TW202300617A - Adhesive composition, adhesive layer and optical member attached with the same - Google Patents

Abstract

The present application provides an adhesive composition, an adhesive layer comprising the adhesive composition, and an optical member attached with the adhesive layer comprising the adhesive composition. The adhesive composition contains: a (meth)acrylic resin (A) of 100 parts by weight, containing constituent unit of 3.5 wt % or less, derived from a (meth)acrylic monomer having a hydroxyl group, having a glass transition temperature of -25 ℃ or less; an aromatic isocyanate-based crosslinking agent (B) of 0.3-1 parts by weight; and a compound (C) containing at least one selected from an organic acid salt (C-1) and a compound containing an alkyleneoxy group (C-2); wherein the organic acid salt (C-1) is of 0.0001 to 5 parts by weight when being contained, and a compound containing an alkyleneoxy group (C-2) is of 0.1-5 parts by weight when being contained.

Description

Adhesive composition, adhesive layer, and optical component with adhesive layer

The present invention relates to an adhesive composition, an adhesive layer comprising the adhesive composition, and an optical member provided with the adhesive layer.

The polarizing plate formed by laminating the protective film on one or both sides of the polarizer is widely used in image display devices such as liquid crystal display devices and organic electroluminescence (organic EL) display devices, especially in recent years such as Optical components of various mobile devices such as mobile phones, smart phones, and tablet terminals. Optical members such as polarizing plates are often used by being bonded to other members (such as optical members such as liquid crystal cells of liquid crystal display devices) via an adhesive layer (for example, refer to JP-A-2010-229321). Therefore, for example, a polarizing plate is distributed on the market in the form of a polarizing plate with an adhesive layer provided on one surface in advance in most cases.

Adhesive compositions used in adhesive layers for laminating optical members are required to be durable. That is, bonded to the optical member, and inside the Adhesive layers built in image display devices, etc. are sometimes placed in high temperature or high temperature and high humidity environments, and placed in repeated high temperature and low temperature environments, but even in such environments, the adhesive layer is required to be able to Defects due to dimensional changes of adjacent optical members are suppressed. As this defect, there exist the floating of the interface of an adhesive layer and the optical member adjacent to it, peeling, and the foaming of an adhesive layer.

However, the conventional adhesive composition sometimes has insufficient durability when attached to an optical member as an adhesive layer, and the surface of the optical member to which the adhesive layer is attached may not In the case of a surface that is difficult to be activated effectively, durability may be insufficient in particular.

The object of the present invention is to provide an adhesive composition with good durability when the surface of an optical member is not easily activated effectively even by surface activation treatment, and when it is attached to the surface as an adhesive layer, including this An adhesive layer of an adhesive composition and an optical component having the adhesive layer.

The present invention provides an adhesive composition, an adhesive layer, and an optical member with an adhesive layer shown below.

〔1〕Adhesive composition system includes:

100 parts by weight of a (meth)acrylic resin (A) having a constituent unit derived from a (meth)acrylic monomer having a hydroxyl group, the content being 3.5% by weight or less, and the glass transition temperature being -25°C or less;

0.3 to 1 part by weight of an aromatic isocyanate-based crosslinking agent (B); and

Selected from organic acid salts (C-1) and compounds (C-2) containing alkoxyl groups at least one compound (C);

When the aforementioned organic acid salt (C-1) is contained, its content is 0.0001 to 5 parts by weight relative to 100 parts by weight of the aforementioned (meth)acrylic resin (A),

When the compound (C-2) containing the said alkyleneoxy group is contained, the content is 0.1-5 weight part with respect to 100 weight part of said (meth)acrylic-type resins (A).

[2] The adhesive composition according to [1], wherein the compound (C-2) containing an alkyleneoxy group is a compound containing at least one double bond and at least one alkylenedioxy group in the molecule. .

[3] The adhesive composition according to [1] or [2], wherein the content of the structural unit derived from the (meth)acrylic monomer having a hydroxyl group is 0.5% by weight or more.

[4] The adhesive composition according to any one of [1] to [3], which further contains an ionic compound (D).

[5] The adhesive composition according to any one of [1] to [4], which further contains a silane compound (E).

[6] The adhesive composition according to any one of [1] to [5], wherein the adhesive composition is formed into a layer on a film made of a cyclic polyolefin resin, and the layer After the adhesive composition was laminated on the non-alkali glass plate and stored for 24 hours at a temperature of 23°C, the peeling force when peeled from the non-alkali glass plate was P(CO)23, and

The aforementioned adhesive composition is formed into a layer on a film made of cyclic polyolefin resin, and the layered adhesive composition is laminated on an alkali-free glass The state of the glass plate is stored in an environment at a temperature of 50°C for 48 hours, and when the peeling force when peeled from the alkali-free glass plate is P(CO)50, the above-mentioned P(CO)50 and the above-mentioned P(CO) The ratio of 23 (P(CO)50/P(CO)23) is 3.2 or more.

[7] The adhesive composition according to any one of [1] to [5], wherein the adhesive composition is formed into a layer on a film made of (meth)acrylic resin, and After the layered adhesive composition is laminated on the non-alkali glass plate and stored in an environment at a temperature of 23° C. for 24 hours, the peeling force when peeled from the non-alkali glass plate is P(AC)23, and

The aforementioned adhesive composition was formed into a layer on a film made of (meth)acrylic resin, and the layered adhesive composition was laminated on an alkali-free glass plate and stored at a temperature of 50°C for 48 hours. Hours later, when the peeling force at the time of peeling from the alkali-free glass plate is P(AC)50, the ratio of the aforementioned P(AC)50 to the aforementioned P(AC)23 (P(AC)50/P(AC) 23) 3.2 or more.

[8] The adhesive composition according to any one of [1] to [7], which contains the aforementioned organic acid salt (C-1) and the aforementioned alkyleneoxy group-containing compound (C-2);

The content of the aforementioned organic acid salt (C-1) is 0.0001 to 0.1 parts by weight relative to 100 parts by weight of the aforementioned (meth)acrylic resin (A);

Content of the said alkyleneoxy group containing compound (C-2) is 0.1-5 weight part with respect to 100 weight part of said (meth)acrylic-type resins (A).

[9] An adhesive layer comprising any one of [1] to [8] Adhesive composition described in item.

[10] An optical member with an adhesive layer, comprising an optical member and the adhesive layer described in [9] laminated on the optical member.

[11] The adhesive layer-attached optical member according to [10], wherein the surface of the optical member on which the adhesive layer is laminated has a contact angle change rate of 40% or less when subjected to corona treatment.

[12] The optical member with an adhesive layer according to [11], wherein the optical member includes a polarizer and a protective film laminated on the polarizer, and the surface is the surface of the protective film.

[13] The optical member with an adhesive layer according to [11] or [12], wherein the surface is a corona-treated surface.

[14] The optical member with an adhesive layer according to any one of [11] to [13], further comprising a glass substrate laminated on the adhesive layer.

[15] An optical member with an adhesive layer, comprising a resin film and an adhesive layer laminated on at least one side of the resin film;

The aforementioned adhesive layer comprises the adhesive composition described in any one of [1] to [8];

After the adhesive layer is laminated on the non-alkali glass plate and stored in an environment at a temperature of 23° C. for 24 hours, the peeling force when peeled from the non-alkali glass plate is P23, and

In the state where the above-mentioned adhesive is laminated on the non-alkali glass plate and stored in an environment at a temperature of 50°C for 48 hours, when the peeling force at the time of peeling from the non-alkali glass plate is P50, the above-mentioned P50 and the above-mentioned P23 Ratio (P50/P23) 3.2 or higher.

According to the present invention, there can be provided an adhesive composition having good durability, an adhesive layer including the adhesive layer, and an optical member including the adhesive layer attached to the adhesive layer.

1: Polarizer

2: Surface treatment layer

3,4: Protective film

7: Retardation film

8: interlayer adhesive

10: polarizer

20: Adhesive layer

25: Polarizing plate with adhesive layer

30: glass plate

Fig. 1 is a schematic cross-sectional view showing an example of an optical member with an adhesive layer of the present invention.

Fig. 2 is a schematic cross-sectional view showing another example of an optical member with an adhesive layer of the present invention.

Fig. 3 is a schematic cross-sectional view showing still another example of an optical member with an adhesive layer of the present invention.

Fig. 4 is a schematic cross-sectional view showing still another example of an optical member with an adhesive layer of the present invention.

<Adhesive composition>

[1] (meth)acrylic resin (A)

The (meth)acrylic resin (A) is a polymer containing a structural unit derived from a (meth)acrylic monomer having a hydroxyl group, and preferably contains the following formula (I) in addition to the structural unit:

The shown (meth)acrylate-derived structural unit is a polymer as a main component. In this specification, "(meth)acrylic acid" means acrylic acid and/or methacrylic acid, and "(meth)" when called (meth)acrylate etc. also have the same meaning.

In the above formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkyl group having 1 to 14 carbons which may be substituted by an alkoxy group having 1 to 10 carbons or an alkane having 1 to 10 carbons Aralkyl group having 7 to 21 carbon atoms substituted by oxy group. R ² is preferably an alkyl group having 1 to 14 carbons which may be substituted with an alkoxy group having 1 to 10 carbons.

The (meth)acrylate represented by the formula (I) is, for example, an alkyl (meth)acrylate, and its specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-(meth)acrylate Propyl ester, n-butyl (meth)acrylate, n-octyl (meth)acrylate, and alkyl (meth)acrylate in which the alkyl portion of (meth)acrylate is linear; (meth)acrylic acid Isopropyl, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, alkyl (meth)acrylate in which the alkyl portion of isooctyl (meth)acrylate is branched, etc. The carbon number of the alkyl portion of the alkyl (meth)acrylate is preferably 1-8, more preferably 1-6.

When R ² is an alkyl group substituted by an alkoxy group, that is, when R ² is an alkoxy alkyl group, specific examples of (meth)acrylic acid esters represented by formula (I) include (meth)acrylic acid 2 - Methoxyethyl ester, ethoxymethyl (meth)acrylate and the like. The number of carbon atoms in the alkyl group of the alkoxyalkyl group is preferably 1-8, more preferably 1-6. The number of carbon atoms in the alkoxy group of the alkoxyalkyl group is preferably 1-8, more preferably 1-4. Specific examples of the (meth)acrylate represented by the formula (I) when R ² is an aralkyl group having 7 to 21 carbon atoms include benzyl (meth)acrylate. The carbon number of the above-mentioned aralkyl group is preferably 7-11.

The (meth)acrylate represented by formula (I) may be used alone or in combination of two or more. Among them, the (meth)acrylate preferably includes alkyl (meth)acrylate, more preferably includes alkyl acrylate, and is even more preferably includes n-butyl acrylate. The (meth)acrylic resin (A) preferably contains 50% by weight of n-butyl acrylate derived in all the structural units constituting it. Of course, other than n-butyl acrylate, the (meth)acrylate represented by the formula (I) may be used together.

The content of the structural unit derived from the (meth)acrylate represented by formula (I) is usually 60% by weight or more and less than 100% by weight in all the structural units constituting the (meth)acrylic resin (A) , preferably 70 to 99.9% by weight, more preferably 80 to 99.6% by weight.

The (meth)acrylic resin (A) contains the structural unit derived from the (meth)acrylic monomer which has a hydroxyl group. Containing this structural unit is advantageous in improving the adhesiveness between the adhesive layer and the optical member and the durability of the adhesive layer. The (meth)acrylic monomer having a hydroxyl group is preferably a (meth)acrylate having a hydroxyl group. Specific examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylate base) 2-(2-hydroxyethoxy) ethyl acrylate, 2- or 3-chloro-2-hydroxypropyl (meth) acrylate, hydroxyl-containing alkyl esters of (meth) acrylic acid, such as diethylene di Alcohol mono(meth)acrylate, polyfunctional alcohol and partial esterification of (meth)acrylic acid, etc. Adhesive bonding from adhesive layers to optical components From the standpoint of properties and durability (especially heat resistance) of the adhesive layer, the monomer having a hydroxyl group is preferably a (meth)acrylate having a hydroxyl group, more preferably a hydroxyl-containing alkyl ester of (meth)acrylic acid . The number of carbon atoms in the alkyl portion of the hydroxyl group-containing alkyl ester of (meth)acrylic acid is preferably 1-8, more preferably 1-6.

