri) Dinecarboxamide), toluene-2,4-bis (1-aziridinecarboxamide), triethylenemelamine, isophthaloylbis-1- (2-methylaziridine), tris-1-aziridinylforce Fin oxide, hexamethylene-1,6-bis (1-aziridinecarboxamide), trimethylolpropane tris-β-aziridinylpropionate, tetramethylolmethane tris-β-aziridinylpropionate, etc. Can be mentioned.

Examples of the metal chelate compound include compounds in which acetylacetone and ethyl acetoacetate are coordinated with polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium. .

Among these crosslinking agents, isocyanate compounds, in particular, xylylene diisocyanate, tolylene diisocyanate or hexamethylene diisocyanate, or an adduct obtained by reacting these isocyanate compounds with a polyol such as glycerol or trimethylolpropane, or these isocyanate compounds are dimers. , Trimers, and the like, and mixtures of these isocyanate compounds are preferably used. When a polar functional group containing monomer (A-3) has a polar functional group chosen from a free carboxyl group, a hydroxyl group, an amino group, and an epoxy ring, it is especially preferable to use an isocyanate type compound as at least one of a crosslinking agent (B). Among the above, as an isocyanate compound suitable, an adduct obtained by reacting tolylene diisocyanate and tolylene diisocyanate with a polyol, a dimer of tolylene diisocyanate and a trimer of tolylene diisocyanate, and also hexamethylene diisocyanate and hexamethylene diisocyanate The adduct which reacted isocyanate to the polyol, the dimer of hexamethylene diisocyanate, and the trimer of hexamethylene diisocyanate are mentioned.

A crosslinking agent (B) is mix | blended in the ratio of 0.01-5 weight part with respect to 100 weight part of acrylic resin (A). The compounding quantity of a crosslinking agent (B), Preferably it is about 0.1-5 weight part with respect to 100 weight part of acrylic resin (A), Furthermore, it is about 0.2-3 weight part. If the amount of the crosslinking agent (B) to 100 parts by weight of the acrylic resin (A) is 0.01 parts by weight or more, especially 0.1 parts by weight or more, since the durability of the pressure-sensitive adhesive layer tends to be improved, it is preferable. Since the whiteout of a liquid crystal panel becomes inconspicuous, it is preferable.

<Other components constituting the adhesive composition>

In order to improve the adhesiveness of an adhesive layer and a glass cell, it is preferable to contain a silane type compound (C) in the adhesive composition for forming the adhesive layer in this invention, and especially to the acrylic resin before mix | blending a crosslinking agent. It is preferable to contain a silane type compound (C).

Examples of the silane compound (C) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane. , N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3- Mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropylethoxydimethyl Silane and the like. You may use 2 or more types of silane type compounds (C).

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

3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer And copolymers containing mercaptopropyl groups such as 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer;

Mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer and mercaptomethyltrier Copolymers containing a mercaptomethyl group such as oxysilane-tetraethoxysilane copolymer;

3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropyltrier Methoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-methacryloyloxypropylmethyldie Copolymers containing methacryloyloxypropyl group, such as oxysilane-tetraethoxysilane copolymer;

3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane- Tetramethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-acryloyl Oxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane co Copolymers containing acryloyloxypropyl groups such as polymers;

Vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane co Polymers, vinylmethyldimethoxysilane-tetramethoxysilane copolymers, vinylmethyldimethoxysilane-tetraethoxysilane copolymers, vinylmethyldiethoxysilane-tetramethoxysilane copolymers and vinylmethyldiethoxysilane-tetraethoxy Vinyl group-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 copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyl Amino group-containing copolymers such as methyldiethoxysilane-tetramethoxysilane copolymer and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer;

These silane compounds (C) are in many cases liquid. The compounding quantity of a silane compound (C) in an adhesive composition is about 0.01-10 weight part normally with respect to 100 weight part (non-volatile components, when using two or more types) of the non volatile matter of an acrylic resin (A), Preferably it is 0.03 It is used in the ratio of -1 weight part. Since the adhesiveness of an adhesive layer and a glass cell improves that the quantity of a silane type compound with respect to 100 weight part of non volatile matters of an acrylic resin (A) is 0.01 weight part or more, especially 0.03 weight part or more, it is preferable. Moreover, since the quantity is 10 weight part or less, especially 1 weight part or less, since the bleed out of a silane type compound tends to be suppressed from an adhesive layer, it is preferable.

The adhesive composition for forming the adhesive layer in this invention can also contain an ionic compound (D) as an antistatic agent. Especially when the aromatic ring containing monomer (A-2) which comprises an acrylic resin (A) is an aromatic ring containing (meth) acryl compound represented by said Formula II, and n in Formula II is 2 or more, It is further effective in suppression, and by mix | blending an ionic compound (D) in the adhesive composition containing the acrylic resin in which this monomer copolymerized, favorable antistatic property can be provided, maintaining the high whiteout suppression effect. The ionic compound referred to herein is a compound present in a combination of cations and anions, and the cations and anions may be inorganic or organic, respectively, but at least one of the cation and the anion may be used in view of compatibility with the acrylic resin (A). It is preferable that a side is an ionic compound containing an organic group.

Examples of the cation constituting the ionic compound include lithium cations, pyridinium-based cations represented by the following formula III, and quaternary ammonium cations represented by the following formula IV.

In formula III, R ₅ to R ₉ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₁₀ represents an alkyl group having 1 to 16 carbon atoms;

In Formula IV, R <_11> represents a C1-C12 alkyl group and R <_12> , R <_13> and R <_14> respectively independently represent a C6-C12 alkyl group.

The pyridinium-based cation represented by the above formula (III) is 6 or more in total carbon number, and in particular, the total carbon number is preferably 8 or more, particularly 10 or more, from the viewpoint of compatibility with the acrylic resin (A). Moreover, it is preferable that the total carbon number is 36 or less, Furthermore, it is 30 or less. Among the pyridinium-based cations represented by the formula (III), R ₇ bonded to a 4-position carbon atom of the pyridine ring is an alkyl group, and R ₅ , R ₆ , R ₈ and R ₉ each bonded to another carbon atom of the pyridine ring are each hydrogen. Being an atom is one of the preferred cations. Specific examples of the pyridinium-based cation represented by the formula III include the following ones.

N-methyl-4-hexylpyridinium cation,

N-butyl-4-methylpyridinium cation,

N-butyl-2,4-diethylpyridinium cation,

N-butyl-2-hexylpyridinium cation,

N-hexyl-2-butylpyridinium cation,

N-hexyl-4-methylpyridinium cation,

N-hexyl-4-ethylpyridinium cation,

N-hexyl-4-butylpyridinium cation,

N-octyl-4-methylpyridinium cation,

N-octyl-4-ethylpyridinium cation,

N-octylpyridinium cation and the like.

The ammonium cation represented by the above formula IV is a tetraalkylammonium cation, and the tetraalkylammonium cation preferably has a total carbon number of 20 or more, more preferably 22 or more from the viewpoint of compatibility with the acrylic resin (A). Moreover, it is preferable that the total carbon number is 36 or less, Furthermore, it is 30 or less. Specific examples of the tetraalkylammonium cation represented by the formula IV include the following ones.

Tetrahexyl ammonium cation,

Tetraoctylammonium cation,

Tributylmethylammonium cation,

Trihexylmethylammonium cation,

Trioctylmethylammonium cation,

Tridecylmethylammonium cation,

Trihexylethylammonium cation,

Trioctylethylammonium cation and the like.

In addition, the following are examples of the anion which comprises an ionic compound.

