TWI679260B - Adhesive composition, adhesive layer and optical member with adhesive layer - Google Patents

Abstract

The present invention provides an adhesive composition containing 0.15 to 8 parts by weight of a compound (B) containing 100 parts by weight of a (meth) acrylic resin (A) and at least one double bond and at least one alkylene dioxy group in the molecule. Material, an adhesive layer including the adhesive composition, and an optical member with an adhesive layer provided with the adhesive layer. The alkylene dioxy group may be, for example, a linear or branched alkylene dioxy group having 1 to 3 carbon atoms.

Description

Adhesive composition, adhesive layer and optical member with adhesive layer

The present invention relates to an adhesive composition, an adhesive layer containing the adhesive composition, and an optical member including the adhesive layer.

A polarizing plate formed by laminating a protective film on one side or two areas of a polarizer is widely used in image display devices such as liquid crystal display devices and organic electroluminescent (organic EL) display devices, especially in recent years. Optical components for mobile phones such as mobile phones, smart phones, and tablet terminals. Optical members such as polarizing plates are mostly used by being bonded to other members (for example, optical members such as a liquid crystal cell in a liquid crystal display device) via an adhesive layer (for example, refer to Japanese Laid-Open Patent Publication No. 2010-229321). Therefore, for example, in most cases, a polarizing plate is circulated on the market in the form of a polarizing plate with an adhesive layer provided with an adhesive layer on one side thereof in advance.

The adhesive composition used for the adhesive layer for optical member bonding requires rework. This is because the optical components After the adhesive layer is bonded to other members, if there is any problem, if you recognize that any other problem, in order to reuse the other members, it is necessary to perform a so-called rework to peel off the bonded optical member with the adhesive layer and reattach the new optical member. The reason for the job. The so-called reworkability refers to the releasability when the optical member is peeled and removed together with the adhesive layer in the heavy work industry. If the surface to which the adhesive layer is attached in other members after peeling has almost no blur and no residue, etc., If the optical member with the adhesive layer can be easily re-attached to the surface, it is considered to have good reworkability.

Moreover, the said adhesive composition also requires durability. That is, the adhesive layer incorporated in an image display device or the like may be placed in a high-temperature, high-temperature, high-humidity environment, or a repeated high-temperature and low-temperature environment. In the environment, it is also possible to suppress defects that may occur due to dimensional changes of adjacent members. This defect is caused by floating or peeling at the interface between the adhesive layer and a member adjacent thereto, and foaming of the adhesive layer.

However, the optical adhesive composition disclosed in Patent Document 1 does not necessarily satisfy those whose adhesive layer has both durability and reworkability. Therefore, the present invention aims to provide an adhesive composition having both durability and reworkability, an adhesive layer including the adhesive composition, and an optical member with an adhesive layer provided with the adhesive layer.

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

[1] An adhesive composition containing 100 parts by weight of a (meth) acrylic resin (A), and The compound (B) containing at least one double bond and at least one alkylenedioxy in the molecule is 0.15 to 8 parts by weight.

[2] The adhesive composition according to [1], wherein the molecular weight of the compound (B) is 3,000 or less.

[3] The adhesive composition according to [1] or [2], wherein the alkylene dioxy group is a linear or branched alkylene dioxy group having 1 to 3 carbon atoms.

[4] The pressure-sensitive adhesive composition according to [1] to [3], wherein the alkylene dioxy group is an ethylene dioxy group.

[5] The adhesive composition according to [1] to [4], wherein the compound (B) includes a compound (B-1) represented by the following formula (B-1):

(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 alkylene dioxy group.)

[6] The adhesive composition according to [5], wherein the compound (B-1) is a compound (B-1a) represented by the following formula (B-1a):

(In the formula, Q ¹ represents a hydrogen atom or a methyl group, L represents a single bond or an alkylene group having 1 to 4 carbon atoms, i represents an integer from 1 to 50, and Q ² represents an alkoxy group having 1 to 3 carbon atoms. Substituted alkyl, aryl, or aralkyl having 1 to 4 carbons).

[7] The adhesive composition according to [1] to [6], wherein the weight average molecular weight Mw of the (meth) acrylic resin (A) is from 500,000 to 1.7 million.

[8] The adhesive composition according to [1] to [7], further comprising a crosslinking agent (C), wherein the content of the crosslinking agent (C) is relative to the (meth) acrylic resin ( A) 100 parts by weight and 0.1 to 5 parts by weight.

[9] The adhesive composition according to [1] to [8], further containing an ionic compound (D), wherein the content of the ionic compound (D) is relative to the (meth) acrylic resin (A ) 100 parts by weight and 0.3 to 5 parts by weight.

[10] An adhesive layer comprising the adhesive composition according to [1] to [9].

[11] An optical member with an adhesive layer, comprising: an optical member; and the adhesive layer as described in [10] laminated on the optical member.

[12] The optical member with an adhesive layer according to [11], wherein the optical member includes a polarizer.

[13] The optical member with an adhesive layer according to [11] or [12], further comprising: a release film laminated on an outer surface of the adhesive layer.