The content of the structural unit derived from the (meth)acrylic monomer having a hydroxyl group is 3.5% by weight or less, preferably 3% by weight or less, in all the structural units constituting the (meth)acrylic resin (A), More preferably, it is 2.5 weight% or less, More preferably, it is 2 weight% or less. When the content of the structural unit derived from the (meth)acrylic-type monomer which has a hydroxyl group exceeds 3.5 weight%, the durability of an adhesive layer, especially heat resistance will become insufficient. On the other hand, content of the structural unit derived from the (meth)acrylic-type monomer which has a hydroxyl group is 0.1 weight% or more normally, Preferably it is 0.2 weight% or more, More preferably, it is 0.5 weight% or more. When content of the structural unit derived from the (meth)acrylic-type monomer which has a hydroxyl group is less than 0.1 weight%, the adhesiveness of an adhesive layer and an optical member, the durability of an adhesive layer, etc. are insufficient.

(Meth)acrylic resin (A) may contain the structural unit derived from the monomer which has other polar functional groups other than the (meth)acrylic monomer which has a hydroxyl group. The monomer having a polar functional group is preferably a (meth)acrylic monomer having a polar functional group. As a polar functional group which this monomer has, a carboxyl group (free carboxyl group), an amine group, a heterocyclic group (for example, an epoxy group), etc. are mentioned, for example.

Specific examples of monomers with other polar functional groups include (meth)acrylic acid, (meth)acrylic acid β-carboxyethyl Based monomers; acryl morpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, vinyl pyridine, tetrahydrofuran methyl (meth) acrylate, caprolactone modified tetrahydrofuran methyl ( Monomers with heterocyclic groups of meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, epoxypropyl (meth)acrylate, and 2,5-dihydrofuran;( Aminoethyl meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, monomers having amino groups different from heterocyclic rings wait. A monomer having another polar functional group may be used alone or in combination of two or more.

In addition to the (meth)acrylic monomers with hydroxyl groups, monomers with other polar functional groups are used in combination. Among them, the (meth)acrylic monomers with carboxyl groups are effective in improving the adhesion between the adhesive layer and the optical member, The adhesive layer is advantageous in terms of durability (especially heat resistance).

The content of constituent units derived from monomers having other polar functional groups, preferably (meth)acrylic monomers having carboxyl groups, is preferably 5% by weight or less, more preferably 4% by weight or less. When the content of the constituent unit derived from the monomer having another polar functional group exceeds 5% by weight, the durability of the adhesive layer, especially the heat resistance tends to be insufficient. On the other hand, the content of constituent units derived from monomers having other polar functional groups, when contained, is usually at least 0.1% by weight, preferably at least 0.2% by weight, more preferably at least 0.3% by weight. When the content of the constituent unit derived from the monomer having another polar functional group is less than 0.1% by weight, it is difficult to see the effect of use. from all containing (meth)acrylic monomers having hydroxyl groups having The structural unit of the monomer of a polar functional group is 0.1 to 8.5 weight% normally, Preferably it is 0.2 to 7 weight% in all structural units which comprise a (meth)acrylic-type resin (A).

The (meth)acrylic resin (A) may further include a monomer (except for the monomer represented by the above formula (I) or the above-mentioned monomer having one olefinic double bond and at least one aromatic ring) in the molecule. Constituent units other than those related to monomers with polar functional groups. As a suitable example, the (meth)acrylic-type monomer which has an aromatic ring is mentioned, for example. Such (meth)acrylic monomers with an aromatic ring also include neopentyl glycol benzoate (meth)acrylate, etc., especially as the following formula (II):

The (meth)acrylates having an aryloxyalkyl group of the indicated (meth)acrylates containing a phenoxyethyl group are preferred. A monomer having one olefinic double bond and at least one aromatic ring in the molecule, such as a phenoxyethyl group-containing (meth)acrylate, may be used alone or in combination of two or more.

In the above formula (II), R ³ represents a hydrogen atom or a methyl group, n represents an integer from 1 to 8, and R ⁴ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group. When R is ^an alkyl group, its carbon number may be about 1 to 9, when it is an aralkyl group, its carbon number may be about 7 to 11, or when it is an aromatic group, its carbon number may be about 6 to 10.

As an ^alkyl group with 1 to 9 carbons constituting R in the formula (II), for example, methyl, butyl, nonyl, etc., as an aralkyl group with 7 to 11 carbons, for example, benzyl , phenethyl, naphthylmethyl, and the like, and examples of the aromatic group having 6 to 10 carbon atoms include phenyl, tolyl, and naphthyl.

Specific examples of (meth)acrylic acid esters containing phenoxyethyl represented by formula (II) include 2-phenoxyethyl (meth)acrylate, 2-(2-phenoxy (meth)acrylate of nonylphenol modified with ethylene oxide, 2-(o-phenylphenoxy)ethyl (meth)acrylate, etc. Wherein, the (meth)acrylate containing phenoxyethyl includes 2-phenoxyethyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate and/or 2-(2-phenoxyethoxy)ethyl (meth)acrylate is preferred.

Content of the structural unit derived from the monomer which has an aromatic ring is 0 to 20 weight% (for example, 6 to 12 weight%) normally in all structural units which comprise a (meth)acrylic-type resin (A). However, in order to make the glass transition temperature of (meth)acrylic-type resin (A) into the predetermined range mentioned later, it may be preferable not to contain the structural unit derived from the monomer which has an aromatic ring.

The (meth)acrylic resin (A) may contain monomers other than the (meth)acrylic monomer represented by the formula (I) described above, the monomer having a polar functional group, and the monomer having an aromatic ring. A constituent unit of a body (hereinafter also referred to as other monomer). Specific examples of other monomers include (meth)acrylic monomers having an alicyclic structure in the molecule (preferably (meth)acrylates having an alicyclic structure in the molecule) Structural units derived from styrene-based monomers, structural units derived from vinyl-based monomers, structural units derived from monomers having multiple (meth)acryl groups in the molecule, and derived from (meth)acrylic Constituent units of amide compounds, etc. As other monomers, one type may be used alone, or two or more types may be used in combination.

The alicyclic structure of (meth)acrylate having an alicyclic structure in the molecule refers to a cycloalkane structure usually having 5 or more carbon atoms, preferably about 5 to 7 carbon atoms. Specific examples of (meth)acrylates having an alicyclic structure include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (meth)acrylic acid Cyclododecyl, Methylcyclohexyl (meth)acrylate, Trimethylcyclohexyl (meth)acrylate, 3rd Butylcyclohexyl (meth)acrylate, Cyclohexylbenzene (meth)acrylate Esters, α-ethoxycyclohexyl acrylate, etc.

Specific examples of styrenic monomers include styrene; such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propyl Alkylstyrene of styrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene; such as halogenation of fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene Styrene; nitrostyrene, acetylstyrene, methoxystyrene, divinylbenzene, etc.

Specific examples of vinyl-based monomers include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate; such as vinyl chloride, brominated Vinyl halides of ethylene; such as vinylidene chloride; such as vinylpyridine, ethylene Nitrogen-containing aromatic vinyls such as pyrrolidone and vinyl carbazole; conjugated diene monomers such as butadiene, isoprene, and chloroprene; acrylonitrile, methacrylonitrile, etc.

Specific examples of monomers having multiple (meth)acryl groups in the molecule include, for example, 1,4-butanediol di(meth)acrylate, 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 , Tripropylene glycol di(meth)acrylate has 2 (meth)acrylic acid monomers in the molecule; such as trimethylolpropane tri(meth)acrylate has 3 (meth)acrylates in the molecule ) acryl-based monomers, etc.

Specific examples of (meth)acrylamide compounds include N-methylol (meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, N-(3-hydroxypropyl base) (meth)acrylamide, N-(4-hydroxybutyl)(meth)acrylamide, N-(5-hydroxypentyl)(meth)acrylamide, N-(6-hydroxy Hexyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide Amide, N-(3-dimethylaminopropyl)(meth)acrylamide, N-(1,1-dimethyl-3-oxobutyl)(meth)acrylamide, N -[2-(2-oxo-1-imidazolidinyl (imidazolidinyl)) ethyl] (meth)acrylamide, 2-acrylamino-2-methyl-1-propanesulfonic acid, N- (Methoxymethyl)acrylamide, N-(ethoxymethyl)(meth)acrylamide, N-(propoxymethyl)(meth)acrylamide, N-(1- Methylethoxymethyl)(meth)acrylamide, N-(1-methylpropoxymethyl)(meth)acrylamide Amide, N-(2-methylpropoxymethyl)(meth)acrylamide [alias: N-(isobutoxymethyl)(meth)acrylamide], N-(butoxy methyl)(meth)acrylamide, N-(1,1-dimethylethoxymethyl)(meth)acrylamide, N-(2-methoxyethyl)(methyl) ) acrylamide, N-(2-ethoxyethyl)(meth)acrylamide, N-(2-propoxyethyl)(meth)acrylamide, N-[2-(1 -Methylethoxy)ethyl](meth)acrylamide, N-[2-(1-methylpropoxy)ethyl](meth)acrylamide, N-[2-(2 -Methylpropoxy)ethyl](meth)acrylamide [alias: N-(2-isobutoxyethyl)(meth)acrylamide], N-(2-butoxyethyl) base) (meth)acrylamide, N-[2-(1,1-dimethylethoxy)ethyl](meth)acrylamide, etc. Among them, use N-(methoxymethyl)acrylamide, N-(ethoxymethyl)acrylamide, N-(propoxymethyl)acrylamide, N-(butoxymethyl) ) acrylamide and N-(2-methylpropoxymethyl)acrylamide are preferred.

The (meth)acrylic resin (A) contains the structural unit originating in another monomer in the total structural unit which comprises this, normally 0 to 20 weight%, Preferably it is contained in the ratio of 0 to 10 weight%.

The adhesive composition may contain two or more types of (meth)acrylic resins belonging to the (meth)acrylic resin (A). In addition, the adhesive composition may contain other (meth)acrylic resins different from the (meth)acrylic resin (A). An example of other (meth)acrylic resins is a (meth)acrylic resin that has a structural unit derived from a (meth)acrylic monomer represented by formula (I) and does not have a polar functional group. However, the adhesive composition contains (meth)acrylic resin (A) Preferably as the main component, the content of the (meth)acrylic resin (A) in the total of all the (meth)acrylic resins is preferably at least 60% by weight, more preferably at least 80% by weight, and even more preferably Preferably, it is at least 90% by weight.

The (meth)acrylic resin (A) has a glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of -25°C or lower, preferably -30°C or lower. According to the adhesive composition of this invention containing the (meth)acrylic resin (A) whose Tg is -25 degreeC or less, the adhesiveness of an adhesive layer and an optical member, and the durability of an adhesive layer can be improved. From the viewpoint of durability, the Tg of the (meth)acrylic resin (A) is usually -55°C or higher, preferably -50°C or higher.

Furthermore, according to the adhesive composition of this invention containing the (meth)acrylic-type resin (A) whose Tg is -25 degreeC or less, shortening of the aging time of an adhesive layer can be aimed at. In other words, the adhesive layer (adhesive sheet) is generally cured in order to obtain a cross-linking reaction to a suitable degree of workability and processability. According to the adhesive composition of the present invention, the time required for the cross-linking reaction to fully proceed can be shortened. The desired curing time of the adhesive layer.

The (meth)acrylic resin (A) is based on gel permeation chromatography (GPC) and the weight average molecular weight (Mw) of standard polystyrene is preferably in the range of 500,000 to 2 million, 600,000 to 1.80 The range of 10,000 is better. When the Mw is more than 500,000, the adhesiveness between the adhesive layer and the optical member in a high-temperature and high-humidity environment increases, and the possibility of floating or peeling between the adhesive layer and the optical member tends to decrease. Furthermore, the adhesive layer The rework (rework) tends to improve. Moreover, when Mw is 2 million or less, when bonding the adhesive layer to the optical member, even if the size of the optical member changes Since the adhesive layer easily changes following the dimensional change, it is advantageous in terms of the adhesiveness between the adhesive layer and the optical member and the durability of the adhesive layer. Moreover, when the optical member with the adhesive layer is applied to a liquid crystal display device due to the above-mentioned followability, the difference between the brightness of the peripheral part of the liquid crystal cell and the brightness of the central part disappears, and there is an effect of suppressing whitening and color unevenness. tendency. The molecular weight distribution represented by the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is usually about 2 to 10, preferably 3 to 7.