Chloride anion [Cl ^-],

Bromide anion [Br ^-],

Iodide anion [I ^-],

Tetrachloro-aluminate anion [AlCl ₄ ^-],

Heptanoic Chlorodifluoromethane aluminate anion [Al ₂ Cl ₇ ^-],

Anion as tetrafluoroborate [BF ₄ ^-],

Phosphate anions hexafluorophosphate [PF ₆ ^-],

Perchlorate anion [ClO ₄ ^-],

Nitrate anions [NO ₃ ^-],

Acetate anion [CH ₃ COO ⁻ ],

Trifluoroacetate anion [CF ₃ COO ⁻ ],

Methanesulfonate anion [CH ₃ SO ₃ ⁻ ],

Trifluoromethanesulfonate anion [CF ₃ SO ₃ ⁻ ],

Bis (fluorosulfonyl) imide anion [(FSO ₂ ) ₂ N ⁻ ],

Bis (trifluoromethane sulfonyl) imide anion _{[(CF 3 SO 2) 2 N} - ],

Tris (methanesulfonyl trifluoromethyl) bumetanide anion _{[(CF 3 SO 2) 3 C} - ],

Hexafluoro-acetoxy anion [AsF ₆ ^-],

Antimonate anion hexafluorophosphate [SbF ₆ ^-],

Hexafluoro niobate anions [NbF ₆ ^-],

Tantalum anion hexafluorophosphate [TaF ₆ ^-],

(Poly) a hydro-fluoro-fluoride anion [F (HF) _n ^-] (n is about 1 to 3),

Thiocyanate anion SCN ^[-]

DC Ana imide anion [(CN) ₂ N ^-],

A wave-fluoro-butane sulfonate anion [C ₄ F ₉ SO ₃ ^-],

Bis (ethanesulfonyl pentafluorophenyl) imide anion _{[(C 2 F 5 SO 2)} 2 N - ],

A wave-fluoro-butanoate anion [C ₃ F ₇ COO ^-],

(Methanesulfonyl trifluoromethyl) (methane-carbonyl trifluoromethanesulfonyl) imide anion _{[(CF 3 SO 2) (CF} 3 CO) N - ] and the like.

Specific examples of the ionic compound can be appropriately selected from combinations of the cations and anions described above. As an ionic compound which is a combination of a specific cation and an anion, the following are mentioned.

Lithium bis (fluorosulfonyl) imide,

Lithium bis (trifluoromethanesulfonyl) imide,

Lithium hexafluorophosphate,

Lithium iodide (lithium iodide),

N-methyl-4-hexylpyridinium bis (fluorosulfonyl) imide,

N-butyl-2-methylpyridinium bis (fluorosulfonyl) imide,

N-hexyl-4-methylpyridinium bis (fluorosulfonyl) imide,

N-octyl-4-methylpyridinium bis (fluorosulfonyl) imide,

N-methyl-4-hexylpyridinium bis (trifluoromethanesulfonyl) imide,

N-butyl-2-methylpyridinium bis (trifluoromethanesulfonyl) imide,

N-hexyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide,

N-octyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide,

N-methyl-4-hexylpyridinium hexafluorophosphate,

N-butyl-2-methylpyridinium hexafluorophosphate,

N-hexyl-4-methylpyridinium hexafluorophosphate,

N-octyl-4-methylpyridinium hexafluorophosphate,

N-methyl-4-hexylpyridinium perchlorate,

N-butyl-2-methylpyridinium perchlorate,

N-hexyl-4-methylpyridinium perchlorate,

N-octyl-4-methylpyridinium perchlorate,

Tetrahexylammonium bis (fluorosulfonyl) imide,

Tributylmethylammonium bis (fluorosulfonyl) imide,

Trihexylmethylammonium bis (fluorosulfonyl) imide,

Trioctylmethylammonium bis (fluorosulfonyl) imide,

Tetrahexyl ammonium bis (trifluoromethanesulfonyl) imide,

Tributylmethylammonium bis (trifluoromethanesulfonyl) imide,

Trihexylmethylammonium bis (trifluoromethanesulfonyl) imide,

Trioctylmethylammonium bis (trifluoromethanesulfonyl) imide,

Tetrahexyl ammonium hexafluorophosphate,

Tributylmethylammonium hexafluorophosphate,

Trihexylmethylammonium hexafluorophosphate,

Trioctylmethylammonium hexafluorophosphate,

Tetrahexyl ammonium perchlorate,

Tributylmethylammonium perchlorate,

Trihexylmethylammonium perchlorate,

Trioctylmethylammonium perchlorate and the like.

These ionic compounds can be used individually or in combination with other 1 or more types, respectively. When mix | blending an ionic compound (D), the quantity is about 0.5-8 weight part normally with respect to 100 weight part of acrylic resin (A), Preferably it is 0.8-4 weight part.

The pressure-sensitive adhesive composition described above may further contain a crosslinking catalyst, a weather stabilizer, a tackyfire (tackifier), a plasticizer, a softener, a dye, a pigment, an inorganic filler, and a resin other than an acrylic resin. It is also useful to mix | blend an ultraviolet curable compound with an adhesive, and to make it a harder adhesive layer by irradiating and hardening an ultraviolet-ray after adhesive layer formation. Moreover, when a crosslinking catalyst is mix | blended with a crosslinking agent with an adhesive, an adhesive layer can be prepared by aging of a short time, In the polarizing plate which has the adhesive obtained, floating or peeling arises between a polarizing plate and an adhesive layer, or foaming in an adhesive layer is carried out. May be suppressed, and the reworkability may be further improved. As the crosslinking catalyst, for example, amine compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resin and melamine resin, etc. Can be mentioned. When mix | blending an amine compound as a crosslinking catalyst with an adhesive, an isocyanate type compound is suitable as a crosslinking agent.

These components which comprise an adhesive can be mixed with an acrylic resin (A) and a crosslinking agent (B) which are essential components, and can be set as an adhesive composition in the state melt | dissolved in the solvent as needed.

An adhesive layer is formed by crosslinking an adhesive composition. As a specific method of forming an adhesive layer, the method of apply | coating an adhesive composition on a suitable base material, and drying this is mentioned.

<Gel fraction of the adhesive layer>

In the present invention, as described above, the gel fraction of the pressure-sensitive adhesive layer is 60 to 99% by weight. If the gel fraction of the pressure-sensitive adhesive layer is 60% by weight or more, the durability of the pressure-sensitive adhesive layer is improved, and if the gel fraction is 99% by weight or less, it is preferable because it is easy to manufacture. The gel fraction is a value measured according to the following (1)-(4) here.

(1) A pressure-sensitive adhesive layer having an area of about 8 cm x about 8 cm and a metal mesh made of SUS304 of about 10 cm x about 10 cm (the weight of which is Wm) are bonded.

(2) The weight of the adhesive obtained in the above (1) is weighed, and the weight thereof is Ws, and then folded four times so as to surround the pressure-sensitive adhesive layer, fixed with a stapler, and weighed, and the weight thereof is Wb.

(3) The mesh fixed by the stapler in (2) above is put into a glass container, 60 mL of ethyl acetate is added and immersed, and the glass container is stored at room temperature for 3 days.

(4) The mesh is taken out of the glass container, dried at 120 ° C. for 24 hours, weighed, and the weight thereof is Wa, and the gel fraction is calculated based on the following equation.

Gel fraction (% by weight) = [{Wa- (Wb-Ws) -Wm} / (Ws-Wm)] × 100

The gel fraction of an adhesive layer can be adjusted according to the kind of acrylic resin (A) which is an active component of an adhesive composition, and the quantity of a crosslinking agent (B), for example. Specifically, when the amount of the polar functional group-containing monomer (A-3) in the acrylic resin (A) is increased or the amount of the crosslinking agent (B) in the pressure-sensitive adhesive composition is increased, the gel fraction increases, so that the polarity is increased. What is necessary is just to adjust a gel fraction according to the quantity of a functional group containing monomer and / or a crosslinking agent. The polar functional group-containing monomer (A-3) is an acrylic resin (A) in an amount of 0.1 to 5% by weight of the amount of the structural unit derived from the polar functional group-containing monomer (A-3) in the acrylic resin (A). What is necessary is just to select and adjust so that a gel fraction may become the said range by the combination with the other component which comprises, and also the kind and quantity of a crosslinking agent. On the other hand, the amount of the crosslinking agent (C) is acrylic in the range of about 0.1 to 5 parts by weight of the blending amount of the crosslinking agent relative to 100 parts by weight of the nonvolatile content (when used in two or more kinds) of the acrylic resin constituting the pressure sensitive adhesive layer. It is preferable to select according to the kind of resin.