[14] The optical member with an adhesive layer according to [13], wherein the peeling force of the release film after the heat test maintained at 70 ° C for 20 days is P ₁ , and the peeling force before the heat test is At P ₀ , the peeling force increase rate defined by the following formula is 200% or less: the peeling force increase rate (%) = (P ₁ / P ₀ ) × 100.

[15] The optical member with an adhesive layer according to [11] or [12], further comprising: a glass substrate laminated on an outer surface of the adhesive layer.

According to the present invention, it is possible to provide an adhesive composition having both durability and reworkability, an adhesive layer containing the adhesive composition, and an optical member with an adhesive layer provided with the adhesive layer.

1‧‧‧Polarizer

2‧‧‧ surface treatment layer

3‧‧‧ protective film

4‧‧‧ protective film

7‧‧‧ retardation film

8‧‧‧ interlayer adhesive

10‧‧‧ polarizing plate

20‧‧‧ Adhesive layer

25‧‧‧ polarizer with adhesive layer

30‧‧‧ glass substrate

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

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

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

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

<Adhesive composition>

(1) (meth) acrylic resin (A)

The (meth) acrylic resin (A) preferably contains a (meth) acrylic resin (A-1), and the (meth) acrylic resin (A-1) is derived from the following formula (I): The polymer with the structural unit of (meth) acrylate as the main component:

In addition, in this specification, "(meth) acrylic acid" means acrylic acid and / or methacrylic acid, and "(meth)" in (meth) acrylate, (meth) acryl group, etc. is also The same gist.

In the above formula (I), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 14 carbon atoms which may be substituted with an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Alkoxy substituted aralkyl having 7 to 21 carbon atoms. R ^{2 is} preferably an alkyl group having 1 to 14 carbon atoms which may be substituted by an alkoxy group having 1 to 10 carbon atoms.

Specific examples of the (meth) acrylate represented by formula (I) include linear acrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, n-octyl acrylate, and lauryl acrylate. Alkyl ester Isobutyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate and other branched alkyl acrylates; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, Linear alkyl methacrylates such as n-octyl methacrylate and lauryl methacrylate; branched ones such as isobutyl methacrylate, 2-ethylhexyl methacrylate, and isooctyl methacrylate Alkyl methacrylate and the like.

When R ² is an alkyl group substituted with an alkoxy group, that is, when R ² is an alkoxy alkyl group, specific examples of the (meth) acrylate represented by the formula (I) include: acrylic acid 2- Methoxyethyl, ethoxymethyl acrylate, 2-methoxyethyl methacrylate, ethoxymethyl methacrylate, and the like. When R ² is an aralkyl group having 7 to 21 carbon atoms, specific examples of the (meth) acrylate represented by formula (I) include benzyl acrylate, benzyl methacrylate, and the like.

The (meth) acrylic acid ester represented by Formula (I) may be used individually by 1 type, and may use 2 or more types together. Among them, the (meth) acrylate preferably includes n-butyl acrylate. The (meth) acrylic resin (A-1) preferably contains 50% by weight of n-butyl acrylate in all the monomers constituting the monomer. Of course, in addition to n-butyl acrylate, a (meth) acrylate represented by formula (I) may be used in combination.

The (meth) acrylic resin (A-1) is usually a copolymer of the (meth) acrylate of the formula (I) and at least one other monomer such as a monomer having a polar functional group. The monomer having a polar functional group is preferably a (meth) acrylic compound having a polar functional group. Examples of the polar functional group included in the monomer include a free carboxyl group, a hydroxyl group, an amine group, and a heterocyclic group represented by an epoxy group.

Specific examples of the monomer having a polar functional group include monomers having a free carboxyl group such as acrylic acid, methacrylic acid, and β-carboxyethyl acrylate; 2-hydroxyethyl (meth) acrylate, and (meth) acrylic acid 3 -Hydroxypropyl ester, 4-hydroxybutyl (meth) acrylate, 2- (2-hydroxyethoxy) ethyl (meth) acrylate, 2- or 3-chloro-2-hydroxypropyl (meth) acrylate Ester, diethylene glycol mono (meth) acrylate, and other monomers having a hydroxyl group; allyl morpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, (meth) Tetrahydrofurfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate modified (meth) acrylate, 3,4-epoxycyclohexyl meth (meth) acrylate, (meth) acrylic acid ring Monocyclic monomers such as oxypropyl ester and 2,5-dihydrofuran; aminoethyl (meth) acrylate, N, N-dimethylamine (meth) acrylate Monomers having an amine group different from a heterocyclic ring, and the like, such as methyl ethyl ester and dimethyl aminopropyl (meth) acrylate. The polar functional group-containing monomer may be used alone or in combination of two or more.

Among the above, from the viewpoint of the reactivity of the (meth) acrylic resin (A-1), it is preferable to use a monomer having a hydroxyl group as the content of the (meth) acrylic resin (A-1). One of the polar functional monomers. In addition to the monomer having a hydroxyl group, other monomers having a polar functional group may be used in combination. For example, it is also effective to use a monomer having a free carboxyl group in combination.