The (meth)acrylic resin (A) and other (meth)acrylic resins that can be optionally used in combination can be produced by known methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization. . In the manufacture of (meth)acrylic resin, a polymerization initiator can be used normally. The polymerization initiator can be used at about 0.001 to 5 parts by weight with respect to a total of 100 parts by weight of all the monomers used in the production of the (meth)acrylic resin. Furthermore, the (meth)acrylic resin can also be manufactured by the method of polymerizing with active energy rays, such as an ultraviolet-ray, for example.

As a polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, etc. can be used. As a photoinitiator, 4-(2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone etc. are mentioned, for example. As a thermal polymerization initiator, such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1 -formonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) , dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-hydroxymethylpropionitrile) azo compounds; such as lauryl peroxide base, 3-butyl peroxide, benzoyl peroxide, 3-butyl peroxybenzoate, peroxygen Cumyl hydrochloride, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, 3-butyl peroxyneodecanoate, 3-butyl peroxypivalate, peroxide (3,5, 5-trimethylhexyl) organic peroxide; such as potassium persulfate, ammonium persulfate, inorganic peroxide of hydrogen peroxide, etc. Furthermore, a redox-based initiator or the like in which a peroxide and a reducing agent are used in combination can also be used as the polymerization initiator.

As a manufacturing method of a (meth)acrylic-type resin, among the methods shown above, the solution polymerization method is preferable. One example of the solution polymerization method is to mix the monomers used with an organic solvent, add a thermal polymerization initiator under a nitrogen atmosphere, and stir at about 40 to 90° C., preferably at about 50 to 80° C., for 3 to 15 hours. In order to control the reaction, monomers and thermal polymerization initiators may be added continuously or intermittently during polymerization, or may be added in a state dissolved in an organic solvent. As the organic solvent, for example, aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropanol; Ketones, ketones such as methyl isobutyl ketone, etc.

[2] Aromatic isocyanate-based crosslinking agent (B)

The adhesive composition may further contain an aromatic isocyanate crosslinking agent (B). The aromatic isocyanate crosslinking agent (B) is a compound which has an aromatic ring and has 2 or more isocyanate groups in a molecule|numerator. By using an aromatic isocyanate compound (B) as a crosslinking agent, the adhesiveness of an adhesive layer and an optical member, and the durability of an adhesive layer can be improved.

Specific examples of the aromatic isocyanate-based crosslinking agent (B) are cresyl diisocyanate, chlorophenylene diisocyanate, diphenylmethane Alkane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, naphthyl diisocyanate, etc. Furthermore, the aromatic isocyanate-based crosslinking agent (B) includes polyol adducts (for example, adducts of trimethylolpropane), trimeric isocyanate compounds, and biuret-type compounds of these isocyanate compounds. , Furthermore, derivatives such as polyurethane polymer type isocyanate compounds that are added to polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, etc. The aromatic isocyanate crosslinking agent (B) may be used alone or in combination of two or more.

Among the aromatic isocyanate-based crosslinking agents (B), the aromatic isocyanate-based crosslinking agent in which the isocyanate group is bonded to the aromatic ring is effective in improving the adhesion between the adhesive layer and the optical member and the durability of the adhesive layer. It is better to use. Specific examples of the aromatic isocyanate-based crosslinking agent in which the isocyanate group is bonded to the aromatic ring include tolyl diisocyanate, chlorophenylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, Naphthyl diisocyanate, etc.

The content of the aromatic isocyanate crosslinking agent (B) is 0.3 to 1 part by weight, preferably 0.35 to 0.9 part by weight, based on 100 parts by weight of the (meth)acrylic resin (A). When the content of the aromatic isocyanate-based crosslinking agent (B) is less than 0.3 parts by weight, depending on the surface material of the optical member on which the adhesive layer is laminated, the adhesiveness between the adhesive layer and the optical member becomes insufficient even if a sufficient curing time is spent. . And depending on the surface material of the optical member on which the adhesive layer is laminated, the durability at the time of bonding the adhesive layer to the optical member decreases. The content of the aromatic isocyanate crosslinking agent (B) When the amount exceeds 1 part by weight, the adhesiveness of an adhesive layer and an optical member will become insufficient even if it takes sufficient aging time. Furthermore, durability, especially heat resistance at the time of bonding an adhesive layer to an optical member falls.

[3] Compound (C)

The adhesive composition further contains at least one compound (C) selected from organic acid salts (C-1) and compounds (C-2) containing alkyleneoxy groups. According to the adhesive composition of the present invention containing the compound (C), the adhesiveness between the adhesive layer and the optical member, and the durability when the adhesive layer is bonded to the optical member, especially heat resistance can be improved. Furthermore, it is possible to shorten the aging time of the adhesive layer. The adhesive composition may contain only the organic acid salt (C-1), may contain only the compound (C-2) containing an alkeneoxy group, or may contain both of them.

The organic acid salt (C-1) is preferably a salt of an organic acid having a carboxylic acid terminal and a base, that is, an organic carboxylate. When an organic carboxylate is used as the organic acid salt (C-1), the counter cation of the carboxylate anion is preferably a counter cation having a valence of 3 or less. An organic acid salt (C-1) may be used individually by 1 type, and may use 2 or more types together.

Examples of the counter cation include metal ions, ammonium ions, cations having a heterocyclic structure, and the like. Preferable examples of metal ions include alkali metal ions and alkaline earth metal ions. Preferred examples of cations with a heterocyclic structure include pyrrolinium ions, imidazolium ions, triazolium ions, pyrrolidinium ions, pyridinium ions, and piperidinium ions.

Carboxylate anions as organic acid salts (C-1), such as formate, acetate, propionate, heptanoate, octanoate, Linear saturated alkyl carboxylate ion of lauric acid ion; straight chain unsaturated alkyl carboxylate ion of (meth)acrylic acid and oleic acid; aromatic carboxylate ion of benzoic acid and cinnamic acid; such as nicotinic acid Carboxylate anions with heterocyclic structure; dicarboxylate ions such as succinic acid, fumaric acid, phthalic acid; Carboxylate ion of oxyethylene skeleton, etc.

The content of the organic acid salt (C-1) is 0.0001 to 5 parts by weight relative to 100 parts by weight of the (meth)acrylic resin (A), preferably 0.0005 to 5 parts by weight, more preferably 0.0007 to 3 parts by weight, More preferably, it is 0.001 to 1 part by weight, and particularly preferably, it is 0.0015 to 0.5 part by weight. As long as the content is within this range, the adhesion between the adhesive layer and the optical member and the durability when the adhesive layer is bonded to the optical member can be obtained, and the adhesive composition can be obtained in which the aging time of the adhesive layer can be shortened.

The compound (C-2) containing an alkyleneoxy group is preferably a compound containing at least one double bond and at least one alkylenedioxy group in the molecule. The alkylene dioxy group is preferably contained in the compound (C-2) as an alkylene dioxy group (-O-alkylene-O-). A preferable example of the above-mentioned double bond is a double bond contained in a (meth)acryloyl group. The compound (C-2) containing an alkyleneoxy group may be used individually by 1 type, and may use 2 or more types together. According to the adhesive layer composed of the adhesive composition containing the compound (C-2) containing the alkeneoxy group, the release force of the peeling film laminated on the surface of the adhesive layer to the adhesive layer can also be suppressed from being accelerated by heat.

A preferable example of the above-mentioned alkylenedioxy group is an alkylene group having 1 to 4 carbon atoms from the viewpoint of the adhesiveness between the adhesive layer and the optical member, and the durability when the adhesive layer is bonded to the optical member. An alkylene dioxy group, more preferably a linear or branched alkylene dioxy group having 1 to 3 carbon atoms, more preferably an ethylene dioxy group (-OC ₂ H ₄ -O-). Furthermore, the same is true for the examples of alkylene groups other than alkylene dioxy groups. The alkylene group is preferably an alkylene group with 1 to 4 carbons, and a straight chain or branched group with 1 to 3 carbons. An alkyleneoxy group is more preferred, and an ethylenyloxy group (-OC ₂ H ₄ -) is even more preferred.

Compound (C-2) contains the following formula (C-2a):

The shown compound (C-2a) containing a (meth)acryloyl group is preferable, and it is more preferably composed of compound (C-2a). In the formula, h represents an integer of 1 to 6, Q ¹ represents a hydrogen atom or a methyl group, and Q ⁰ represents an h-valent group having at least one alkylenedioxy group. Compound (C-2) may contain two or more compounds (C-2a), and h is preferably an integer of 1 to 3.

The h-valent base having at least one alkylenedioxy group represented by Q ⁰ can be a h-valent hydrocarbon group having at least one alkylenedioxy group, preferably having at least one alkylenedioxy group 1 to 3 valent hydrocarbon groups. Examples of the hydrocarbon group include groups represented by Q ⁰¹ , Q ⁰² , Q ⁰³ and Q ⁰⁴ described below.

In Q ⁰¹ , Q ² represents an alkyl, aryl or aralkyl group with 1 to 4 carbons which may be substituted by an alkoxy group with 1 to 3 carbons, and L represents a single bond or an alkylene group with 1 to 4 carbons , i represents an integer of 1 to 50 (for example, 1 to 30). The carbon number of the aryl group that can become Q ² is preferably 6 to 20, and the carbon number of the aralkyl group is preferably 7 to 20. In Q ⁰² , j represents an integer of 1 to 40 (for example, 1 to 30). In Q ⁰³ , y and z independently represent an integer of 1 to 40 (eg, 1 to 30), and y+z may be an integer of 1 to 40 (eg, 1 to 30). In Q ⁰⁴ , e, f and g independently represent an integer of 1 to 20 (eg, 1 to 10), and e+f+g may be an integer of 1 to 30 (eg, 1 to 25).

As a preferably used compound (C-2a), for example, the following formula (C-2a-1):

Compound (C-2a-1) shown. The compound (C-2) may contain two or more kinds of compounds (C-2a-1). Compound (C-2a-1) is a compound in which Q ⁰ of the above formula (C-2a) is Q ⁰¹ . Q ¹ , L, i, and Q ² in the formula have the same meanings as above. In compound (C-2a-1), L is preferably a single bond, i is preferably an integer of 7 to 35, more preferably an integer of 9 to 25. ^Q2 is an alkyl group with 1 to 3 carbons or an aryl group with 6 to 20 carbons. Specific examples of ^Q2 include methyl, ethyl, n-propyl, isopropyl, phenyl, biphenyl base.

As specific examples of the compound (C-2a-1), for example, Q ¹ , L, i, and Q ² are those shown in Table 1 below.

Another example of the preferably used compound (C-2a) is a compound in which Q ⁰ of the above formula (C-2a) is Q ⁰⁴ . In this case, h in the above formula (C-2a) is 3. The compound (C-2) may contain two or more compounds in which Q ⁰ is Q ⁰⁴ . For Q ⁰⁴ , e+f+g is preferably an integer of 5 to 25.

Another example of the preferably used compound (C-2a) is a compound in which Q ⁰ of the above formula (C-2a) is Q ⁰³ . In this case, h in the above formula (C-2a) is 2. The compound (C-2) may contain two or more compounds in which Q ⁰ is Q ⁰³⁴ . For Q ⁰³ , y+z is preferably an integer from 5 to 25.

The content of compound (C-2), relative to (methyl) propane 100 parts by weight of the acrylic resin (A) is 0.1 to 5 parts by weight, preferably 0.15 to 5 parts by weight, more preferably 0.2 to 4.5 parts by weight, even more preferably 0.5 to 4 parts by weight. As long as the content is within this range, the adhesion between the adhesive layer and the optical member and the durability when the adhesive layer is bonded to the optical member can be obtained, and the adhesive composition that can shorten the aging time of the adhesive layer can be obtained. In addition, the acceleration effect of suppressing the peeling force can be obtained.

[4] Ionic compound (D)

The adhesive composition may further contain an ionic compound (D) of an antistatic agent for imparting antistatic properties to the adhesive layer. The ionic compound (D) is a compound having an inorganic cation or an organic cation, and an inorganic anion or an organic anion. Two or more kinds of ionic compounds (D) can be used.

As inorganic cations, alkali metal ions such as lithium cations [Li ⁺ ], sodium cations [Na ⁺ ], potassium cations [K ⁺ ] and beryllium cations [Be ²⁺ ], magnesium cations [Mg ²⁺ ], calcium cations [Ca ²⁺ ] alkaline earth metal ions, etc.