The pressure-sensitive adhesive layers 31 and 32 on the polarizing plates 21 and 22 are formed by, for example, applying the above pressure-sensitive adhesive composition on a release film to form a pressure-sensitive adhesive layer, and bonding the obtained pressure-sensitive adhesive layer to the surfaces of the polarizing plates 21 and 22. It can install by the method of apply | coating an adhesive composition on the method and polarizing plates 21 and 22, forming an adhesive layer, bonding a peeling film to the adhesive surface, and protecting. The peeling film used here is based on the film which consists of various transparent resins, such as a polyethylene terephthalate, a polybutylene terephthalate, a polycarbonate, and a polyarylate, for example, and it is a silicon surface to a bonding surface with the adhesive layer of this base material. The same mold release treatment may be performed.

Although the thickness of the adhesive layers 31 and 32 is not specifically limited, Usually, it is preferable that it is 30 micrometers or less, Furthermore, it is preferable that it is 10 micrometers or more, More preferably, it is 15-25 micrometers.

When the thickness of the pressure-sensitive adhesive layer is 30 μm or less, the adhesiveness under high temperature and high humidity tends to be improved, and the possibility of floating or peeling between the glass cell and the pressure-sensitive adhesive layer tends to be lowered, and the reworkability tends to be improved. In addition, if the thickness is 10 μm or more, even if the size of the polarizing plate adhered thereto changes, the pressure-sensitive adhesive layer follows and changes in the size change, so that there is no difference between the brightness of the periphery of the liquid crystal cell and the brightness of the central part. This is preferable because whiteout and color staining tend to be suppressed. Conventionally, although the thickness of the adhesive layer which sticks to the glass cell for liquid crystal displays generally is considered 25 micrometers as a standard, in this invention, even if the thickness is 20 micrometers or less, sufficient performance is exhibited as an adhesive layer.

After the polarizing plate with the pressure-sensitive adhesive layer defined in the present invention is adhered to a liquid crystal cell to form a liquid crystal panel, and there is any problem and the polarizing plate is peeled from the liquid crystal cell, the pressure-sensitive adhesive layer is peeled off along the polarizing plate, Since a dark part, adhesive debris, etc. hardly generate | occur | produce on the surface of the liquid crystal cell which contacted, it is easy to fix the polarizing plate which has an adhesive layer again to the liquid crystal cell after peeling. That is, it is excellent in what is called rework property.

[Polarizing Plate]

The first polarizing plate 21 and the second polarizing plate 22 shown in FIG. 1 respectively transmit linearly polarized light having a certain vibration surface and linearly polarized light having a vibration surface perpendicular to the light incident perpendicularly to the surface thereof. It is comprised including the polarizing film which absorbs. Such a polarizing film is normally produced by adsorbing or aligning a dichroic dye made of iodine or a dichroic organic dye to a polyvinyl alcohol-based resin film. Since the polarizing film itself is highly stretched in order to orientate a dichroic dye, it is easy to tear. Therefore, in general, a transparent protective layer is formed on at least one surface of the polarizing film as described above to form a polarizing plate.

An example of the laminated constitution of the polarizing plate in which the adhesive layer for sticking to a liquid crystal cell suitable for application to this invention was formed was shown in FIG. In FIG. 2, since both the 1st polarizing plate 21 and the 2nd polarizing plate 22 shown in FIG. 1 are meant, the code | symbol 20 is attached | subjected to a polarizing plate. In addition, since both mean the 1st adhesive layer 31 and the 2nd adhesive layer 32 shown in FIG. 1, the code | symbol 30 is attached | subjected to the adhesive layer used for adhesion to a liquid crystal cell. The 1st polarizing plate 21 and the 2nd polarizing plate 22 may be the same layer structure, or may be another layer structure.

As shown in FIG. 2 (A), one form of the polarizing plate 20 is provided with transparent protective layers 26 and 27 formed on both surfaces of the polarizing film 25, and is attached to the liquid crystal cell. In one example, the pressure-sensitive adhesive layer 30 for liquid crystal cell adhesion is formed on the outer surface of the transparent protective layer 27. In another embodiment, as shown in FIG. 2B, transparent protective layers 26 and 27 are formed on both surfaces of the polarizing film 25, and the surface of the liquid crystal cell (in the illustrated example, the transparent protective layer). The optical compensation film 28 which makes a retardation film the representative example is laminated | stacked on the outer surface of (27), and the adhesive layer 30 for adhesion to a liquid crystal cell is formed in the outer side of the optical compensation film 28. . In this case, the interlayer adhesive 29 is normally used for adhesion of the transparent protective layer 27 to the optical compensation film 28.

Another form of the polarizing plate 20 is, as shown in FIG. 2C, in which a transparent protective layer 26 is formed on one side of the polarizing film 25, and directly adheres to the liquid crystal cell in this state. In the case, the adhesive layer 30 for adhesion to a liquid crystal cell is formed in the other surface of the polarizing film 25. In another embodiment, as shown in FIG. 2D, the transparent protective layer 26 is formed on one surface of the polarizing film 25, and the interlayer adhesive 29 is formed on the other surface. The optical compensation film 28 which makes a retardation film the representative example is laminated | stacked, and the adhesive layer 30 for adhesion to a liquid crystal cell is formed in the outer side of the optical compensation film 28. As shown in FIG.

Although the transparent protective layers 26 and 27 may be formed by coating of resin, for example, they are generally comprised by adhering a protective film through an adhesive agent. As a protective film, various transparent resin films, such as a cellulose resin film, an olefin resin film, a cycloolefin resin film, an acrylic resin film, and a polyester resin film, can be used, for example.

When using a cellulose resin film as a protective film, the cellulose acetate type resin in which at least one part of cellulose was acetate-esterified is suitable. For example, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, etc. are mentioned. Such a cellulose acetate-based resin film can use a suitable commercial product. For example, "Fujitag TD80", "Fujitag TD80UF" and "Fujitag TD80UZ" sold by Fujifilm Co., Ltd., "KC8UX2M" and "KC8UY" sold by Konica Minolta Opt Co., Ltd. ) Is suitable as an example.

Cycloolefin resin is thermoplastic resin which has the monomer unit of the cycloolefin which makes norbornene, tetracyclo dodecene (alias dimethanooctahydronaphthalene), or derivatives thereof, for example, and the ring-opening polymer of the said cycloolefin In addition to being a hydrogenated product of a ring-opening copolymer using two or more cycloolefins, an addition copolymer of a cycloolefin with an aromatic compound having a chain olefin or a vinyl group may be used. In addition, a polar group may be introduced.

Commercially available thermoplastic cycloolefin-based resins include, for example, "Aton" (ARTON) sold by JSR Corporation, "Zonex" (ZEONEX) and "ZEONOR" sold by Nihon Xeon Corporation. And "TOPAS" produced by TOPAS ADVANCED POLYMERS GmbH in Germany and sold by Polyplastics Co., Ltd., and "Apel" sold by Mitsui Chemicals Co., Ltd. (all brand names).

In forming such a cycloolefin resin into a film, well-known film forming methods, such as a solvent casting method and a melt extrusion method, are used suitably for film forming. The cycloolefin resin film formed into a film and the cycloolefin resin film which extended and provided retardation are also marketed. For example, "Aton Film" sold by JSR, "Zenooa Film" sold by Nihon Xeon, "Esshina" and "SCA40" sold by Sekisui Chemical Co., Ltd. Etc. (all are brand names), and these can be used suitably.