The (meth) acrylic resin (A-1) may further include a monomer derived from the molecule having one olefinic double bond and at least one aromatic ring in the molecule (but excluding those corresponding to the above formula (I) or having the above polarity) Functional monomers) structural units. As a suitable example, a (meth) acrylic-type compound which has an aromatic ring is mentioned, for example. Such (meth) acrylic compounds having an aromatic ring also include neopentyl glycol benzoate (meth) acrylate and the like, and are particularly represented by the following formula (II):

The (meth) acrylate having an aryloxyalkyl group such as the phenoxyethyl group-containing (meth) acrylate is preferable.

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

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

Specific examples of the phenoxyethyl group-containing (meth) acrylate represented by the formula (II) include 2-phenoxyethyl (meth) acrylate and 2- (2- Phenoxyethoxy) ethyl ester, (meth) acrylate of ethylene oxide-modified nonylphenol, 2- (o-phenylphenoxy) ethyl (meth) acrylate, and the like. The phenoxyethyl-containing (meth) acrylate may be used alone or in combination of two or more. Among them, (meth) acryl containing phenoxyethyl The acid ester preferably includes 2-phenoxyethyl (meth) acrylate, 2- (o-phenylphenoxy) ethyl (meth) acrylate, and / or 2- (2-) (meth) acrylate Phenoxyethoxy) ethyl ester.

The (meth) acrylic resin (A-1), based on the total amount of its solid content, is usually derived from the (meth) acrylic acid ester represented by the formula (I) in the structural unit system containing 60 to 99.9% by weight. It is preferable to contain 80 to 99.6% by weight. The structural unit system derived from a monomer having a polar functional group usually contains 0.1 to 20% by weight, more preferably 0.4 to 10% by weight. Furthermore, it is derived from benzene. The structural unit system of the monomer having an aromatic ring such as an oxyethyl (meth) acrylate generally contains 0 to 40% by weight, and more preferably contains 6 to 12% by weight.

The (meth) acrylic resin (A-1) may include a (meth) acrylate derived from the formula (I) described above, a monomer having a polar functional group, and a (meth) group containing a phenoxyethyl group. A structural unit of a monomer other than a monomer having an aromatic ring such as an acrylate (hereinafter also referred to as another monomer). Examples of other monomers include, for example, a structural unit derived from a (meth) acrylate having an alicyclic structure in the molecule, a structural unit derived from a styrene-based monomer, a structural unit derived from a vinyl-based monomer, A structural unit of a monomer having a plurality of (meth) acrylfluorenyl groups in the molecule, a structural unit derived from a (meth) acrylfluorene compound, and the like. Other single systems can be used alone or in combination of two or more.

The alicyclic structure in the (meth) acrylic acid ester having an alicyclic structure in the molecule refers to a cycloparaffin structure in which the carbon number is usually 5 or more, and preferably about 5 to 7. Alicyclic structure Specific examples of the (meth) acrylate include isopropyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, and cyclododecyl (meth) acrylate Alkyl ester, methyl cyclohexyl (meth) acrylate, trimethyl cyclohexyl (meth) acrylate, third butyl cyclohexyl (meth) acrylate, cyclohexyl phenyl (meth) acrylate, α -Cyclohexyl ethoxylate and the like.

Specific examples of the styrene-based monomer include: styrene; such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, Alkyl styrenes such as propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene; such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene Isohalogenated styrene; nitrostyrene, ethenylstyrene, 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, and the like; Halogenated ethylene such as ethylene bromide; vinylidene chloride such as vinylidene chloride; nitrogen-containing aromatic vinyl such as vinylpyridine, vinylpyrrolidone, and vinylcarbazole; such as butadiene and isoprene , Chloroprene and other conjugated diene monomers; acrylonitrile, methacrylonitrile, etc.

Specific examples of the monomer having a plurality of (meth) acrylfluorenyl groups in the molecule include, for example, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (methyl) Acrylate, 1,9-nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (methyl) Acrylate, tripropylene glycol di (meth) acrylate aliquot Monomers having two (meth) acrylfluorene groups in the daughter; such as trimethylolpropane tri (meth) acrylate and other monomers having three (meth) acrylfluorene groups in the molecule.

Specific examples of the (meth) acrylamide compound are preferably used: N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N- ( 3-hydroxypropyl) (meth) acrylamide, N- (4-hydroxybutyl) (meth) acrylamide, N- (5-hydroxypentyl) (meth) acrylamide, N- (6-hydroxyhexyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl ( Meth) acrylamide, N- (3-dimethylaminopropyl) (meth) acrylamide, N- (1,1-dimethyl-3-oxobutyl) (methyl ) Acrylamide, N- [2- (2- pendant oxy-1-imidazolidinyl) ethyl] (meth) acrylamide, 2-propenylamino-2-methyl- 1-propanesulfonic acid, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) (meth) acrylamide, N- (propoxymethyl) (meth) propylene Ammonium amine, N- (1-methylethoxymethyl) (meth) acrylamide, N- (1-methylpropoxymethyl) (meth) acrylamide, N- (2- Methylpropoxymethyl) (meth) acrylamide [alias: N- (isobutoxymethyl) (meth) acrylamide], N- (butoxymethyl) (methyl) Acrylic , N- (1,1-dimethylethoxymethyl) (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N- (2-ethyl (Oxyethyl) (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) (meth) acrylamide, N -[2- (1,1-dimethylethoxy) Ethyl] (meth) acrylamide and the like. Among them, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (butoxymethyl) ) Acrylamide, N- (2-methylpropoxymethyl) acrylamide.