Examples of organic cations include imidazolium cations, pyridinium cations, pyrrolidinium cations, ammonium cations, sulfonium cations, phosphonium cations and the like.

Among the above-mentioned cationic components, organic cationic components are preferably used because they have excellent compatibility with the adhesive composition. Among the organic cation components, pyridinium cations and imidazolium cations are particularly preferred from the viewpoint of being less likely to be charged when peeled from the release film provided on the adhesive layer.

As inorganic anions, such as chloride anion [Cl ^- ], bromide anion [Br ^- ], iodide anion [I ^- ], tetrachloroaluminate anion [AlCl ₄ ^- ], heptachloroaluminate anion [Al ₂ Cl ₇ ^- ], tetrafluoroborate anion [BF ₄ ^- ], hexafluorophosphate anion [PF ₆ ^- ], perchlorate anion [ClO ₄ ^- ], nitrate anion [NO ₃ ^- ], hexafluoroarsenate anion 〔AsF ₆ ^- 〕, hexafluoroantimonate anion [SbF ₆ ^- ], hexafluoroniobate anion [NbF ₆ ^- ], hexafluorotantalate anion [TaF ₆ ^- ], dicyanamide anion [(CN) ₂ N ^- ] and so on.

As organic anions, for example, acetate anion [CH ₃ COO ^- ], trifluoroacetate anion [CF ₃ COO ^- ], methanesulfonate anion [CH ₃ SO ₃ ^- ], trifluoromethanesulfonate anion [ CF ₃ SO ₃ ^- ], p-toluenesulfonate anion [p-CH ₃ C ₆ H ₄ SO ₃ ^- ], bis(fluorosulfonyl)imide anion [(FSO ₂ ) ₂ N ^- ], bis (Trifluoromethanesulfonyl)imide anion [(CF ₃ SO ₂ ) ₂ N ^- ], tris(trifluoromethanesulfonyl)methanide anion [(CF ₃ SO ₂ ) ₃ C ^- ] , dimethyl phosphonite [(CH ₃ ) ₂ POO ^- ], polyhydrofluorofluoride anion [F(HF) _n ^- ] (n is in the range of 1 to 3), thiocyanate anion [SCN ^- ], perfluorobutanesulfonate anion [C ₄ F ₉ SO ₃ ^- ], bis(pentafluoroethanesulfonyl) imide anion [(C ₂ F ₅ SO ₂ ) ₂ N ^- ], perfluoro Butyrate anion [C ₃ F ₇ COO ^- ], (trifluoromethanesulfonyl)(trifluoromethanecarbonyl)imide anion [(CF ₃ SO ₂ )(CF ₃ CO)N ^- ], perfluoropropane -1,3-disulfonate anion [ ^- O ₃ S(CF ₂ ) ₃ SO ₃ ^- ], carbonate anion [CO ₃ ^2- ], etc.

Among the above-mentioned anion components, it is preferable to use an anion component containing a fluorine atom because it can impart an ionic compound (D) having a good antistatic function. Specifically, for example, bis(fluorosulfonyl)imide anion, hexafluorophosphate anion or bis(trifluoromethanesulfonyl)imide anion.

Specific examples of the ionic compound (D) can be appropriately selected from combinations of the above-mentioned cation components and anion components. When the example of the ionic compound (D) which has an organic cation is classified and disclosed by the structure of an organic cation, it is as follows, for example.

Pyridinium salt:

N-hexylpyridinium hexafluorophosphate,

N-octylpyridinium hexafluorophosphate,

N-octyl-4-methylpyridinium hexafluorophosphate,

N-butyl-4-methylpyridinium hexafluorophosphate,

N-decylpyridinium bis(fluorosulfonyl)imide,

N-dodecylpyridinium bis(fluorosulfonyl)imide,

N-tetradecylpyridinium bis(fluorosulfonyl)imide,

N-hexadecylpyridinium bis(fluorosulfonyl)imide,

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

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

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

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

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

N-hexylpyridinium bis(trifluoromethanesulfonyl)imide,

N-octylpyridinium bis(trifluoromethanesulfonyl)imide,

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

N-Butyl-4-methylpyridinium Bis(trifluoromethanesulfonyl)imide.

Imidazolium salt:

1-ethyl-3-methylimidazolium hexafluorophosphate,

1-ethyl-3-methylimidazolium p-toluenesulfonate,

1-Ethyl-3-methylimidazolium bis(fluorosulfonyl)imide,

1-Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide,

1-Butyl-3-methylimidazolium methanesulfonate,

1-Butyl-3-methylimidazolium Bis(fluorosulfonyl)imide.

Pyrrolidinium salt:

N-butyl-N-methylpyrrolidinium hexafluorophosphate,

N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide,

N-Butyl-N-methylpyrrolidinium Bis(trifluoromethanesulfonyl)imide.

Grade 4 ammonium salt:

Tetrabutylammonium hexafluorophosphate,

Tetrabutylammonium p-toluenesulfonate,

(2-Hydroxyethyl)trimethylammonium bis(trifluoromethanesulfonyl)imide,

(2-Hydroxyethyl)trimethylammonium dimethylphosphonite.

Moreover, when giving the example of the ionic compound (D) which has an inorganic cation, it is as follows, for example.

lithium bromide,

lithium iodide,

lithium tetrafluoroborate,

lithium hexafluorophosphonate,

lithium thiocyanate,

lithium perchlorate,

Lithium trifluoromethanesulfonate,

Lithium bis(fluorosulfonyl)imide,

Lithium bis(trifluoromethanesulfonyl)imide,

Lithium bis(pentafluoroethanesulfonyl)imide,

Lithium tris(trifluoromethanesulfonyl)methanide,

Lithium p-toluenesulfonate,

sodium hexafluorophosphate,

Sodium bis(fluorosulfonyl)imide,

Sodium bis(trifluoromethanesulfonyl)imide,

Sodium p-toluenesulfonate,

Potassium hexafluorophosphate,

Potassium bis(fluorosulfonyl)imide,

Potassium bis(trifluoromethanesulfonyl)imide,

Potassium p-toluenesulfonate.

The ionic compound (D) is preferably solid at room temperature. Compared with the case of using the ionic compound (D) which is liquid at normal temperature, the antistatic function can be maintained for a long time. From the viewpoint of long-term stability of such antistatic properties, the ionic compound (D) preferably has a melting point of 30° C. or higher, or 35° C. or higher. On the other hand, if the melting point is too high, the compatibility with the (meth)acrylic resin (A) will deteriorate. The melting point is preferably 90°C or lower, more preferably 70°C or lower, and more preferably less than 50°C.

The content of the ionic compound (D) in the adhesive composition is preferably 0.2 to 8 parts by weight, more preferably 0.2 to 5 parts by weight, and 0.3 to 5 parts by weight relative to 100 parts by weight of the (meth)acrylic resin (A). parts by weight Preferably, 0.5 to 3 parts by weight is particularly preferred. The content of the ionic compound (D) is 0.2 parts by weight or more, which is beneficial to improve the antistatic function, and 8 parts by weight or less, is beneficial to maintain the durability of the adhesive layer.

[5] Silane compound (E)

The adhesive composition may further contain a silane compound (E). Thereby, the adhesiveness of an adhesive layer and optical members, such as a glass substrate, can be improved.

As the silane compound (E), for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinylparaffin (2-methoxyethoxy)silane, N-(2-aminoethyl)-3 -Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-cyclo Oxypropylpropyltrimethoxysilane, 3-epoxypropylpropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropane Methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-epoxypropyl Propyltrimethoxysilane, 3-Glycidylpropyltriethoxysilane, 3-Glycidylpropyldimethoxymethylsilane, 3-Glycidylpropylethoxydimethylsilane base silane, etc. Two or more types of silane compounds can also be used.

The silane compound (E) may also be polysiloxane oligomer type. When the polysiloxane oligomer is expressed in the form of a (monomer) oligomer, it is shown below, for example.

3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer,

3-Mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer,

3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer,

Copolymers containing mercaptopropyl groups such as 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer;

Mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer,

Mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer,

Mercaptomethyltriethoxysilane-tetramethoxysilane copolymer,

Mercaptomethyl-containing copolymers such as mercaptomethyltriethoxysilane-tetraethoxysilane copolymer;

3-Glycidylpropyltrimethoxysilane-Tetramethoxysilane Copolymer,

3-Glycidylpropyltrimethoxysilane-tetraethoxysilane copolymer,

3-Glycidylpropyltriethoxysilane-Tetramethoxysilane Copolymer,

3-Glycidylpropyltriethoxysilane-tetraethoxysilane copolymer,

3-Glycidylpropylmethyldimethoxysilane-tetramethoxysilane copolymer,

3-Glycidylpropylmethyldimethoxysilane-tetraethoxysilane copolymer,

3-Glycidylpropylmethyldiethoxysilane-tetramethoxysilane copolymer,

Copolymers containing 3-epoxypropylmethyldiethoxysilane-tetraethoxysilane copolymers, etc.;

3-methacryloxypropyltrimethoxysilane-tetramethoxysilane copolymer,

3-Methacryloxypropyltrimethoxysilane-tetraethoxysilane copolymer,

3-Methacryloxypropyltriethoxysilane-tetramethoxysilane copolymer,

3-Methacryloxypropyltriethoxysilane-tetraethoxysilane copolymer,

3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,

3-Methacryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,

3-Methacryloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,

Copolymers containing methacryloxypropyl groups such as 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer;

3-Acryloxypropyltrimethoxysilane-tetramethoxysilane copolymer,

3-Acryloxypropyltrimethoxysilane-tetraethoxysilane copolymer,

3-acryloxypropyltriethoxysilane-tetramethoxysilane copolymer,

3-acryloxypropyltriethoxysilane-tetramethoxysilane copolymer,

3-acryloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,

3-Acryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,

3-Acryloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,

Copolymers containing acryloxypropyl groups such as 3-acryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer;

Vinyltrimethoxysilane-tetramethoxysilane copolymer,

Vinyltrimethoxysilane-tetraethoxysilane copolymer,

Vinyltriethoxysilane-tetramethoxysilane copolymer,

Vinyltriethoxysilane-tetraethoxysilane copolymer,

Vinylmethyldimethoxysilane-tetramethoxysilane copolymer,

Vinylmethyldimethoxysilane-tetraethoxysilane copolymer,

Vinylmethyldiethylmethoxysilane-tetramethoxysilane copolymer,

Vinyl-containing copolymers such as vinylmethyldiethoxysilane-tetraethoxysilane copolymer;

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-aminopropylmethyldiethylmethoxysilane-tetramethoxysilane copolymer,

Amino group-containing copolymers such as 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer, etc.

Most of the silane compounds (E) exemplified above are liquid. The content of the silane compound (E) in the adhesive composition is 0.01 to 10 parts by weight relative to 100 parts by weight of the (meth)acrylic resin (A), preferably 0.05 to 5 parts by weight, more preferably 0.2 to 5 parts by weight. 0.4 parts by weight. When the quantity of a silane compound (E) is 0.01 weight part or more, the adhesive improvement effect of the adhesive layer and optical members, such as a glass substrate, is easy to be acquired. And when content is 10 weight part or less, bleed-out of a silane compound (E) from an adhesive layer can be suppressed.

[6] Other ingredients

The adhesive composition may contain crosslinking catalysts, weather stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, light-scattering fine particles, (meth)acrylic resins (A) Additives for resins, etc. In addition, an ultraviolet curable compound is prepared in the adhesive composition to form an adhesive layer, and then irradiated with ultraviolet rays to harden it, which can also be used to form a harder adhesive layer. As a crosslinking catalyst, such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isofor Amine-based compounds such as ketonediamine, trimethylenediamine, polyamine-based resins, and melamine resins.

(adhesive layer)

The adhesive layer of the present invention includes the above-mentioned adhesive composition of the present invention, and is typically composed of the adhesive composition of the present invention. In the adhesive layer, each component constituting the above-mentioned adhesive composition is dissolved or dispersed in a solvent to form a solvent-containing adhesive composition, and then the solvent-containing adhesive composition is coated on the base film, and by making it It is obtained by drying. The adhesive layer of the present invention has excellent adhesiveness and durability, and can shorten the required curing time.