As above-mentioned, the above protective film is laminated | stacked on at least one surface of a polarizing film, usually the surface which becomes further from the liquid crystal cell 10 at least with reference to FIG.

On the surface which becomes the liquid crystal cell side of the polarizing film 25, as shown to FIG. 2 (A), the transparent protective film 27 can be laminated | stacked through an adhesive agent, and also as shown to FIG. 2 (B) Likewise, the optical compensation film 28 may be adhered to the outside through the interlayer adhesive 29. In addition, on this surface, as shown in FIG. 2 (C), the pressure-sensitive adhesive layer 30 is directly formed on the liquid crystal cell, or as shown in FIG. 2 (D), through the interlayer pressure sensitive adhesive 29 The compensation film 28 may be adhered to. Here, the pressure-sensitive adhesive layer 30 directly adhered to the liquid crystal cell 10 is preferably formed of the pressure-sensitive adhesive composition defined in the present invention described above, but the optical compensation film 28 is adhered to the protective film 27, The interlayer adhesive 29 for adhering the optical compensation film 28 to the polarizing film 25 may be formed of an adhesive composition other than that. The interlayer adhesive 29 used for adhering the optical compensation film 28 to the protective film 27 or the polarizing film 25 is described above except that the aromatic ring-containing monomer (A-2) is not copolymerized, for example. It can be formed from the acrylic adhesive composition in which the crosslinking agent was mix | blended with the acrylic resin according to the above.

In the liquid crystal panel shown in FIG. 1, at least one of the first polarizing plate 21 and the second polarizing plate 22 has a protective film 26 / polarizing film (as shown in FIG. 2A). 25) / protective film 27 is preferable.

From the viewpoint of the ease of placing a surface treatment layer and the optical properties, the protective film 26 disposed away from the liquid crystal cell of the polarizing film 25 is preferably composed of a cellulose acetate-based resin film including a triacetyl cellulose film. Do. In particular, a cellulose acetate-based resin film having an in-plane retardation value Ro in a range of 0 to 20 nm and a retardation value Rth in a thickness direction in a range of 20 to 80 nm can be produced directly by a solvent casting method. Since it can be, it is one of the preferable protective films arrange | positioned away from a liquid crystal cell.

Here, with respect to the film showing optical anisotropy, the in-plane retardation value Ro and the thickness direction retardation value Rth are the directions in which the refractive index of the in-plane slow axis direction is n _x and the plane orthogonal to the slow axis (in the fast axis direction). When the index of refraction is n _y , the index of refraction in the thickness direction is n _z , and the thickness is d, the following formulas (5) and (6) are defined.

Ro = (n _x -n _y ) × d (5)

Rth = ((n _x + n _y ) / 2-n _z ) × d (6)

In addition, in a general liquid crystal display device, in order to obtain the excellent display performance, as shown to FIG. 2 (B) and (D), the optical compensation film 28 is arrange | positioned to the liquid crystal cell side of the polarizing plate 20, It is preferable to provide a compensation function by making the protective film 27 itself used as the liquid crystal cell side of the polarizing plate 20 in the example shown to FIG. 2 (A) phase difference, etc. The value of the retardation in the optical compensation film or the protective film provided with retardation can arbitrarily select an appropriate value according to the mode of a liquid crystal, the image quality made into the objective, etc.

For example, when giving the polarizing plate a compensating function for the liquid crystal display device in the vertical alignment (VA) mode, at least one of a protective film disposed on the liquid crystal cell side of the light incident side polarizing plate and a protective film disposed on the liquid crystal cell side of the light exit side polarizing plate. It is preferable that one side has the function of a retardation film. In this case, the protective film which has the function of retardation film has a slow axis and a fastening axis in surface. The slow axis and the fast axis are orthogonal in plane.

When providing the effective compensation function with respect to the liquid crystal cell of VA mode, at least one of the protective film 27 located in the liquid crystal cell side of each of a light incident side polarizing plate and a light emission side polarizing plate has an in-plane phase difference value Ro It is preferable that the phase difference value Rth in this 30-80 nm and thickness direction exists in the range of 80-250 nm. In this case, it is preferable that the slow axis direction of the protective film 27 having a phase difference is disposed so as to be substantially orthogonal to the absorption axis direction of the polarizing film 25 being bonded. It is further more preferable to comprise both of the protective films 27 located in the liquid crystal cell side of the polarizing plates arrange | positioned on both surfaces of a liquid crystal cell by the film which has such a phase difference value.

In the polarizing plate used by adhering to the liquid crystal cell of VA mode, when the in-plane retardation value Ro of the protective film used as a liquid crystal cell is less than 30mn, the visual compensation of a polarization axis will become inadequate, and the blind spot in a black display ( There is a tendency that light fallout from i) is increased and the viewing angle is narrowed. On the other hand, when the value exceeds 80 nm, the visual overcompensation may adversely affect light loss. In addition, similarly to the in-plane retardation value, the phase difference value Rth in the thickness direction is too small, so that the visual compensation of the liquid crystal layer is insufficient. On the contrary, the retardation value Rth tends to be overcompensated.

An arbitrary retardation value can be provided by extending | stretching a cellulose acetate type resin film. As a cellulose acetate type resin film in which the phase difference suitable for the optical compensation of the liquid crystal cell of VA mode was expressed, what expressed the biaxially-oriented phase difference by extending | stretching is marketed.

For example, "KC8UCR-5", "KC4FR-T", "KC4HR-T" etc. which are marketed by Konica Minolta Opt Co., Ltd. (all are brand names). The cellulose acetate-based resin film provided with such a phase difference can be preferably applied as a protective film (protective film 27 in FIG. 2A) serving as a liquid crystal cell.

Moreover, arbitrary phase difference values can be provided by extending | stretching a cycloolefin resin film. Stretching is normally carried out continuously while winding a film from a roll, and it extends | stretches in the advancing direction of a roll or the direction orthogonal to a advancing direction in a heating furnace. As for the temperature of a heating furnace, the range of glass transition temperature +100 degreeC is employ | adopted normally in the glass transition temperature vicinity of cycloolefin resin. Preferably, it extends | stretches so that the direction orthogonal to the advancing direction of a roll may become a main extending | stretching axis, ie, a lateral stretch as a main body. The draw ratio is usually about 1.1 to 6 times, preferably 1.1 to 3.5 times, in the main stretching axis direction. The cycloolefin resin film provided with such a phase difference can also be suitably applied as a protective film [protective film 27 in FIG. 2 (A)] used as a liquid crystal cell.

In the liquid crystal panel of VA mode, in one preferable aspect, at least one of the 1st polarizing plate 21 and the 2nd polarizing plate 22 shown in FIG. 1 is a protective film as shown to FIG. 2 (A). (26) / polarizing film 25 / protective film 27 is configured. And in one more preferable aspect in this case, the in-plane phase difference value Ro of the protective film 26 which becomes far from a liquid crystal cell among two protective films which have the polarizing film 25 interposed is 0-20. The protective film 27 which is nm and is composed of a cellulose acetate-based resin having a phase difference value Rth in the thickness direction of 20 to 80 nm, and serves as a liquid crystal cell, has an in-plane phase difference value Ro of 30 to 80 nm and a thickness. The phase difference value Rth of a direction is comprised from the cellulose acetate resin which is 80-250 mm.

On the other hand, when giving a polarizing plate an effective compensating function for the liquid crystal cell in the transverse electric field (IPS) mode, at least one of the protective films located on the liquid crystal cell side of each of the light incident side polarizing plate and the light exiting side polarizing plate is in-plane. It is preferable that the retardation value Ro is in the range of 0 to 10 nm and the retardation value Rth in the thickness direction is -25 to 25 mn, and more preferably, a substantially unoriented film having Rth of almost zero is used. Do. It is further more preferable to comprise both of the protective films which are located in the liquid crystal cell side of the polarizing plates arrange | positioned on both surfaces of a liquid crystal cell by having such a phase difference value. By setting the in-plane retardation value Ro and the retardation value Rth in the thickness direction within the above ranges, the amount of light leakage in the oblique direction is small, and clear display is possible.