The (meth) acrylic resin (A-1) contains other monomers in an amount of usually 0 to 20% by weight, more preferably 0 to 10% by weight, based on the total amount of the solid content.

The (meth) acrylic resin (A-1) may contain two or more kinds of structural units derived from the (meth) acrylic acid ester represented by the formula (I) as the main component, and may be derived from polar groups. A structural unit of a functional group monomer, and a (meth) acrylic resin that arbitrarily includes a structural unit derived from a monomer having an aromatic ring. Further, the (meth) acrylic resin (A-1) and a (meth) acrylic resin (A-2) different from the (meth) acrylic resin (A-1) may have, for example, a (meth) group derived from the formula (I). ) It is a mixture of (meth) acrylic resin, etc. which is a structural unit of an acrylic ester and does not have a polar functional group. A structural unit derived from a (meth) acrylic acid ester represented by formula (I) as a main component, a structural unit derived from a monomer having a polar functional group, and a structural unit derived from a monomer having an aromatic ring are optionally included The (meth) acrylic resin (A-1) is the main component of the adhesive composition, and the content is 60% by weight or more and 80% by weight or more of the (meth) acrylic resin (A). More ideal.

(Meth) acrylic resin (A-1) whose weight-average molecular weight (Mw) of standard polystyrene converted by gel permeation chromatography (GPC) ranges from 500,000 to 1.7 million Ideally, a range of 600,000 to 1.5 million is more desirable. When Mw is more than 500,000, the The adhesiveness is improved, and the possibility of floating or peeling between the member (for example, a glass substrate) to which the adhesive layer is attached and the adhesive layer tends to be low, and the reworkability tends to be improved. In addition, when Mw is 1.7 million or less, if an optical member with an adhesive layer is applied to a liquid crystal display device, even if the size of the optical member is changed, the adhesive layer will change in accordance with the change in the size. The difference between the brightness of the portion and the brightness of the center portion disappears, and there is a tendency that whitening and color unevenness are suppressed. 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 in the range of about 2 to 10.

The preferred Mw of the (meth) acrylic resin (A-1) is also based on the surface of the adhesive layer forming member (optical member) on which the adhesive layer composed of the adhesive composition containing the Mw is formed. Material varies. In the past, the (meth) acrylic resin generally constituting an acrylic adhesive requires at least about 1 million Mw. However, if an adhesive layer containing a (meth) acrylic resin (A-1) is used, the adhesive layer is used as the adhesive layer. The surface system is made of, for example, a cellulose-based resin film that exhibits a moisture permeability higher than about 300 g / (m ² ‧24hr) at a temperature of 40 ° C and a relative humidity of 90%, even when the Mw is 500,000. The above-mentioned effect can also be obtained in the case where it is small to about 1 million. When such a resin film having a high moisture permeability is used as the adhesive layer formation surface, the Mw of the (meth) acrylic resin (A-1) may of course be a large value within a range of 1.7 million or less.

On the other hand, the adhesive layer-forming surface is less than about 300 g at a temperature of 40 ° C and a relative humidity of 90%, such as a chain or cyclic polyolefin resin film or a retardation film obtained by extending the film. When (/ m ² ‧24hr) is composed of a moisture-permeable resin film, if the Mw of the (meth) acrylic resin (A-1) is small, when the adhesive layer is bonded to a glass substrate, etc., There is a tendency that floating or peeling is likely to occur. Therefore, in this case, the Mw of the (meth) acrylic resin (A-1) is preferably 600,000 or more. From the viewpoint of improving the adhesion under high temperature and high humidity, Mw is preferably 600,000 or more.

The (meth) acrylic resin (A) may be composed of only the above-mentioned (meth) acrylic resin (A-1) having a relatively high molecular weight, or it may be used in combination with a (meth) acrylic resin different therefrom ( A-3). Examples of the (meth) acrylic resin (A-3) include a structural unit derived from the (meth) acrylic acid ester represented by the formula (I) as a main component, and Mw is in a range of 0.5 to 120,000. By.

A solution of (meth) acrylic resin (A) (a mixture of two or more in the case of a combination of two or more types) in ethyl acetate was adjusted to a concentration of 20% by weight, and 20 Pa was displayed at 25 ° C. Viscosity below ‧s is ideal to show viscosity from 0.1 to 7Pa‧s When the viscosity is 20 Pa · s or less, the adhesion in a high-temperature and high-humidity environment is improved, and the possibility of floating or peeling between the member (for example, a glass substrate) that adheres the adhesive layer and the adhesive layer tends to be low. And the reworkability tends to improve. Viscosity can be measured by a Brookfield viscometer.