The base film is generally a plastic film, and a typical example thereof is a release film (separation film) subjected to a release treatment. For example, the release film can be coated with polysilicon on the surface formed by the adhesive layer of a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyarylate. Release treatment such as oxygen treatment. For example, the adhesive composition is directly coated on the release-treated surface of the release film to form an adhesive layer, and the optical member with the adhesive layer can be obtained by laminating the adhesive layer with the release film on the optical member. Furthermore, an adhesive composition is directly coated on the surface of an optical member to form an adhesive layer, and a peeling film is formed on the outer surface of the adhesive layer as needed to form an optical member with an adhesive layer. When an adhesive layer is provided on the surface of the optical member, it is preferable to perform plasma treatment, corona treatment, etc. on the bonding surface of the optical member and/or the bonding surface of the adhesive layer, and more preferably to perform corona treatment.

The thickness of the adhesive layer is preferably 10 to 45 μm, more preferably 10 to 30 μm, and more preferably 15 to 25 μm. When the thickness of the adhesive layer is in this range, it is advantageous for the durability of the adhesiveness of the adhesive layer and the optical member and bonding the adhesive layer to the optical member. For the same reason, the gel ratio is preferably in the range of 30 to 85%.

In the adhesive composition of the present invention, it is formed into a layer on a film composed of a cyclic polyolefin resin, and the layered adhesive composition is laminated on an alkali-free glass plate and heated at a temperature of 23°C. After storage in an environment for 24 hours, the peeling force when peeling off the layered adhesive composition and the aforementioned film made of cyclic polyolefin resin from the alkali-free glass plate is P(CO)23, and

Form a layer on a film made of cyclic polyolefin resin, laminate the layered adhesive composition on an alkali-free glass plate and store it at 50°C for 48 hours. When the soda glass plate peels off the layered adhesive composition and the film made of the aforementioned cyclic polyolefin resin, when the peeling force is P(CO)50,

The ratio of the P(CO)50 to the P(CO)23 (P(CO)50/P(CO)23) is preferably at least 3.2, more preferably at least 3.5, and still more preferably at least 3.8. When an optical member including a film made of cyclic polyolefin resin is bonded to a liquid crystal cell made of inorganic glass on the side of the film through an adhesive layer containing such an adhesive composition, it is immediately bonded. After peeling off the optical member and reattaching it to a new optical member, that is, the reworkability is good. At the same time, by heating after lamination, the peeling force increases, and the optical member can be more firmly attached to the liquid crystal cell, which is preferable.

Furthermore, in the adhesive composition of the present invention, it is formed into a layer on a film composed of a (meth)acrylic resin, and the layered adhesive composition is laminated on a non-alkali glass plate, and the After storage at 23°C for 24 hours, the peeling force when peeling the layered adhesive composition and the film made of cyclic polyolefin-based resin from the alkali-free glass plate is P(AC)23 ,as well as

Form a layer on a film made of (meth)acrylic resin, laminate the layered adhesive composition on an alkali-free glass plate and store it in an environment at a temperature of 50°C for 48 hours. When the peeling force when peeling the layered adhesive composition and the aforementioned film made of cyclic polyolefin resin from the alkali-free glass plate is P(AC)50,

The ratio of the P(AC)50 to the P(AC)23 (P(AC)50/P(AC)23) is preferably 3.2 or more, more preferably 3.5 or more, and still more preferably 3.8 or more. When an optical member including a film made of (meth)acrylic resin is bonded to a liquid crystal cell made of inorganic glass on the side of the film through an adhesive layer containing such an adhesive composition, the immediate bonding Afterwards, the optical member is peeled off and reattached to a new optical member, that is, the reworkability is good. At the same time, by heating after lamination, the peeling force increases, and the optical member can be more firmly attached to the liquid crystal cell, so it is preferable.

The aforementioned P(CO)23 or P(AC)23 is preferably 0.3 to 5N/25mm, more preferably 0.5 to 5N/25mm, still more preferably 0.5 to 3N/25mm. When P(CO)23 or P(AC)23 is this range, rework property and the adhesiveness with a liquid crystal cell are favorable. Moreover, the aforementioned P(CO)50 or P(AC)50 is preferably 1 to 15N/25mm, more preferably 1.5 to 15N/25mm, still more preferably 2 to 13N/25mm. When P(CO)50 or P(AC)50 is this range, rework property and the adhesiveness with a liquid crystal cell are favorable.

The adhesive composition of the present invention contains organic acid salt (C-1) and compound (C-2), and the content of organic acid salt (C-1) is relative to 100 parts by weight of (meth)acrylic resin (A) 0.0001 to 0.1 parts by weight, and 0.0005 to 0.05 parts by weight, particularly preferably 0.001 to 0.02 parts by weight. The content of compound (C-2) is 0.1 to 0.1 to 100 parts by weight relative to (meth)acrylic resin (A). 5 parts by weight, and 0.15 to 4 parts by weight, particularly preferably 0.2 to 3 parts by weight.

By containing the above-mentioned amount of organic acid salt (C-1) and compound (C-2), the ratio (P (CO)50/P(CO)23) is preferably at least 3.2, more preferably at least 3.5, and still more preferably at least 3.8.

And, by containing the organic acid salt (C-1) and the compound (C-2) in the above-mentioned amount, the ratio (P(AC)50/ P(AC)23) is preferably at least 3.2, more preferably at least 3.5, and still more preferably at least 3.8.

<Optical member with adhesive layer>

The adhesive layer of this invention can be used suitably as an adhesive layer for bonding members, especially optical members. The optical member with an adhesive layer of the present invention, for example, can be laminated with an adhesive layer on a certain optical member, and can be laminated and bonded to another optical member on the outside of the adhesive layer.

[1] The first embodiment

A preferred embodiment of the optical member with an adhesive layer of the present invention includes a resin film as an optical member and an adhesive layer laminated on at least one surface thereof. The resin film system can be a surface protection film (protective film) used for the purpose of protecting the surface from damage or contamination, for example, on an optical film such as a polarizer, a protective film, a retardation film, or an optical film of a protected object. .

A polarizer is a film that has the function of extracting linearly polarized light from incident natural light, and a suitable example is a monoaxially stretched polyvinyl alcohol-based resin film that absorbs and aligns dichroic pigments such as iodine or dichroic dyes. The thickness of the polarizer is not particularly limited, but is usually 0.5 to 35 μm.

The protective film can be transparent (preferably optically transparent) Ming) resins, such as chain polyolefin resins (polypropylene resins, etc.), polyolefin resins of cyclic polyolefin resins (norbornene resins, etc.); such as triacetyl cellulose, diethyl cellulose, Cellulose-based resins of acyl cellulose; polyester-based resins; polycarbonate-based resins; (meth)acrylic-based resins; polystyrene-based resins; formed membrane. .

Examples of the chain polyolefin resins include copolymers composed of two or more chain olefins, in addition to polyethylene resins and polypropylene resins, which are single polymers of chain olefins.

The cyclic polyolefin-based resin is a general term for resins polymerized with cyclic olefins as polymerized units. Specific examples of cyclic polyolefin resins include ring-opening (co)polymers of cyclic olefins, addition polymers of cyclic olefins, copolymers of cyclic olefins and chain olefins such as ethylene and propylene (representative properties of random copolymers) and these graft polymers modified with unsaturated carboxylic acids or their derivatives and these hydrogenated products. Among them, a norbornene-based resin using a norbornene-based monomer such as norbornene or a polycyclic norbornene-based monomer is preferable as the cyclic olefin.

Partial or complete esterification of cellulose-based resin-based cellulose, for example, acetate, propionate, butyrate of cellulose, mixed esters thereof, and the like. Among them, it is preferable to use triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, and the like.

Polyester-based resins are resins other than the aforementioned cellulose-based resins having ester bonds, and are generally composed of polycondensates of polycarboxylic acids or their derivatives and polyhydric alcohols. As polycarboxylic acid or its derivatives, dicarboxylic acid can be used Or its derivatives, such as terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl naphthalene dicarboxylate, etc. Diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, and the like can be used as the polyhydric alcohol.

Specific examples of polyester-based resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polytrimethylene terephthalate. ester, polytrimethylene naphthalate, polycyclohexanedimethyl terephthalate, polycyclohexanedimethyl naphthalate.

Polycarbonate-based resins are composed of polymers linked to monomer units via carbonate groups. The polycarbonate-based resin may be a resin called a modified polycarbonate modified with a polymer skeleton, or a copolymerized polycarbonate, or the like.

The (meth)acrylic resin can be a polymer mainly composed of methacrylate, preferably a copolymer copolymerized with a small amount of other comonomer components. The (meth)acrylic resin is more preferably a copolymer of methyl methacrylate and methyl acrylate, and may be further copolymerized with a third functional group monomer.

As a third functional monomer such as ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate , methacrylates other than methyl methacrylate of 2-hydroxyethyl methacrylate; such as ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethyl acrylate Acrylates other than methyl acrylate of 2-hydroxyethyl acrylate and 2-hydroxyethyl acrylate; such as 2-(hydroxymethyl)methyl acrylate, 2-(1-hydroxyethyl)methyl acrylate, 2-(hydroxymethyl) Base) ethyl acrylate, 2-(hydroxymethyl) butyl acrylate and hydroxyalkyl propylene esters; unsaturated acids such as methacrylic acid and acrylic acid; halogenated styrenes such as chlorostyrene and bromostyrene; substituted styrenes such as vinyltoluene and α-methylstyrene; such as acrylonitrile, Unsaturated nitriles of methacrylonitrile; unsaturated acid anhydrides of maleic anhydride and maleic anhydride; unsaturated imides such as phenylmaleimide and cyclohexylmaleimide Amines etc. The third functional group monomer may be used alone or in combination of two or more.

The (meth)acrylic resin can be copolymerized with multifunctional monomers. As polyfunctional monomers, such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, Acrylic acid ester, nonaethylene glycol di(meth)acrylate, tetradecanediol di(meth)acrylate ethylene glycol or the two terminal hydroxyl groups of its oligomers are esterified with acrylic acid or methacrylic acid Those who; the two terminal hydroxyl groups of propylene glycol or its oligomers are esterified with acrylic acid or methacrylate; such as neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, butanediol di (Meth)acrylic esters of divalent alcohols whose hydroxyl groups are esterified with acrylic acid or methacrylic acid; bisphenol A, the alkylene oxide adduct of bisphenol A, or the halogen-substituents whose two-terminal hydroxyl groups are esterified with acrylic acid or methacrylic acid Methacrylated ones; such as trimethylolpropane, pentaerythritol polyalcohols with acrylic or methacrylic esters, and rings of glycidyl acrylate or glycidyl methacrylate at the terminal hydroxyl groups Oxygen ring-opening additions; acrylic rings made from succinic acid, adipic acid, terephthalic acid, phthalic acid, dibasic acids of their halogen substitutes, and their alkylene oxide adducts Epoxy ring-opening adders of oxypropyl or glycidyl methacrylate; aromatic (meth)acrylates; aromatic divinyls such as divinylbenzene compound etc. Among them, it is preferable to use ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate.

The (meth)acrylic resin may further undergo a reaction between the functional groups that the copolymer has, and may be modified. As this reaction, for example, the demethanol condensation reaction in the polymer chain between the methyl group of methyl acrylate and the hydroxyl group of 2-(hydroxymethyl)methyl acrylate, the carboxyl group of acrylic acid and the Intra-chain dehydration condensation reaction of hydroxyl groups. Furthermore, the (meth)acrylic resin may have any structure of a glutarimide derivative, a glutaric anhydride derivative, or a lactone ring structure.

The (meth)acrylic resin may contain additives as necessary. Examples of additives include lubricants, antiblocking agents, heat stabilizers, antioxidants, antistatic agents, light stabilizers, impact resistance modifiers, surfactants, and the like.