As a film suitable for the compensation of the above IPS mode, a cellulose acetate-based resin film or a cycloolefin-based resin film can be preferably used. By adding a retardation reducing agent to a cellulose acetate-based resin, a film having a phase difference value Rth of substantially zero in the thickness direction is commercially available. For example, "KC4UEW" and "KC4UESW" sold by Konica Minolta Opt Co., Ltd. And the like (both trade names). The cellulose acetate-based resin film in which such retardation is controlled can be preferably applied as a protective film (protective film 27 in FIG. 2 (A)) serving as a liquid crystal cell.

Moreover, as a cycloolefin resin film which reduced the in-plane phase difference value Ro and the phase difference value Rth of the thickness direction as much as possible, about the commercially available cycloolefin resin film mentioned above of the in-plane and thickness direction which remain in a film What was produced by the method of alleviating distortion by heat processing, etc. can be applied.

Also in the liquid crystal panel of IPS mode, in one preferable aspect, the structure of at least one of the 1st polarizing plate 21 and the 2nd polarizing plate 22 shown in FIG. 1 is the same as that shown in FIG. 2 (A). It becomes the protective film 26 / polarizing film 25 / protective film 27. In one more preferable aspect in this case, the in-plane phase difference value Ro of the protective film 26 which becomes far from a liquid crystal cell among two protective films with the polarizing film 25 is 0-20 nm. The protective film 27 which consists of cellulose acetate-type resin whose retardation value of thickness direction is 20-80 nm, and becomes a liquid crystal cell side, has in-plane retardation value Ro of 0-10 nm, and retardation value of thickness direction ( Rth) is comprised from the cellulose acetate type resin of -25-25 mm.

The protective film 26 / polarizing film 25 / protective film as shown in FIG. 2 (A) of the structure of at least one of the 1st polarizing plate 21 and the 2nd polarizing plate 22 shown in FIG. 27), in another preferred embodiment, the protective film 26, which is far from the liquid crystal cell, is composed of cellulose acetate-based resin, and the protective film 27, which is the liquid crystal cell, is composed of cycloolefin-based resin. do.

When the liquid crystal cell side protective film of the light incident side polarizing plate has a phase difference, and when the liquid crystal cell side protective film of the light exit side polarizing plate has a phase difference, the polarizing film constituting the light incident side polarizing plate, the liquid crystal cell side protective film, and the light exit side The polarizing film and liquid crystal cell side protective film which comprise a polarizing plate may be arrange | positioned so that the absorption axis of a polarizing film and the in-plane slow axis of a protective film may become substantially parallel relationship or substantially orthogonal relationship. In particular, it is preferable to arrange | position so that both may become substantially orthogonal. That is, when the liquid crystal cell side protective film of a light incident side polarizing plate and / or the liquid crystal cell side protective film of a light exit side polarizing plate is comprised with the refractive index anisotropic film which has a phase difference, it is preferable to manufacture by the extending operation which mainly uses lateral stretch, In this case, since the slow axis is in the width direction of the roll film, the absorption axis of the polarizing film and the slow axis of the protective film are orthogonal to each other by performing roll-to-roll adhesion with the polarizing film whose longitudinal direction (flow direction) of the roll film is the absorption axis. do.

In order to improve the adhesiveness with a polarizing film, a cellulose acetate type resin film is usually saponified. As a saponification process, the method of immersing in aqueous solution of alkalis, such as sodium hydroxide and potassium hydroxide, can be employ | adopted.

In the protective film used for a polarizing plate, although the thickness is smaller, it is preferable, but when it is too thin, there exists a tendency for strength to fall and inferior to workability, and when too thick, transparency will fall or the weight of a polarizing plate will become large. Inclined. From such a viewpoint, the thickness of a protective film is 5-200 micrometers normally, Preferably it is 10-150 micrometers, More preferably, it is 20-100 micrometers, and the cellulose acetate type in the case of the protective film which consists of cycloolefin resin In the case of the protective film which consists of resin, it is 20-200 micrometers normally, Preferably it is 30-150 micrometers, More preferably, it is 40-100 micrometers.

The protective film constituting the polarizing plate may be one having a surface treatment such as an antiglare treatment, a hard coat treatment, an antistatic treatment, an antireflection treatment, or the like on a surface opposite to the surface that is attached to the polarizing film. Moreover, the coating layer which consists of a liquid crystalline compound, its high molecular weight compound, etc. may be formed in the surface on the opposite side to the surface adhering to the polarizing film of a protective film.

[Liquid crystal display device]

The liquid crystal panel shown in FIG. 1 can arrange | position a back light outside any one of the 1st polarizing plate 21 and the 2nd polarizing plate 22, and can be set as a liquid crystal display device. Various known optical layers, such as a light collecting layer, a light diffusing layer, and a brightness enhancing layer, may be disposed between the back light and the polarizing plate in accordance with the display characteristics required for the liquid crystal display device.

The liquid crystal display device using the liquid crystal panel of the present invention includes, for example, a liquid crystal display for a personal computer including a laptop, a desktop, a personal digital assistant (PDA), a television, a vehicle-mounted display, an electronic dictionary, a digital It can be used for cameras, digital video cameras, electronic desk calculators and watches. In particular, the present invention is effective for liquid crystal televisions, which have recently become larger in size.

[Example]

Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these examples. In the examples, "parts" and "%" indicating the amount of use to the content are based on weight unless otherwise specified.

In the following examples, the weight average molecular weight and the number average molecular weight are 4 lines and "Showa Denko Co., Ltd." manufactured by Tosso Corporation as a column to the GPC apparatus from Shokotsu Shosho Co., Ltd. One line, 5 lines in total, were placed in series in a line of "Shodex GPC KF-802" for sale, and the sample concentration was 5 mg / mL, the sample introduction amount was 100 µL, the temperature was 40 ° C, and the flow rate using tetrahydrofuran as the eluent. It is the value measured by standard polystyrene conversion on condition of 1 mL / min.

First, the manufacture example of the acrylic resin used as the main component of an adhesive composition is shown.

[Polymerization Example 1]

81.8 parts of ethyl acetate, 93.4 parts of butyl acrylates as (A-1), 5.0 parts of 2-phenoxyethyl acrylates as (A-2), to the reaction container provided with a cooling tube, a nitrogen inlet tube, a thermometer, and a stirrer. As -3), 1.0 part of acrylic acid 2-hydroxyethyl and 0.6 part of acrylic acid were put, and the internal temperature was raised to 55 degreeC, replacing the air in an apparatus with nitrogen gas, and containing oxygen. Then, the whole amount of the solution which melt | dissolved 0.14 part of azobisisobutyronitrile which is a polymerization initiator in 10 parts of ethyl acetate was added. Ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts / hr while maintaining the temperature at this temperature for 1 hour after adding the initiator, and then maintaining the internal temperature at 54 to 56 ° C. At that point, the addition of ethyl acetate was stopped and the temperature was kept at this temperature until 12 hours had elapsed from the start of the addition of ethyl acetate. Finally, ethyl acetate was added and adjusted so that the density | concentration of an acrylic resin might be 20%. As for the obtained acrylic resin, the weight average molecular weight (Mw) of polystyrene conversion by GPC was 1,650,000, and Mw / Mn was 4.3. Let this be acrylic resin A. The structural unit derived from 2-phenoxyethyl acrylate which is an aromatic ring containing monomer in acrylic resin A is 5%, and the structural unit derived from 2-hydroxyethyl acrylate which is a hydroxyl group containing monomer is 1%, and the acrylic acid which is a carboxyl group-containing monomer. The structural unit derived from is 0.6%.