The (meth) acrylic resin (A-1) and other (meth) acrylic resins that can be used arbitrarily are based on conventional methods such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method. It can be manufactured. In the production of a (meth) acrylic resin, a polymerization initiator is usually used. The polymerization initiator is used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the total of all the monomers used in the production of the (meth) acrylic resin. right. Moreover, (meth) acrylic-type resin system can also be manufactured by the method of superposing | polymerizing by active energy rays, such as an ultraviolet-ray.

As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator is used. Examples of the photopolymerization initiator system include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone and the like. Examples of the thermal polymerization initiator system include: 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexyl) Alkane-1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxy) Valeronitrile), dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-hydroxymethylpropionitrile) and other azo compounds; such as Lauryl peroxide, third butyl hydroperoxide, benzamyl peroxide, third butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxide dicarbonate, dicarbonate dicarbonate Organic peroxides such as propyl ester, tertiary butyl peroxyneodecanate, tertiary butyl peroxypivalate, and peroxy (3,5,5-trimethylhexyl); such as potassium persulfate, Inorganic peroxides such as ammonium persulfate and hydrogen peroxide. Further, a redox-based initiator in which a peroxide and a reducing agent are used in combination can also be used as a polymerization initiator.

As for the manufacturing method of a (meth) acrylic-type resin, among the methods shown above, a solution polymerization method is preferable. An example of the solution polymerization method is to mix a monomer with an organic solvent, add a thermal polymerization initiator under a nitrogen atmosphere, and stir at about 40 to 90 ° C, preferably about 60 to 80 ° C, for about 3 to 10 hours. In order to control the reaction, a monomer and / or a thermal polymerization initiator may be added continuously or intermittently during the polymerization, or may be added in a state of being dissolved in an organic solvent. Organic solvents can be used, for example: aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; such as propanol, Aliphatic alcohols such as isopropanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.

(2) Compound (B) containing at least one double bond and at least one alkylenedioxy in the molecule

The adhesive composition system of the present invention contains a compound (B) [hereinafter also referred to as a compound containing at least one double bond and at least one alkylene dioxy group (-O-alkylene-O-) in the molecule] (B)]. By containing the compound (B), an adhesive composition having a high degree of durability and reworkability can be obtained. In addition, according to the adhesive layer composed of the adhesive composition containing the compound (B), it is possible to suppress the increase in the peeling force of the release film laminated on the surface of the adhesive layer from the adhesive layer due to heat. A preferable example of the above-mentioned double bond is a double bond contained in a (meth) acrylfluorenyl group, and even if the adhesive composition of the present invention is stored for a long period of time under a light environment, a high temperature environment, or an environment containing oxygen, From the viewpoint that the adhesive layer of the present invention and the optical member with an adhesive layer of the present invention are not easily reduced in durability and reworkability, a more preferable example is a double bond included in a methacrylfluorenyl group. The preferred examples of the above-mentioned alkylene dioxy group are those having a carbon number of 1 to 4 and more preferably a carbon number of 1 from the viewpoint of having both durability and reworkability and suppressing an increase in peeling force. A straight or branched alkylene dioxy group of 3 to 3 is more preferably an ethylene dioxy group (-OC ₂ H ₄ -O-).

From the viewpoint of having both durability and reworkability and suppressing an increase in peeling force, the molecular weight of the compound (B) is preferably 3,000 or less, for example, 2,000 or less, more preferably 1700 or less, and more preferably 1400 or less. Moreover, a molecular weight of 400 or more is preferable, and a molecular weight of 600 or more is more reasonable. Think, more than 1050 is more ideal.

From the viewpoint of having both durability and reworkability and suppressing an increase in peeling force, the compound (B) preferably includes a (meth) acrylfluorenyl group-containing compound (B-) represented by the following formula (B-1) 1), and it is more preferably composed of a compound (B-1).

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 alkylene dioxy group. The compound (B) may include two or more compounds (B-1). h is more preferably an integer of 1 to 3.

The h-valent group having at least one alkylene dioxy group represented by Q ⁰ may be an h-valent hydrocarbon group having at least one alkylene dioxy group, and more preferably has at least one alkylene dioxy 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 having 1 to 4 carbon atoms, which may be substituted by an alkoxy group having 1 to 3 carbon atoms, and L represents a single bond or an alkylene group having 1 to 4 carbon atoms. Base, i represents an integer from 1 to 50 (for example, 1 to 30). The carbon number of the aryl group which can be 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 each independently represent an integer of 1 to 40 (for example, 1 to 30), and y + z may be an integer of 1 to 40 (for example, 1 to 30). In Q ⁰⁴ , e, f, and g each independently represent an integer of 1 to 20 (for example, 1 to 10), and e + f + g may be an integer of 1 to 30 (for example, 1 to 25).

Examples of the more suitable compound (B-1) include the compound (B-1a) represented by the following formula (B-1a).