The (meth)acrylic resin may contain acrylic rubber particles from the viewpoints of film forming property to a film, impact resistance of the film, and the like. Acrylic rubber particles refer to particles in which an elastic polymer mainly composed of acrylate is an essential component, for example, a single-layer structure consisting essentially only of the elastic polymer, and a multi-layer structure in which the elastic polymer is one layer By. Examples of the elastic polymer include, for example, a crosslinked elastic copolymer which contains an alkyl acrylate as a main component and is copolymerizable with other vinyl monomers and crosslinkable monomers that can be copolymerized therewith. As the alkyl acrylate used as the main component of the elastic polymer, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, etc., the carbon number of the alkyl group is about 1 to 8, especially used have Acrylic acid having an alkyl group having 4 or more carbon atoms is preferable. As other vinyl monomers that can be copolymerized with the alkyl acrylate, for example, a compound having a polymerizable carbon-carbon double bond in the molecule, more specifically, methacrylate such as methyl methacrylate, such as styrene Aromatic vinyl compounds, vinyl cyanide compounds such as acrylonitrile, etc. As the cross-linking monomer, for example, a cross-linking compound having at least two polymerizable carbon-carbon double bonds in the molecule, more specifically, for example, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, (meth)acrylic acid esters of polyalcohols such as (meth)acrylic acid esters, enyl (meth)acrylic acid esters such as allyl (meth)acrylates, divinylbenzene, and the like.

A laminate of a film made of a (meth)acrylic resin not containing rubber particles and a film made of a (meth)acrylic resin containing rubber particles may also be used as the protective film.

The retardation film is an optical film that exhibits optical anisotropy. In addition to the resins that can be used for the above-mentioned protective film, examples include polyvinyl alcohol-based resins, polyarylate-based resins, polyimide-based resins, and polyether-based resins. resin, polyvinylidene fluoride/polymethyl methacrylate resin, liquid crystal polyester resin, ethylene-vinyl acetate copolymer saponified product, polyvinyl chloride resin, etc. by extending to 1.01 to About 6 times the stretched film obtained. Among them, polycarbonate-based resin films, cyclic polyolefin-based resin films, (meth)acrylic-based resin films, or cellulose-based resin films are preferable. In addition, in this specification, the retardation film also includes a zero-retardation film (however, a zero-retardation film may also be used as a protective film). In addition, a film called a uniaxial retardation film, a wide viewing angle retardation film, a low photoelasticity retardation film, etc. may also be applied as a retardation film.

The so-called zero-retardation film refers to a film whose in-plane retardation value _Re and thickness direction retardation value _Rth are both -15 to 15 nm. This retardation film is suitably used for an IPS (in-plane switching) mode liquid crystal display device. The in-plane retardation value Re and _{the thickness direction retardation value R th are} preferably -10 to 10 nm, more preferably -5 to 5 nm. Here, the in-plane retardation value Re and the thickness direction retardation value _{R th refer} to values at a wavelength of 590 nm.

The in-plane retardation value R _e and the thickness direction retardation value R _th are expressed in the following formulas:

R _e =(n _x -n _y )×d

R _th =[(n _x +n _y )/2-n _z ]×d is defined. In the formula, n _x is the refractive index in the direction of the delayed phase axis (x-axis direction) in the film plane, and n _y is the refractive index in the direction of the advancing phase axis in the film plane (the y-axis direction perpendicular to the x-axis in the plane) , _nz is the refractive index in the thickness direction of the film (z-axis direction perpendicular to the film surface), and d is the thickness of the film.

For zero-retardation films, for example, polyolefin resins such as cellulose resins, chain polyolefin resins, and cyclic polyolefin resins, polyethylene terephthalate, or (meth)acrylic resins can be used. resin film. In particular, it is preferable to use a cellulose-based resin, a polyolefin-based resin, or a (meth)acrylic resin because the retardation value is easy to control and obtain. For example, a (meth)acrylic resin layer layered on one side or both sides of a retardation display layer made of a resin different from a (meth)acrylic resin can be used as a retardation film.

Furthermore, a film that exhibits optical anisotropy by coating/alignment of a liquid crystal compound or a film that exhibits light by coating an inorganic layered compound The anisotropic film can also be used as a retardation film. Such a retardation film is called a temperature-compensating retardation film, and a film of rod-shaped liquid crystal oblique alignment sold by JX Nippon Oil & Energy Co., Ltd. under the trade name "NH FILM" and manufactured by Fuji A discotic liquid crystal oblique alignment film sold under the trade name of "WV FILM" by Thin Film Co., Ltd., a fully biaxially aligned film sold under the trade name of "VAC FILM" by Sumitomo Chemical Co., Ltd., the same A biaxially-aligned film sold by Sumitomo Chemical Co., Ltd. under the trade name of "new VAC FILM" and the like.

On the other hand, the surface protection film is a film used for the purpose of protecting the surface of the optical film of the protected body from damage and contamination, such as polarizers, protective films, retardation films, light diffusion Various optical films such as sheets and reflective sheets are usually circulated with a surface protection film attached to the surface (when one side has an adhesive layer, the surface opposite to the adhesive layer). Generally, after the said optical film is bonded to a liquid crystal cell etc., a surface protection film is peeled off and removed.

As the base material of the surface protection film, polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; fluorinated polyolefin resins such as polyvinyl fluoride, polyvinylidene fluoride, and polyvinyl fluoride; polynaphthalene Polyester-based resins of ethylene dicarboxylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate/isophthalate copolymer; nylon 6 , nylon 6,6 polyamide; polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, vinyl polymerization of vinylon (vinylon) substances; cellulose series of triacetyl cellulose, diacetyl cellulose, cellophane Resins; (meth)acrylic resins of polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate; other polystyrene, polycarbonate, polyarylate, polyamide A film made of thermoplastic resin such as amine. The adhesive layer-attached optical member of the present invention in which the resin film is a surface protection film is one in which the adhesive layer is provided on the substrate.

In the optical member with an adhesive layer of the present embodiment, it is preferable to stick the above-mentioned release film on the surface of the adhesive layer and temporarily protect it until use. The adhesive layer-attached optical member of the present embodiment to which the release film is attached can be formed by coating an adhesive composition on the release film to form an adhesive layer, and then laminating a resin film on the obtained adhesive layer, Alternatively, it can be manufactured by coating an adhesive composition on a resin film to form an adhesive layer, and attaching a peeling film to the adhesive surface.

The optical member system of the adhesive layer of the present embodiment

By constituting this adhesive layer, in the state of being laminated on the non-alkali glass plate, after storing for 24 hours at a temperature of 23°C, the peeling force when peeling off the non-alkali glass plate is P23, and

By constituting this adhesive layer, in the state of being laminated on the non-alkali glass plate, after storing it at a temperature of 50°C for 48 hours, when the peeling force when peeling off from the non-alkali glass plate is P50,

The ratio of P50 to P23 (P50/P23) is 3.2 or more, 3.5 or more, especially 3.8 or more, the so-called reworkability becomes good, and the peeling force is increased by heating after bonding, which can be bonded more firmly. The optical member is preferably in a liquid crystal cell.

The aforementioned P23 is preferably 0.3 to 5N/25mm, more preferably 0.5 to 5 N/25mm, more preferably 0.5 to 3N/25mm. When P23 is this range, rework property and the adhesiveness with a liquid crystal cell become favorable. Moreover, the aforementioned P50 is preferably 1 to 15N/25mm, more preferably 1.5 to 15N/25mm, still more preferably 2 to 13N/25mm. When P50 is this range, rework property and the adhesiveness with a liquid crystal cell become favorable.

[2] The second embodiment

Another preferred embodiment of the optical member with an adhesive layer of the present invention is a laminate comprising a resin film and an adhesive layer laminated on at least one surface thereof. The laminate of resin films is preferably a laminate of optical films selected from optical films such as polarizers, protective films, and retardation films. A typical example of a laminate of optical films is a polarizing plate. In the optical member with an adhesive layer of this embodiment, it is preferable to stick a peeling film on the surface of the adhesive layer and temporarily protect it until use.

As a polarizer, for example, it has the property of absorbing linearly polarized light of a vibrating plane having a certain direction on the incident film surface and penetrating linearly polarized light having a vibrating plane perpendicular to it; The linearly polarized light of the vibrating plane in the same direction, the polarized light separating plate with the property of penetrating the linearly polarized light of the vibrating plane perpendicular to it;

A linear polarizing plate generally has a configuration in which the above-mentioned protective film is attached to one or both surfaces of the above-mentioned polarizer. When the protective film is pasted on both sides of the polarizer, an adhesive layer is formed on at least one surface of the protective film. When attaching the protective film to only one side of the polarizer, an adhesive layer can be formed on the surface of the polarizer (the side that is not attached with the protective film). Elliptical polarizer system retardation film Laminated on a linear polarizing plate, the linear polarizing plate generally has the same configuration as above. When the adhesive layer is laminated on the elliptically polarizing plate, the adhesive layer is usually laminated on the retardation film side.

When the optical member is a polarizing plate, a specific example of the optical member with an adhesive layer will be described with reference to the drawings. In the example shown in FIG. 1 , a protective film 3 having a surface treatment layer 2 is attached to one side of the polarizer 1 and attached to the surface opposite to the surface treatment layer 2 to form a polarizer 10 . An adhesive layer 20 is provided on the surface of the polarizer 1 opposite to the protective film 3 to form an adhesive layer-attached polarizer (adhesive layer-attached optical member) 25 . The adhesive layer 20 can be bonded to the glass substrate 30 on the surface opposite to the polarizing plate 10 , and the glass substrate 30 will be described later.

The optical member 25 with an adhesive layer shown in FIG. 2 is the same as that in FIG. 1 except that the polarizer 10 includes the second protective film 4 attached to the other side of the polarizer 1 . The adhesive layer 20 is laminated on the outer surface of the second protective film 4 . The optical member 25 with an adhesive layer shown in FIG. 3 is the same as that in FIG. 1 except that the polarizing plate 10 includes a retardation film 7 attached to the other side of the polarizing plate 1 with an interlayer adhesive 8 interposed therebetween. . The optical member 25 with an adhesive layer shown in FIG. 4 is the same as that in FIG. 2 except that the polarizing plate 10 includes the retardation film 7 attached to the outer surface of the second protective film 4 through the interlayer adhesive 8 . In the example shown in FIG. 3 and FIG. 4 , the adhesive layer 20 is attached to the retardation film 7 .

The surface treatment layer 2 formed on the surface of the protective film 3 may be a hard coat layer, an antiglare layer, an antireflection layer, an antistatic layer, and the like. Among these, plural layers may be provided. As the example shown in Fig. 3 and Fig. 4, the polarizing plate 10 When the retardation film 7 is included, a suitable example of the retardation film 7 is, for example, a 1/4 wavelength plate in the case of a small-to-medium sized liquid crystal display device. In this case, the absorption axis of the polarizer 1 and the retardation phase axis of the retardation film 7 are generally arranged to intersect at about 45 degrees, and the angle may deviate from 45 degrees to some extent depending on the characteristics of the liquid crystal cell. On the other hand, in the case of a large liquid crystal display device such as a television, the retardation compensation or viewing angle compensation of the liquid crystal cell is the purpose, and the retardation film 7 having various retardation values can be used according to the characteristics of the liquid crystal cell. In this case, the absorption axis of the polarizer 1 and the phase retardation axis of the retardation film 7 are generally arranged in a relationship of approximately perpendicular or parallel. When the retardation film 7 is constituted by a 1/4 wavelength plate, a uniaxial or biaxial stretched film is suitably used. Moreover, due to the purpose of phase difference compensation or viewing angle compensation of the liquid crystal cell, when setting the phase difference film 7, in addition to the one-axis or two-axis stretched film, the film that is also aligned in the thickness direction in addition to one-axis or two-axis stretching is placed on the support film. What is called an optical compensation film, such as a film in which a substance such as a liquid crystal is applied to detect a retardation and whose alignment is fixed, can also be used as the retardation film 7 .

The interlayer adhesive 8 in Fig. 3 and Fig. 4 is conventionally used a general (meth)acrylic adhesive, but of course the adhesive layer of the present invention can also be used. When the absorption axis of the polarizer 1 and the retardation phase axis of the retardation film 7 are arranged approximately perpendicular or parallel to the large liquid crystal display device described above, an adhesive may be used instead of the interlayer adhesive 8 . As the adhesive, for example, a water-based adhesive that is composed of an aqueous solution or a water dispersion and develops adhesive force by evaporating water as a solvent, and an ultraviolet curable adhesive that hardens by ultraviolet irradiation to develop adhesive force, and the like. The bonding of the polarizer 1 and the protective films 3 and 4 is also usually performed using an adhesive.