[Polymerization Example 2]

The monomer composition was 72.4 parts of butyl acrylate and 20 parts of methyl acrylate as (A-1), 6.0 parts of acrylic acid 2-phenoxyethyl as (A-2) and 1.0 part of 2-hydroxyethyl acrylate and acrylic acid as (A-3). An ethyl acetate solution of an acrylic resin was obtained in the same manner as in Polymerization Example 1, except that it was changed to 0.6 part and the holding time was changed to 18 hours. As for the obtained acrylic resin, the weight average molecular weight (Mw) of polystyrene conversion by GPC was 1,470,000, and Mw / Mn was 5.3. Let this be acrylic resin B.

The structural unit derived from 2-phenoxyethyl acrylate which is an aromatic ring containing monomer in acrylic resin B is 6%, and the structural unit derived from 2-hydroxyethyl acrylate which is a hydroxyl group containing monomer is 1% and acrylic acid which is a carboxyl group-containing monomer. The structural unit derived from is 0.6%.

[Polymerization Examples 3 to 10]

The monomer composition was changed as shown in Table 1, and the ethyl acetate solution of the acrylic resin was obtained in the same manner as the polymerization example 1 elsewhere. The weight average molecular weight (Mw) and Mw / Mn of polystyrene conversion by GPC of obtained acrylic resin are as showing in Table 1, respectively, and let each acrylic resin be acrylic resin C-J as shown in Table 1. . On the other hand, Polymerization Examples 7-10 are the examples which produced that the quantity of an aromatic ring containing monomer does not satisfy | fill the requirements of the acrylic resin (A) prescribed | regulated by this invention.

[Polymerization Example 11]

The monomer composition was shown in Table 1, these mixed solutions were put into the same reaction container as used in the polymerization example 1, the internal temperature was raised to 55 degreeC, replacing the air in an apparatus with nitrogen gas, and containing oxygen. Then, the whole amount of the solution which melt | dissolved 0.14 part of azobisisobutyronitrile which is a polymerization initiator in 10 parts of ethyl acetate was added. Ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts / hr while maintaining the temperature at this temperature for 1 hour after adding the initiator, and then maintaining the internal temperature at 54 to 56 ° C. At that point, the addition of ethyl acetate was stopped and the temperature was kept at this temperature until 4 hours had elapsed from the start of the addition of ethyl acetate. Then, the whole amount of the solution which melt | dissolved 0.2 parts of azobisisobutyronitrile in 10 parts of ethyl acetate was added, it was made to hold | maintain for 8 hours at the same temperature, and finally ethyl acetate was added and it adjusted so that the density | concentration of an acrylic resin might be 20%. As for the obtained acrylic resin, the weight average molecular weight (Mw) of polystyrene conversion by GPC was 1,070,000, and Mw / Mn was 8.2. Let this be acrylic resin K. The structural unit derived from 2-phenoxyethyl acrylate which is an aromatic ring containing monomer in acrylic resin K is 8%, and the structural unit derived from 2-hydroxyethyl acrylate which is a hydroxyl group containing monomer is 1% and acrylic acid which is a carboxyl group-containing monomer. The structural unit derived from is 0.4%. This polymerization example 11 is an example which manufactured what Mw / Mn does not satisfy | fill the requirements of the acrylic resin (A) prescribed | regulated by this invention.

[Polymerization Example 12]

The monomer composition was 70.8 parts of butyl acrylate and 20 parts of methyl acrylate as (A-1), 8.0 parts of acrylic acid 2- (2-phenoxyethoxy) ethyl as (A-2) and 4-hydric acid as (A-3). It changed to 1.0 part of oxybutyl and 0.2 part of acrylic acid, and else carried out similarly to the polymerization example 1, and obtained the ethyl acetate solution of an acrylic resin. As for the obtained acrylic resin, the weight average molecular weight (Mw) of polystyrene conversion by GPC was 1,670,000, and Mw / Mn was 3.9. Let this be acrylic resin L. The structural unit derived from 2- (2-phenoxyethoxy) ethyl acrylate which is an aromatic ring containing monomer in acrylic resin L is 8%, and the structural unit derived from 4-hydroxybutyl acrylate which is a hydroxyl group containing monomer is 1%. The structural unit derived from acrylic acid which is a carboxyl group-containing monomer is 0.2%.

[Polymerization Examples 13-16]

The monomer composition was changed as shown in Table 2, and the ethyl acetate solution of the acrylic resin was obtained in the same manner as the polymerization example 12 elsewhere. The weight average molecular weight (Mw) and Mw / Mn of polystyrene conversion by GPC of obtained acrylic resin are as showing in Table 2, respectively, and let each acrylic resin be the acrylic resin M-P as shown in Table 2. .

[Polymerization Example 17]

The monomer composition was changed into 88.6 parts of butyl acrylate and 10 parts of 2-methoxyethyl acrylate as (A-1) and 1.0 part of 2-hydroxyethyl acrylate and 0.2 part of acrylic acid as (A-3), and (A-2) It was not used. Otherwise, ethyl acetate solution of acrylic resin was obtained in the same manner as in Polymerization Example 1. As for the obtained acrylic resin, the weight average molecular weight (Mw) of polystyrene conversion by GPC was 1,750,000, and Mw / Mn was 4.9. Let this be acrylic resin Q. In the acrylic resin Q, the structural unit derived from an aromatic ring containing monomer does not exist, and the structural unit derived from 2-hydroxyethyl acrylate which is a hydroxyl-containing monomer is 1%, and the structural unit derived from acrylic acid which is a carboxyl group-containing monomer is 0.4%. to be.

[Polymerization Examples 18 and 19]

In the monomer composition, (A-1), Polymerization Example 18 was 78.6 parts of butyl acrylate and 20 parts of 2-methoxyethyl acrylate, and Polymerization Example 19 was made of 98.6 parts of butyl acrylate. Otherwise, acrylic was obtained in the same manner as in Polymerization Example 17. An ethyl acetate solution of the resin was obtained. The weight average molecular weight (Mw) and Mw / Mn of polystyrene conversion by GPC of obtained acrylic resin are as showing in Table 1, respectively, and each acrylic resin is referred to as acrylic resin R and S as shown in Table 1, respectively. do.

Polymerization Examples 17 and 18 are examples of producing an acrylic resin by copolymerizing 10% or 20% of 2-methoxyethyl acrylate, which is effective for improving antistatic performance, instead of an aromatic ring-containing monomer, and Polymerization Example 19, The acrylic resin was manufactured by copolymerizing only butyl acrylate and 2-hydroxyethyl acrylate and acrylic acid which are polar functional group containing monomers, without using this 2-methoxyethyl acrylate.

Next, the adhesive composition is prepared using acrylic resins A-K manufactured by the polymerization examples 1-11, it is applied to a polarizing plate, and the Example and comparative example which produced the liquid crystal panel corresponding | compatible article are shown. In these Examples and Comparative Examples, the following were used as crosslinking agents and silane compounds, respectively (all of which are trade names).

<Bridge school>

Colonate L: Obtained from ethyl acetate solution (solid content concentration 75%) of the trimethylolpropane adduct of tolylene diisocyanate, and Nippon Polyurethanes.

<Silane-based compound>

KBM-403: Glycidoxypropyl trimethoxysilane (liquid) obtained from Shin-Etsu Chemical Co., Ltd ..

[Examples 1-6 and Comparative Examples 1-5]

(a) Preparation of pressure-sensitive adhesive composition

With respect to 100 parts of solid content of the acrylic resins A-K (20% ethyl acetate solution) obtained in the polymerization examples 1-11, 0.5 part and 5 crosslinking agents (colonate L) were mentioned for the silane type compound (KBM-403) mentioned above. Each amount shown in Table 3 was mixed, and ethyl acetate was added so that solid content concentration might be 13%, and the adhesive composition was prepared.