The compound (B) may include two or more compounds (B-1a). The compound (B-1a) is a compound in which Q ⁰ is Q ⁰¹ in the formula (B-1). In the formula, Q ¹ , L, i, and Q ^{2 have the} same meanings as described above. In compound (B-1a), L is preferably a single bond, i is preferably an integer of 7 to 35, and more preferably an integer of 9 to 25. Q ² is preferably an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, phenyl, and biphenyl.

Specific examples of the compound (B-1a) include, for example, Q ¹ , L, i, and Q ² as shown in Table 1 below.

Another example of a more suitable compound (B-1) is a compound in which Q ⁰ is Q ⁰⁴ in the above formula (B-1). In this case, h in the above formula (B-1) is 3. The compound (B) may include two or more compounds in which Q ⁰ is Q ⁰⁴ . In Q ⁰⁴ , e + f + g is preferably an integer from 5 to 25.

Another example of a more suitable compound (B-1) is a compound in which Q ⁰ is Q ⁰³ in the formula (B-1). In this case, h in the above formula (B-1) is 2. The compound (B) may include two or more compounds in which Q ⁰ is Q ⁰³ . In Q ⁰³ , y + z is preferably an integer from 5 to 25.

The compound (B) is preferably formulated in an amount of 0.15 to 8 parts by weight based on 100 parts by weight of the solid content of the (meth) acrylic resin (A) (when two or more types are used). The ratio is 0.3 to 7 parts by weight, and more preferably 0.5 to 6 parts by weight (for example, 1 to 5 parts by weight). When the compounding amount of the compound (B) is within this range, both the durability and the reworkability can be achieved, and at the same time, the effect of suppressing an increase in peeling force can be obtained.

(3) Crosslinking agent (C)

The adhesive composition may further contain a crosslinking agent (C). The cross-linking agent (C) reacts with the structural unit derived from the monomer containing a polar functional group in the (meth) acrylic resin (A), and crosslinks the (meth) acrylic resin (A). Linked compounds. Specific examples include isocyanate-based compounds, epoxy-based compounds, aziridine-based compounds, and metal clamp-based compounds. Among these, the isocyanate-based compound, epoxy-based compound, and aziridine-based compound have at least two functional groups in the molecule that can react with the polar functional group in the (meth) acrylic resin (A). Crosslinking agent (C) makes It can be used alone or in combination of two or more.

An isocyanate-based compound is a compound having at least two isocyanate groups (-NCO) in the molecule. Specific compound systems include, for example, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, and hydrogenated diphenyl group. Methane diisocyanate, napthyl diisocyanate, triphenylmethane triisocyanate, etc. In addition, an adduct obtained by reacting such an isocyanate compound with a polyhydric alcohol such as glycerol or trimethylolpropane, or a dimer, trimer, or the like made of an isocyanate compound may also be crosslinked. Agent (C). You may mix and use 2 or more types of isocyanate-type compounds.

An epoxy compound is a compound having at least two epoxy groups in the molecule. Specific compound systems include, for example, bisphenol A epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, and glycerol triglyceride. Glycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N, N-glycidylaniline, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N'-glycidylaminomethyl) cyclohexane, and the like. You may mix and use 2 or more types of epoxy compounds.

An aziridine-based compound is a compound having at least two 3-membered ring skeletons composed of one nitrogen atom and two carbon atoms, also called ethyleneimine. Specific compound systems include, for example, diphenylmethane-4,4'-bis (1-aziridinecarboxamide), toluene-2,4-bis (1-aziridinecarboxamide), and triethylene glycol Melamine, m-xylylene Bis-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, hexamethylene-1,6-bis (1-aziridinecarboxamide), trimethylol Propane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, and the like. A mixture of two or more aziridine-based compounds may be used.

Examples of the metal clamp system include polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. And other compounds. It is also possible to use a mixture of two or more metal clamp compounds.

Among them, it is preferable to use isocyanate-based compounds, in particular: xylylene diisocyanate, xylylene diisocyanate, or hexamethylene diisocyanate; and to make these isocyanate compounds and polyvalent compounds such as glycerol or trimethylolpropane Adducts formed by the reaction of alcohols; these isocyanate compounds are made into dimers, trimers, etc., or mixtures thereof; mixtures of two or more isocyanate-based compounds disclosed above; Suitable isocyanate-based compounds include, for example, a tolyl diisocyanate, an adduct obtained by reacting the tolyl diisocyanate and a polyol, a dimer of the tolyl diisocyanate, and a compound of the tolyl diisocyanate. Terpolymer; hexamethylene diisocyanate, adduct obtained by reacting hexamethylene diisocyanate with polyol, dimer of hexamethylene diisocyanate, and hexamethylene diisocyanate Trimer.

The crosslinking agent (C) is usually formulated in an amount of 0.05 to 5 parts by weight based on 100 parts by weight of the solid content of the (meth) acrylic resin (A) (when two or more types are used). , More preferably 0.1 to 5 parts by weight. When the compounding amount of the crosslinking agent (C) is 0.05 parts by weight or more, The durability of the adhesive layer tends to be improved, and if it is 5 parts by weight or less, the whitening of the optical member with the adhesive layer applied to a liquid crystal display device tends to be insignificant.