Regarding the optical member with the adhesive layer of the present invention, since the adhesive layer contains the above-mentioned adhesive composition of the present invention, the adhesiveness and durability of the adhesive layer and the optical member are good. According to the present invention, the surface of the optical member to which the adhesive layer is bonded is treated by conventional surface activation treatment such as corona treatment and plasma treatment. An optical member with an adhesive layer that has good adhesiveness and durability of the member. Here, the surface that is difficult to activate by surface activation treatment refers to, for example, a surface whose contact angle change rate is 40% or less and 30% or less when corona treatment is performed. The rate of change of the contact angle is usually at least 0.1%, preferably at least 0.5%.

The rate of change of contact angle is given by the following formula:

Contact angle change rate (%)={(contact angle before corona treatment-contact angle after corona treatment)/contact angle after corona treatment}×100. The so-called contact angle after corona treatment refers to the time when the above surface is corona treated once under the conditions of output 0.3kW and line speed 10m/min, and then placed in an environment with a temperature of 23°C and a relative humidity of 60% for 24 hours. contact angle. The contact angle is the contact angle to water, and the unit is "°".

The change rate of the contact angle at the time of the above-mentioned corona treatment varies depending on the constituent material of the surface of the optical member. As the thermoplastic resin whose contact angle change rate becomes 40% or less, there are (meth)acrylic resins, cellulose resins, polyester resins, polycarbonate resins, and the like. The surface of the optical member made of these thermoplastic resins may be the surface of an optical film such as a protective film or a retardation film.

[3] Third Embodiment

Yet another preferred embodiment of the optical member with an adhesive layer of the present invention is that it is laminated on the outside of the adhesive layer in the optical member with an adhesive layer in the above-mentioned first or second embodiment. Compatible with other optical components. The other optical member is preferably a glass substrate, and in Fig. 1 to Fig. 4 , the state of bonding the polarizing plate with the adhesive layer in the second embodiment to the glass substrate 30 is shown collectively.

As the glass substrate 30, for example, a glass substrate of a liquid crystal cell, antiglare glass, glass for sunglasses, or the like. As a material of the glass substrate 30, soda-lime glass, low-alkali glass, non-alkali glass, etc. are mentioned, for example. Among them, the glass substrate is preferably a glass substrate of a liquid crystal cell.

In liquid crystal cells, polarizing plates are usually laminated on both sides with an adhesive layer interposed therebetween, but among these polarizing plates, the polarizing plate disposed only on the front side (identification side) of the liquid crystal cell is an optical member with an adhesive layer of the present invention, Only the polarizing plate disposed on the back side (backlight side) of the liquid crystal cell may be the optical member with the adhesive layer of the present invention, or both of them may be the optical member with the adhesive layer of the present invention. The driving method of the liquid crystal unit can be any conventionally known method. The polarizing plate arranged on the back side (backlight side) usually does not have the surface treatment layer 2 . On the outer surface of the polarizing plate arranged on the back side, various optical films known to be arranged on the back side of the liquid crystal cell, such as a brightness enhancement film, a light-condensing film, and a diffusion film, can be provided.

The optical member with an adhesive layer, such as a polarizing plate with an adhesive layer, can be suitably used for a liquid crystal display device. For example, the liquid crystal display device can be suitably used as a personal computer including a notebook type, a desktop type, a PDA (Personal Digital Assistant) and the like; Mobile machines; televisions; monitors for vehicles; electronic dictionaries; digital cameras; digital video cameras; electronic desktop computers; liquid crystal display devices for clocks, etc.

【Example】

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited to these examples. Hereinafter, parts and % representing usage amount to content are based on weight unless otherwise stated.

<Production Examples 1 to 7: Production of (meth)acrylic resin for adhesive layer>

In a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, and a stirrer, put the monomer composition shown in Table 2 (the weight % when the total amount of the monomer is 100% by weight), and dilute it with ethyl acetate After replacing the air in the apparatus with nitrogen gas so as not to contain oxygen, the internal temperature was raised to 55°C. Then, the entire amount of the solution in which azobisisobutyronitrile (polymerization initiator) was dissolved in ethyl acetate was added. After adding the initiator, keep at this temperature for 1 hour, then continuously add ethyl acetate into the reaction container while maintaining the internal temperature at 54 to 56°C until the concentration of the (meth)acrylic resin reaches 35% by weight , the addition of ethyl acetate was stopped, and the temperature was maintained until 12 hours had elapsed from the start of the addition of ethyl acetate. Finally, ethyl acetate was added to adjust the concentration of the (meth)acrylic resin to 20% by weight, and an ethyl acetate solution of the (meth)acrylic resin was prepared.

The weight average molecular weight (Mw) and glass transition temperature (Tg) of the obtained (meth)acrylic resin were measured. Mw is a GPC device equipped with 4 "TSKgel XL" manufactured by Tosoh Co., Ltd. and 1 "Shodex GPC KF-802" sold by Showa Denko Co., Ltd., sold by Showa Denko Co., Ltd. A total of 5 roots are connected in series as a column, using tetrahydrofuran as the eluent, the sample concentration is 5mg/mL, the sample introduction volume is 100μL, under the conditions of temperature 40°C and flow rate 1mL/min, by converting standard polystyrene Determination. Tg was measured using a differential scanning calorimeter (DSC) "EXSTAR DSC 6000" manufactured by SII Nanotechnology Co., Ltd. under a nitrogen atmosphere at a temperature range of -80 to 50°C and a temperature increase rate of 10°C/min. Table 2 summarizes the monomer composition (% by weight) of the monomer mixture used and the Mw and Tg of the obtained (meth)acrylic resin.

The abbreviations in the column of "monomer composition" in Table 2 refer to the following monomers.

BA: n-butyl acrylate

EHA: 2-ethylhexyl acrylate

MA: methyl acrylate

AA: Acrylic

HEA: 2-Hydroxyethyl Acrylate

<Examples 1 to 10, Comparative Examples 1 to 8>

(1) Preparation of adhesive composition

The crosslinking agent (B), The compound (C) and the silane compound (E) were further added with ethyl acetate so that the solid content concentration became 14% by weight, and a solution of the adhesive composition was prepared. The compounded amount of each compounded component shown in Table 3 is the number of parts by weight of the active ingredient contained in the commercial product used when it contains a solvent or the like.

In Table 3, the details of each compounded component represented by an abbreviation are as follows.

B1: Ethyl acetate solution of trimethylolpropane adduct of cresyl diisocyanate (solid content concentration 75%), "CORONATE L" obtained from Nippon Polyurethane Co., Ltd.,

B2: Trimeric isocyanate of hexamethylene diisocyanate, liquid with about 100% active ingredient, "CORONATE HXR" obtained from Nippon Polyurethane Co., Ltd.

C1: Sodium acetate: Obtained from Wako Pure Chemical Industries Co., Ltd. (dissolved in ethanol in the adhesive composition, and added to prepare a 0.5% by weight solution.),

C2: "AM-130G" (the following formula:

Methoxylated polyethylene glycol acrylate shown),

S1: 3-glycidylpropyltrimethoxysilane, "KBM403" obtained from Shin-Etsu Chemical Co., Ltd.

(2) Production of adhesive layer

Use an applicator to apply each adhesive composition prepared in the above (1) to the polyethylene terephthalate that has been subjected to release treatment. The release-treated surface of the release film made of ester ["PLR-382051" obtained from Lintec Corporation, also called a release film] was dried to a thickness of 20 μm at 100°C for 1 minute to prepare an adhesive layer. (adhesive tablet).

(3) Production of polarizing plate with adhesive layer

On one side of a polarizer having iodine adsorption and alignment on a uniaxially stretched polyvinyl alcohol film with a thickness of 23 μm, a first protective film composed of a thermoplastic resin described in Table 4 was attached through an adhesive, and on the other side On the surface, a second protective film made of (meth)acrylic resin was bonded via an adhesive different from the above, to produce a polarizing plate. Then, on the outer surface of the first protective film, corona treatment was performed once under the conditions of an output of 0.3kW and a line speed of 10m/min, and then, on the corona treated surface, the adhesive layer prepared in the above (2) was applied The surface (adhesive layer) on the opposite side of the separation film was laminated by a laminator, and then cured at a temperature of 23°C and a relative humidity of 65%, to obtain a polarizing plate with an adhesive layer.

The abbreviations described in the column of "protective film" in Table 4 refer to the following thermoplastic resins.

AC: (meth)acrylic resin (contact angle change rate according to the above definition: 17.2%)

PE: Polyester resin (according to the definition above, the change rate of contact angle: 14.7%)

CE: Cellulose resin (Contact angle change rate according to the definition above: 21.7%)

(4) Evaluation of durability

Peel off the separation film from the polarizing plate with the adhesive layer produced in (3) above Thereafter, this adhesive layer was attached to both surfaces of a glass substrate for a liquid crystal cell ["Eagle XG" manufactured by Corning Incorporated] to form a Cross Nicol, and an evaluation sample was produced. Using this sample, the following three kinds of durability tests were carried out.

〔Durability test〕

‧Heat resistance test for 1000 hours under dry conditions at a temperature of 80°C;

‧Damp heat resistance test for 1000 hours in an environment with a temperature of 60°C and a relative humidity of 90%;

‧Heat shock resistance (HS) test of 30 minutes under dry conditions at 70°C, and then 30 minutes under dry conditions at -40°C as one cycle, repeating this operation for 500 cycles.

The samples after each test were visually observed, and durability was evaluated based on the following evaluation criteria. The results are shown in Table 4.

A: Changes in appearance such as floating, peeling, and blistering are not seen at all

B: Changes in appearance such as floating, peeling, and blistering are hardly seen

C: Many changes in appearance such as floating, peeling, blistering, etc. are seen

D: Appearance changes such as floating, peeling, and blistering are clearly observed

(5) Adhesion between protective film and adhesive layer and evaluation during aging

A test piece with a width of 25 mm x a length of 150 mm was cut from the polarizing plate with the adhesive layer produced in (3) above. Then, after the separation film was peeled off from the test piece, it was fixed to an adhesive strength evaluation jig manufactured by Nippon System Group Co., Ltd., and the following peeling test was implemented. Rubber sheet for testing [Material: neoprene, Hardness: JIS A hardness 65] pressed against the surface of the adhesive layer, the rubber sheet was reciprocated 20 times on the test piece, and the surface of the adhesive layer was rubbed with the rubber sheet. The moving direction of the test rubber sheet is parallel to the width direction of the test sheet.

The surface of the adhesive layer side of the test piece after the said peel test was observed. In any of the examples/comparative examples, the adhesive layer was peeled off at one end side in the width direction of the test piece after the peel test, and the adhesive layer remained at the other end side. The position of the remaining adhesive layer (position in the longitudinal direction of the test piece) was obtained, and the distance from the above-mentioned one end to the position was measured as a peeling distance. The results are shown in Table 4.

In any of the examples/comparative examples, those with a curing period of 3 days or 7 days were used as the adhesive layer to manufacture a polarizing plate with an adhesive layer, and a peel test was performed. When the peeling distance when the aging period is 7 days is 15 mm or less, it means that the adhesiveness between the protective film and the adhesive layer is good. When the difference between the peeling distance when the aging period is 3 days and the peeling distance when the aging period is 7 days is 5 mm or less, it is extremely advantageous in shortening the aging period. Furthermore, in Comparative Example 2, when a cyclic polyolefin-based resin film with a contact angle change rate of 56.3% was used instead of a (meth)acrylic resin as a protective film, the peeling time when the aging period was 3 days or 7 days The distances are 14mm and 11mm, respectively, and the durability according to the above-mentioned measurement method is also good.

<Production Examples 8 to 10: Production of (meth)acrylic resin for adhesive layer>

In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirrer, put the monomer composition shown in Table 5 (the weight % when the total amount of the monomer is 100% by weight), and dilute it with ethyl acetate The resulting monomer mixture is replaced with nitrogen in the air in the device to become free of oxygen, then the internal temperature is raised to 55°C, and then azobisisobutyronitrile (polymerization initiator) is added Dissolve the entire amount of the solution in ethyl acetate. After adding the initiator, the temperature was maintained for 1 hour, and then while maintaining the internal temperature at 54 to 56° C., ethyl acetate was continuously added to the reaction vessel until the concentration of the (meth)acrylic resin reached 35% by weight. The addition of ethyl acetate was stopped, and the temperature was maintained until 12 hours had elapsed from the start of addition of ethyl acetate. Finally, ethyl acetate was added to adjust the concentration of the (meth)acrylic resin to 20% by weight, and an ethyl acetate solution of the (meth)acrylic resin was prepared.