(b) Preparation of Polarizing Plate with Pressure-Sensitive Adhesive Layer

Each pressure-sensitive adhesive composition prepared in the above (a) is a release treatment surface of a polyethylene terephthalate film (trade name "PET 3811", available from Lintech Co., Ltd., referred to as a separator) after release using an applicator. It applied so that thickness might be 20 micrometers, it dried at 90 degreeC for 1 minute, and produced the sheet-like adhesive layer. Subsequently, the surface opposite to the separator of the sheet-like adhesive layer obtained above on one surface of the polarizing plate of the three-layered structure which sandwiched both surfaces of the polarizing film which iodine adsorbs and orients to polyvinyl alcohol by the protective film which consists of triacetylcellulose. After bonding the (adhesive side) with a laminator, the mixture was cured for 7 days under conditions of a temperature of 23 ° C. and a relative humidity of 65% to produce a polarizing plate having an adhesive layer. About the pressure-sensitive adhesive layer after curing, the gel fraction was measured by the method described above, and the results are summarized in Table 2.

(c) Adhesion and Evaluation to Glass Substrates

What peeled the separator from the polarizing plate which has the adhesive layer produced by said (b) on both surfaces of the glass substrate for liquid crystal cells ("Eagle 2000" (brand name) by a Corning Corporation) was bonded by the adhesive layer surface. At this time, one side of the glass substrate was adhered to the other side of the glass substrate such that the absorption axis of the second polarizing plate was perpendicular to the absorption axis of the first polarizing plate so that the absorption axis of the first polarizing plate was parallel to the long side of the glass substrate. . The heat resistant test stored for 96 hours under drying of the temperature of 80 degreeC was performed about the obtained laminated body. Then, it observed by visually confirming the expression state of the whiteout when light was made incident on one polarizing plate side. The results were classified according to the following criteria and shown in the "White Out (80 ° C Drying)" column of Table 3.

<Expression state of whiteout>

(Double-circle): Whiteout is not seen at all.

(Circle): Whiteout is hardly noticeable.

(Triangle | delta): Whiteout is a little outstanding.

X: Whiteout is remarkably recognized.

In addition, with respect to the laminated body which affixed the polarizing plate on both surfaces of the glass substrate in the same manner as above, the heat resistance test (indicated as "heat resistance" in Table 3) for 300 hours under drying at 80 degreeC, temperature 60 degreeC, relative humidity Moisture-resistant test stored at 90% for 300 hours (marked as `` moisture-resistant heat '' in Table 3), and the temperature was lowered to -30 ° C while heated to 70 ° C, followed by raising the temperature to 70 ° C in one cycle (1 Time), a thermal shock test (denoted "HS" in Table 3) was repeated 100 cycles. And it observed by visually confirming the laminated body after each test, and classified the result into the following references | standards, and put it together in the "durability" column of Table 3.

<Evaluation Criteria for Heat Test, Moisture and Heat Test and Heat Shock Test>

(Double-circle): No external appearance change, such as floating, peeling, and foaming, is seen.

(Circle): Almost no external appearance change, such as floating, peeling, and foaming, is seen.

(Triangle | delta): Appearance changes, such as floating, peeling, and foaming, are slightly outstanding.

X: Appearance changes, such as floating, peeling, foaming, are remarkably recognized.

(d) Evaluation of the rework property of the polarizing plate having an adhesive layer

The rework property of the polarizing plate which has the adhesive layer produced by said (b) was evaluated as follows. First, the polarizing plate with an adhesive layer was cut out into the test piece of 25 mm x 150 mm size. Subsequently, this test piece was adhere | attached on the glass substrate for liquid crystal cells using the attachment apparatus "" Ramipaka "(brand name) by Fujipla Co., Ltd.) from the adhesive layer side, 50 degreeC, 5 kg / cm <2> (490.3 kPa) ) Was autoclaved for 20 minutes. Furthermore, after heat-processing at 70 degreeC for 2 hours, and storing continuously for 48 hours in 50 degreeC oven, in the atmosphere of temperature of 23 degreeC and 50% of relative humidity, a polarizing plate is carried out at this speed of 300 mm / min from this adhesion test piece. It peeled in the 180 degree direction, observed the state of the glass plate surface, and classified into the following references | standards. In addition, it showed in Table 3.

<Evaluation Criteria for Reworkability>

(Double-circle): A dark part etc. are not recognized at all on the glass plate surface.

(Circle): A dark part etc. are hardly recognized on the glass plate surface.

(Triangle | delta): The dark part etc. are recognized by the glass plate surface.

X: The residue of an adhesive is recognized by the glass plate surface.

As can be seen from Table 1 and Table 3, a predetermined amount of a crosslinking agent is blended with the specific acrylic resin specified in the present invention to form an adhesive composition, and the adhesive layer of the polarizing plate is used as a glass cell substrate (liquid crystal cell to liquid crystal display). Examples 1 to 6, in which one polarizing plate is attached so that its absorption axis is parallel to the long side of the glass substrate, and the other polarizing plate is orthogonal to the one polarizing plate, are applied to both sides of the screen. The result was excellent in whiteout prevention, durability, and reworkability. In particular, Examples 3 and 4 which have 8% or 10% of structural units derived from an aromatic ring containing monomer in acrylic resin have the outstanding performance in whiteout prevention property.

On the other hand, Comparative Example 4 and acrylic in which the content of the structural unit derived from an aromatic ring containing monomer do not contain the structural unit derived from an aromatic ring containing monomer in Comparative Examples 1-3 and acrylic resin which became 20% or more in acrylic resin. In Comparative Example 5 in which the Mw / Mn of the resin was greater than 7, all of the whiteout preventive properties were insufficient.

Subsequently, using the acrylic resins L-S manufactured in the polymerization examples 12-19, the adhesive composition was prepared with or without these ionic compounds, and it apply | coated to a polarizing plate, and also produced the liquid crystal panel corresponding product For example. Also in the following examples, the crosslinking agent and the silane type compound used the same thing as the previous Examples 1-6 and Comparative Examples 1-5. As the ionic compound, N-octyl-4-methylpyridinium hexafluorophosphate (having the structure of the following formula) was used.

[Examples 7-11 and Comparative Examples 6-9]

(a) Preparation of pressure-sensitive adhesive composition

With respect to 100 parts of solid content of each of acrylic resins L to S (20% ethyl acetate solution) obtained in Polymerization Examples 12 to 19, 0.5 part of the above-described silane compound (KBM-403) and a crosslinking agent (colonate L) were used. Each amount shown in Table 4 and the ionic compound were mixed in the amount shown in Table 4 (However, Example 7 and Comparative Example 8 did not use an ionic compound), and ethyl acetate was added so that the solid content concentration was 13%. It added and prepared the adhesive composition.

(b) Preparation of Polarizing Plate with Pressure-Sensitive Adhesive Layer

The thickness after drying each adhesive composition prepared by said (a) using the applicator to the mold release process surface of the polyethylene terephthalate film (brand name "PET 3811", Lintech (it is available from the company, and is called a separator)) to which the mold release process was carried out. Was applied so as to have a thickness of 20 μm, and dried for 1 minute at 90 ° C. to prepare a sheet-shaped pressure-sensitive adhesive layer. Then, both surfaces of the polarizing film in which iodine was adsorbed and oriented on polyvinyl alcohol were used as a protective film made of triacetylcellulose. After bonding the separator of the sheet-shaped adhesive layer obtained above and the surface (adhesive surface) on the opposite side to the one surface of the polarizing plate of the 3-layered structure sandwiched by a laminator, curing for 7 days on conditions of 23 degreeC of temperature and 65% of a relative humidity. The polarizing plate which has an adhesive layer was produced.