(4) Ionic compound (D)

The adhesive composition may further include an ionic compound (D) as an antistatic agent for imparting antistatic properties to the adhesive layer. The ionic compound (D) is a compound having an inorganic or organic cation and an inorganic or organic anion.

Examples of the inorganic cation include alkali metal ions such as lithium cation [Li ⁺ ], sodium cation [Na ⁺ ], potassium cation [K ⁺ ], beryllium cation [Be ²⁺ ], magnesium cation [Mg ²⁺ ], and calcium cation. [Ca ²⁺ ] and other alkaline earth metal ions.

Examples of the organic cation include an imidazolium cation, a pyridinium cation, a pyrrolidium cation, an ammonium cation, a sulfonium cation, and a sulfonium cation.

Among the above-mentioned cationic components, organic cationic components are more suitable because they have good compatibility with the adhesive composition. Among the organic cation components, in particular, the use of a pyridinium cation and an imidazolium cation is preferable from the viewpoint that it is not easy to be charged when the release film provided on the adhesive layer is peeled.

Inorganic anions, such as chlorine-based anions include [Cl ^-], bromine anion [Br ^-], iodide anion [I ^-], tetrachloroaluminate anion [AlCl ₄ ^-], heptachlorodialuminate anion [Al ₂ cl ₇ ^-], tetrafluoroborate anion [BF ₄ ^-], hexafluorophosphate anions [PF ₆ ^-], perchlorate anion [ClO ₄ ^-], nitrate anion [NO ₃ ^-], hexafluoro arsenic anions [AsF ₆ ^-], hexafluoroantimonate anion [SbF ₆ ^-], hexafluoro niobate anions [NbF ₆ ^-], six tantalum fluoride anions [TaF ₆ ^-], dicyanamide anion [ (CN) ₂ N ^-] and the like.

Organic anions such as acetate-based anion include [CH ₃ COO ^-], trifluoroacetate anion [CF ₃ COO ^-], methane sulfonate anion [CH ₃ SO ₃ ^-], trifluoromethane sulfonate anion [CF ₃ SO ₃ ^-], of - toluenesulfonate anion _{[p-CH 3 C 6 H} 4 SO 3 -], bis (sulfo-fluoro-acyl) acyl imide anion ^{_{[(FSO 2) 2 N -}} ] , bis (trifluoromethane sulfonic acyl) acyl imide anion _{[(CF 3 SO 2) 2} N -], tris (trifluoromethane sulfonic acyl) methanide (methanide) anion _{[(CF 3 SO 2) 3} C ^-], dimethylmethylene phosphonate ^{_{[(CH 3) 2 POO -}} ], hydrogen-fluoride anion fluorine ^{_{[F (HF) n -]}} (n is about 1 to 3), a thiocyanate anion [SCN ^-], perfluorobutanesulfonate anion ^{_{[C 4 F 9 SO 3 -}} ], bis (pentafluoroethane sulfonic acyl) acyl imide anion _{[(C 2 F 5 SO 2} ) 2 N -], whole butyrate fluorine anion ^{_{[C 3 F 7 COO -]}} , ( trifluoromethane sulfonic acyl) (trifluoromethane-carbonyl) acyl imide anion _{[(CF 3 SO 2) (} CF 3 CO) N -], perfluoro propane-1,3-disulfonate anion ^{_{[- O 3 S (CF 2}} ) 3 SO 3 -], the anion carbonate [CO ₃ ^2-] and the like.

Among the above-mentioned anionic components, in particular, an anionic component containing a fluorine atom is more suitable because it can impart an ionic compound (D) having an excellent antistatic function. Specifically, for example, a bis (fluorosulfofluorenyl) fluorenimide anion, a hexafluorophosphate anion, or a bis (trifluoromethanesulfonyl) fluorenimide anion is mentioned.

Specific examples of the ionic compound (D) can be appropriately selected from the combination of the above-mentioned cationic component and anionic component. Organic ionization When an example of the ionic compound (D) is disclosed according to the structural classification of the organic cation, the following examples may be mentioned.

Pyridinium salts: N-hexylpyridinium hexafluorophosphate, N-octylpyridinium hexafluorophosphate, N-octyl-4-methylpyridinium hexafluorophosphate, N-butyl-4-methyl Pyridinium hexafluorophosphate, N-decylpyridinium bis (fluorosulfonyl) fluorenimide, N-dodecylpyridinium bis (fluorosulfonyl) fluorenimide, N-tetradecylpyridine Onium bis (fluorosulfonyl) fluorenimide, N-hexadecylpyridinium bis (fluorosulfonyl) fluorenimide, N-dodecyl-4methylpyridinium bis (fluorosulfonyl) Fluorenimine, N-tetradecyl-4methylpyridinium bis (fluorosulfonyl) fluorenimide, N-hexadecyl-4methylpyridinium bis (fluorosulfonyl) fluorenimine, N-benzyl-2-methylpyridinium bis (fluorosulfonyl) fluorenimide, N-benzyl-4-methylpyridinium bis (fluorosulfonyl) fluorenimide, N-hexylpyridine Onium bis (trifluoromethanesulfonyl) fluorenimine, N-octylpyridinium bis (trifluoromethanesulfonyl) fluorenimide, N-octyl-4-methylpyridinium bis (trifluoromethanesulfonate Fluorenyl) fluorenimine, N-butyl-4-methylpyridinium bis (trifluoromethanesulfonyl) fluorenimine.