The weight average molecular weight (Mw) and glass transition temperature (Tg) of the obtained (meth)acrylic resin were measured. Mw is a GPC device, and a total of 5 pieces of "TSKgel XL" made by Tosoh Co., Ltd. and 1 piece of "Shodex GPC KF-802" sold by Showa Denko Co., Ltd. sold by Showa Denko Co., Ltd. are arranged in series. The column uses tetrahydrofuran as the eluent, the sample concentration is 5mg/mL, and the sample introduction volume is 100μL. Under the conditions of temperature 40°C and flow rate 1mL/min, it is measured by converting standard polystyrene. Tg was measured using a differential scanning calorimeter (DSC) "EXSTAR DSC 6000" manufactured by SII Nanotechnology Co., Ltd., under a nitrogen atmosphere, at a temperature range of -80 to 50°C, and at a heating rate of 10°C/min. Table 5 summarizes the monomer composition (% by weight) of the monomer mixture used and Mw, Mw/Mn, and Tg of the obtained (meth)acrylic resin.

The abbreviations in the column of "monomer composition" in Table 5 refer to the following monomers.

BA: n-butyl acrylate

EHA: 2-ethylhexyl acrylate

MA: methyl acrylate

AA: Acrylic

HEA: 2-Hydroxyethyl Acrylate

PEA: 2-phenoxyethyl acrylate

PEA2: 2(2-phenoxyethoxy)ethyl acrylate

BMAM: N-(butoxymethyl)acrylamide

<Examples 11 to 26>

(1) Preparation of adhesive composition

The crosslinking agent (B), Compound (C), ionic compound (D), and silane compound (E) were further added with ethyl acetate so that the solid content concentration became 14% by weight, and a solution of an adhesive composition was prepared. The compounded amount of each compounded component shown in Table 6 is the number of parts by weight of the active ingredient contained in the commercial product used when it contains a solvent or the like.

In Table 6, the details of each compounded component indicated by the abbreviation are as follows.

B1: Ethyl acetate solution of trimethylolpropane adduct of cresyl diisocyanate (solid content concentration 75%), "CORONATE L" obtained from Nippon Polyurethane Co., Ltd.,

C1: Sodium acetate: Obtained from Wako Pure Chemical Industries Co., Ltd. (dissolved in acetic acid in the adhesive composition, and added to prepare a 3.3% by weight solution.),

C2-1: "AM-130G" (the following formula:

Methoxylated polyethylene glycol acrylate shown),

C2-2: "M-130G" acquired from Shin-Nakamura Chemical Co., Ltd. (the following formula:

Methoxylated polyethylene glycol methacrylate shown),

D1: N-octyl-4-methylpyridinium hexafluorophosphate,

S1: 3-glycidylpropyltrimethoxysilane, "KBM403" obtained from Shin-Etsu Chemical Co., Ltd.

(2) Production of adhesive layer

Each adhesive composition prepared in the above (1) was applied to a release film made of a release-treated polyethylene terephthalate film using an applicator (" PLR-382051", also known as the separation membrane], so that the thickness after drying is 20 μm, dry at 100°C for 1 minute, and make an adhesive layer (adhesive sheet).

(3) Production of polarizing plate with adhesive layer

On one side of a polarizer with a thickness of 23 μm in which iodine is adsorbed and aligned to a uniaxially stretched polyvinyl alcohol film, a first protective film composed of a thermoplastic resin described in Table 7 is attached via an adhesive, and on the other side , a second protective film made of a (meth)acrylic resin was bonded via an adhesive different from the above to produce a polarizing plate. Then, on the outer surface of the first protective film, corona treatment was performed once under the conditions of an output of 0.3kW and a line speed of 10m/min, and then, on the corona treated surface, the adhesive layer prepared in the above (2) was applied The surface (adhesive layer) on the opposite side of the separation membrane is bonded by a laminator, and then cured at a temperature of 23°C and a relative humidity of 65% to obtain an adhesive layer The polarizer.

The abbreviations described in the column of "protective film" in Table 7 refer to the following thermoplastic resins.

CO: Cyclic polyolefin resin (change rate of contact angle according to the definition above: 56.3%)

AC: (meth)acrylic resin (contact angle change rate according to the above definition: 17.2%)

(4) Evaluation of durability

From the polarizing plate with the adhesive layer prepared in (3) above, the separation film was peeled off, and the adhesive layer was attached to both sides of the glass substrate for liquid crystal cells ["Eagle XG" manufactured by Corning Incorporated] to form a cross Nico Cross Nicol, produced samples for evaluation. Using this sample, the following three types of durability tests were implemented.

〔Durability test〕

‧Heat resistance test at a temperature of 80°C for 1000 hours;

‧Damp heat resistance test for 1000 hours in an environment with a temperature of 60°C and a relative humidity of 90%;

‧Heat shock resistance (HS) test of 500 cycles of 30 minutes under dry conditions at a temperature of 70°C and then 30 minutes at -40°C as one cycle.

The samples after each test were visually observed, and durability was evaluated based on the following evaluation criteria. The results are shown in Table 7.

A: No change in appearance such as floating, peeling, and blistering can be seen at all

B: Changes in appearance such as floating, peeling, and blistering are hardly seen

C: Many changes in appearance such as floating, peeling, blistering, etc. are seen

D: Appearance changes such as floating, peeling, and blistering are clearly observed

(5) Evaluation of peeling force of optical member with adhesive layer

The polarizing plate with the adhesive layer produced in (3) above was cut into a test piece with a width of 25 mm x a length of 150 mm. Then, after the separation film was peeled off from the test piece, the adhesive layer was attached to a glass substrate for a liquid crystal cell [trade name "EAGLE XG", Obtained from Corning Incorporated, alkali-free glass plate]. The obtained glass substrate-attached test piece (an optical member with an adhesive layer attached to a glass substrate) was pressurized in an autoclave at a temperature of 50° C. and a pressure of 5 kg/cm ² (490.3 kPa) for 20 minutes. Then, they were left still under the conditions of 24 hours in an environment with a temperature of 23° C. and 48 hours in an environment with a temperature of 50° C., respectively. After standing still, the sample was clamped with a tensile testing machine ["AUTOGRAPH AGS-X" manufactured by Shimadzu Corporation], and the temperature was 23°C, the relative humidity was 55%, and the tensile speed was 300mm/min. , to peel in the direction of 180 degrees. The peeling strength measured at this time was evaluated as a peeling force. Here, the peel force under the condition of storage at 23° C. for 24 hours is P23, and the peel force under the condition of storage at 50° C. for 48 hours is P50. The results are shown in Table 7.

1: Polarizer

2: Surface treatment layer

3: Protective film

10: polarizer

20: Adhesive layer

25: Polarizing plate with adhesive layer

30: glass plate

Claims (14)

An adhesive composition comprising: 100 wt. of a (meth)acrylic resin (A) containing a constituent unit derived from a (meth)acrylic monomer having a hydroxyl group in a content of 0.1% by weight to 3.5% by weight and having a glass transition temperature of -25°C or lower share; 0.3 to 1 part by weight of an aromatic isocyanate-based crosslinking agent (B); and At least one compound (C) selected from organic acid salts (C-1) and compounds (C-2) containing alkyleneoxy groups; The aforementioned organic acid salts (C-1) include carboxylate anions and relative cations, The aforementioned carboxylate anions are selected from linear saturated alkyl carboxylate ions, straight chain unsaturated alkyl carboxylate ions, carboxylate anions with heterocyclic structure, dicarboxylate ions, and carboxylate ions with an oxyethylene skeleton. Acid ion, The aforementioned opposite cation-based metal ion, or a cation having a heterocyclic structure, The above-mentioned compound (C-2) containing an alkyleneoxy group is a compound containing a (meth)acryloyl group represented by the following formula (C-2a),

[wherein, h represents an integer from 1 to 6, ^Q1 represents a hydrogen atom or a methyl group, and ^Q0 is a group represented by ^Q01 , ^Q03 or ^Q04 ;

In the formula, In Q ⁰¹ , Q ² represents an alkyl, aryl or aralkyl group with 1 to 4 carbons which may be substituted by an alkoxy group with 1 to 3 carbons, and L represents a single bond or an alkylene group with 1 to 4 carbons , i represents an integer from 1 to 50; In Q ⁰³ , y and z independently represent an integer from 1 to 40; In Q ⁰⁴ , e, f and g independently represent an integer from 1 to 20;] When the aforementioned organic acid salt (C-1) is contained, its content is 0.0001 to 5 parts by weight relative to 100 parts by weight of the aforementioned (meth)acrylic resin (A), When the compound (C-2) containing the said alkyleneoxy group is contained, the content is 0.1-5 weight part with respect to 100 weight part of said (meth)acrylic-type resins (A). The adhesive composition according to claim 1, wherein the content of the structural unit derived from the (meth)acrylic monomer having a hydroxyl group is 0.5% by weight or more. The adhesive composition as described in item 1 of the patent claims further contains an ionic compound (D). The adhesive composition as described in item 1 of the patent claims further contains a silane compound (E). The adhesive composition as described in item 1 of the scope of the patent application, wherein The aforementioned adhesive composition was formed into a layer on a film made of cyclic polyolefin resin, and the layered adhesive composition was laminated on an alkali-free glass plate and stored at a temperature of 23°C for 24 Hours later, the peeling force when peeled off from this alkali-free glass plate is set as P(CO)23, and The aforementioned adhesive composition was formed into a layer on a film made of a cyclic polyolefin resin, and the layered adhesive composition was laminated on an alkali-free glass plate and stored at a temperature of 50°C for 48 hours. Hours later, when the peeling force when peeled off from this alkali-free glass plate is set as P(CO)50, The ratio of the P(CO)50 to the P(CO)23 (P(CO)50/P(CO)23) is 3.2 or more. The adhesive composition as described in item 1 of the scope of the patent application, wherein The aforementioned adhesive composition is formed into a layer on a film made of (meth)acrylic resin, and the layered adhesive composition is laminated on an alkali-free glass plate and stored at a temperature of 23°C. After 24 hours, the peeling force when peeled off from this alkali-free glass plate is set as P(AC)23, and Form the aforementioned adhesive composition into a layer on a film made of (meth)acrylic resin, and store the layered adhesive composition on an alkali-free glass plate at a temperature of 50°C. 48 hours Afterwards, when the peeling force when peeling from this alkali-free glass plate is set as P(AC)50, The ratio of the P(AC)50 to the P(AC)23 (P(AC)50/P(AC)23) is 3.2 or more. The adhesive composition as described in claim 1 of the patent application, which contains the aforementioned organic acid salt (C-1) and the aforementioned compound (C-2) containing an alkeneoxy group; Wherein the content of the aforementioned organic acid salt (C-1) is 0.0001 to 0.1 parts by weight relative to 100 parts by weight of the aforementioned (meth)acrylic resin (A); Content of the said alkyleneoxy group containing compound (C-2) is 0.1-5 weight part with respect to 100 weight part of said (meth)acrylic-type resins (A). An adhesive layer comprising the adhesive composition described in any one of items 1 to 7 of the patent application. An optical component with an adhesive layer, comprising an optical component and the adhesive layer described in claim 8 of the patent application laminated on the optical component. The optical member with an adhesive layer as described in claim 9, wherein the surface of the optical member on which the adhesive layer is laminated has a contact angle change rate of 40% or less when corona treatment is performed. The optical member with an adhesive layer as described in claim 10 of the patent application, wherein the aforementioned optical member includes a polarizer and a protective film laminated on the polarizer; The aforementioned surface is the surface of the aforementioned protective film. The optical component with an adhesive layer as described in claim 10, wherein the aforementioned surface is a corona-treated surface. The optical component with an adhesive layer as described in any one of claims 9 to 12 of the patent application further includes a glass substrate laminated on the aforementioned adhesive layer. An optical member with an adhesive layer, comprising a resin film and an adhesive layer laminated on at least one side of the resin film; The aforementioned adhesive layer includes the adhesive composition described in any one of the first to seventh items of the patent application; After the adhesive layer is laminated on the non-alkali glass plate and stored in an environment at a temperature of 23° C. for 24 hours, the peeling force when peeled from the non-alkali glass plate is P23, and When the adhesive layer is laminated on the non-alkali glass plate and stored in an environment at a temperature of 50°C for 48 hours, when the peeling force at the time of peeling off the non-alkali glass plate is P50, the above P50 and the above The ratio (P50/P23) of P23 is 3.2 or more.

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