(c) Evaluation of Polarizing Plate with Adhesive

About the polarizing plate which has each obtained adhesive, when peeling a separator, the surface resistance value of an adhesive layer is measured by the surface specific resistance measuring apparatus ["Hirest-up MCP-HT450" (brand name) of Mitsubishi Chemical Co., Ltd. product)]. The antistatic property was evaluated. If the surface resistance value is 10 ¹¹ Ω / □ orders or less, good antistatic property can be obtained. Evaluation of antistatic property was performed immediately after the curing of the polarizing film which has an adhesive layer was completed. The results are summarized in Table 4. In addition, the expression state, durability, and reworkability of the whiteout were evaluated in the same manner as in Examples 1 to 6 and Comparative Examples 1 to 5, and these results are also summarized in Table 4 in accordance with the description of Table 3. did.

As can be seen from Table 2 and Table 4, the aromatic ring-containing monomer (A-2) in the acrylic resin (A) constituting the pressure-sensitive adhesive composition is an aromatic ring-containing (meth) acryl compound represented by Formula II, In Example 7, in which n was 2, excellent results in all of the whiteout prevention property, the durability, and the rework property were obtained. In particular, high effect was recognized in the whiteout prevention property.

In addition, Examples 8 and 9 using the composition which corresponded substantially to the compound of the adhesive composition of Example 7 which mix | blended an ionic compound are excellent in anti-whiteout property, durability, and rework property, and also the favorable antistatic performance is also excellent. It is given. On the other hand, as an aromatic ring containing monomer (A-2) in the acrylic resin (A) which comprises an adhesive composition, it is an aromatic ring containing (meth) acryl compound represented by Formula II, Example 10 using what is n in formula. And 11 degrees show good antistatic properties by blending the ionic compound.

On the other hand, it is known that the acrylic resin (A) constituting the pressure-sensitive adhesive composition does not have a structural unit derived from an aromatic ring-containing monomer, but instead exhibits an effect in improving the antistatic performance in combination with an ionic compound. Although the comparative examples 6 and 7 which mix | blended an ionic compound with this and made an adhesive composition using the acrylic resin which copolymerized 2-methoxyethyl 10% or 20% provide good antistatic performance, it is whiteout prevention property, This is lacking. On the other hand, Comparative Examples 8 and 9 using an acrylic resin in which only a polar functional group-containing monomer is copolymerized with butyl acrylate are insufficient in whiteout prevention, regardless of the presence or absence of an ionic compound blend.

In the above Examples and Comparative Examples, experiments were carried out by attaching a polarizing plate to the front and back of the glass substrate with no liquid crystal interposed therebetween; Do not receive. In addition, since each test of heat resistance, heat-and-moisture resistance, and a thermal shock is looking at the state of the adhesive layer adhering to a glass substrate, it is not influenced by the presence or absence of the liquid crystal layer in a liquid crystal cell again.

[Industry availability]

The liquid crystal panel of this invention exhibits the outstanding whiteout prevention property, durability, and is also excellent in rework property. Therefore, the liquid crystal display device to which this liquid crystal panel is applied gives a favorable display quality and can maintain the favorable display quality for a long time.

10: glass cell for liquid crystal display (liquid crystal cell)
10A: long side of glass cell for liquid crystal display
11, 12: transparent glass substrate
20: polarizing plate (not related to first and second)
21: first polarizing plate
21A: absorption axis of first polarizing plate
22: second polarizing plate
22A: absorption axis of second polarizing plate
25: polarizing film
26, 27: transparent protective layer
28 optical compensation film (retardation film)
29: interlayer adhesive
30: adhesive layer for adhesion to liquid crystal cell (no first or second relationship)
31: first pressure-sensitive adhesive layer
32: 2nd adhesive layer

Claims (12)

Rectangle glass cell for liquid crystal display,
A first polarizing plate adhered to one surface of the glass cell through a first adhesive layer such that an absorption axis is parallel to the long side of the glass cell;
A liquid crystal panel comprising a second polarizing plate adhered such that an absorption axis is orthogonal to an absorption axis of the first polarizing plate through a second pressure sensitive adhesive layer on the other side of the glass cell.
At least one of the first pressure sensitive adhesive layer and the second pressure sensitive adhesive layer,
(A) (A-1) Formula I

(In the formula, R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents an alkyl group having 1 to 14 carbon atoms which may be substituted with an alkoxy group having 1 to 10 carbon atoms.)
80-96 weight% of (meth) acrylic-acid alkylester represented by
(A-2) 3 to 15% by weight of an unsaturated monomer having one olefinic double bond and at least one aromatic ring in the molecule, and
(A-3) 0.1 to 5% by weight of unsaturated monomer having a polar functional group
It is obtained by copolymerizing the monomer mixture containing, The weight average molecular weight (Mw) exists in the range of 1 million-2 million, and is represented by ratio (Mw / Mn) with respect to the number average molecular weight (Mn) of weight average molecular weight (Mw). 100 parts by weight of acrylic resin having a molecular weight distribution in the range of 3 to 7, and
(B) 0.01-5 weight part of crosslinking agents
It is formed of a pressure-sensitive adhesive composition containing, wherein the pressure-sensitive adhesive layer has a gel fraction of 60 to 99% by weight. The said 1st adhesive layer and the said 2nd adhesive layer are formed with the adhesive composition of Claim 1 containing 100 weight part of said acrylic resins (A) and 0.01-5 weight part of said crosslinking agents (B), The said adhesive The layer having a gel fraction of 60 to 99% by weight. The unsaturated monomer (A-2) according to claim 1 or 2, wherein formula (II)

(Wherein R ₃ represents a hydrogen atom or a methyl group, n is an integer of 1 to 8, and R ₄ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group)
The liquid crystal panel which is an aromatic ring containing (meth) acryl compound shown by these. The liquid crystal panel according to claim 1 or 2, wherein the unsaturated monomer (A-3) has at least one polar functional group selected from the group consisting of a free carboxyl group, a hydroxyl group, an amino group and an epoxy ring. The liquid crystal panel according to claim 1 or 2, wherein the crosslinking agent (B) contains an isocyanate compound. The liquid crystal panel according to claim 1 or 2, wherein the pressure-sensitive adhesive composition further contains 0.03 to 1 part by weight of the (C) silane compound. The liquid crystal panel according to claim 1 or 2, wherein the pressure-sensitive adhesive composition further contains (D) an ionic compound. The liquid crystal panel according to claim 7, wherein the unsaturated monomer (A-2) is an aromatic ring-containing (meth) acrylic compound represented by formula II described in claim 3, wherein n in the formula is 2 or more. The liquid crystal panel according to claim 1 or 2, wherein at least one of the first polarizing plate and the second polarizing plate is a protective film / polarizing film / protective film. The in-plane retardation value is 0-20 nm, and the retardation value of the thickness direction is 20-80 in the film located in the far side from the glass cell for liquid crystal display among the two protective films which sandwiched the said polarizing film. The film containing the cellulose acetate-based resin which is nm, and positioned in the glass cell side for liquid crystal display, contains the cellulose acetate-based resin whose in-plane phase difference value is 30-80 mm and the phase difference value of thickness direction is 80-250 mm. Liquid crystal panel. The in-plane retardation value is 0-20 nm, and the retardation value of the thickness direction is 20-80 in the film located in the far side from the glass cell for liquid crystal display among the two protective films which sandwiched the said polarizing film. The film which contains cellulose acetate-based resin which is nm, and is located in the glass cell side for liquid crystal displays contains in-plane retardation value 0-10 mm, and contains cellulose acetate-based resin whose retardation value in thickness direction is -25-25 nm. Liquid crystal panel. The film positioned on the glass cell side for liquid crystal display, wherein the film positioned farther from the glass cell for liquid crystal display among the two protective films sandwiching the polarizing film, the film positioned on the glass cell side for liquid crystal display is cycloolefin. A liquid crystal panel comprising a system resin.

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