Imidazolium salts: 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium p-toluenesulfonate, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimine, 1-ethyl-3-methylimidazole Onium bis (trifluoromethanesulfonyl) fluorenimide, 1-butyl-3-methylimidazolium methanesulfonate, 1-butyl-3-methylimidazolium bis (fluorosulfonyl) fluorene amine.

Pyrrolidinium salts: N-butyl-N-methylpyrrolidinium hexafluorophosphate, N-butyl-N-methylpyrrolidinium bis (fluorosulfonyl) fluorenimine, N-butyl- N-methylpyrrolidinium bis (trifluoromethanesulfonyl) fluorenimine.

Grade 4 ammonium salts: tetrabutylammonium hexafluorophosphate, tetrabutylammonium p-toluenesulfonate, (2-hydroxyethyl) trimethylammonium bis (trifluoromethanesulfonyl) fluorenimine, ( 2-hydroxyethyl) trimethylammonium dimethyl phosphinate.

In addition, when the example of the ionic compound (D) which has an inorganic cation is mentioned, the following is mentioned, for example.

Lithium bromide, lithium iodide, lithium tetrafluoroborate, lithium hexafluorophosphate, Lithium thiocyanate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (fluorosulfonyl) fluorenimide, lithium bis (trifluoromethanesulfonyl) fluorenimide, bis (pentafluoroethanesulfonate) Fluorenyl) lithium sulfonium imine, lithium tris (trifluoromethanesulfonyl) lithium methanide, lithium p-toluenesulfonate, sodium hexafluorophosphate, sodium bis (fluorosulfonyl) fluorenimide, bis (trifluoromethane) Sulfosulfonyl) sulfonium imine, sodium p-toluenesulfonate, potassium hexafluorophosphate, potassium bis (fluorosulfonyl) phosphonium imine, potassium bis (trifluoromethanesulfonyl) phosphonium imine, p-toluene Potassium sulfonate.

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

The content of the ionic compound (D) in the adhesive composition is based on 100 parts by weight of the solid content of the (meth) acrylic resin (A) (when two or more kinds are used) It is preferably 0.2 to 8 parts by weight, more preferably 0.2 to 5 parts by weight, more preferably 0.3 to 5 parts by weight, and particularly preferably 0.5 to 3 parts by weight. If the content of the ionic compound (D) is 0.2 parts by weight or more, it is advantageous to improve the antistatic function, and if it is 8 parts by weight or less, it is advantageous to improve the durability of the adhesive layer.

(5) Silane compound (E)

When the adhesive layer is bonded to the glass substrate in the adhesive composition, in order to improve the adhesion between the adhesive layer and the glass substrate, a silane compound (E) may be further contained. The silane compound (E) may be contained in the (meth) acrylic resin (A) before the crosslinking agent (C) is prepared.

Examples of the silane compound (E) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, and N- (2-aminoethyl) 3-Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxy Propylethoxydimethylsilane and the like. also Two or more silane compounds can be used.

The silane compound (E) may be a silicone oligomer type. When a polysiloxane oligomer is represented as a (monomer) oligomer, the following is mentioned, for example.

3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxyoxide Mercaptopropyl-containing copolymers such as 3-mercaptosilane, 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyl Trimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer, mercaptomethyltriethoxysilane-tetraethoxysilane copolymer, etc. Copolymers of methyl; 3-glycidoxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-epoxy Propoxypropylmethyldimethoxysilane-tetramethoxysilane Copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane Copolymers, 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymers and other copolymers containing 3-glycidoxypropyl; 3-methacryloxy Propyltrimethoxysilane-tetramethoxysilane copolymer, 3-methacrylmethoxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropyltriethyl Oxysilane-tetramethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldimethyl Oxysilane-tetramethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyl Diethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer, etc. Copolymer Propyltrimethoxysilane-tetramethoxysilane copolymer Polymer, 3-propenyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-propenyloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-propenyloxysilane Propyltriethoxysilane-tetramethoxysilane copolymer, 3-propenyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-propenyloxypropylmethyl Dimethoxysilane-tetraethoxysilane copolymer, 3-propenyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-propenyloxypropylmethyldiene Copolymers containing acryloxypropyl, such as ethoxysilane-tetraethoxysilane copolymer; vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxy Silane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane Silane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane-tetramethoxysilane copolymer, Copolymers containing vinyl, such as vinyl methyldiethoxysilane-tetraethoxysilane copolymer; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane- Tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, 3-aminopropyl Amine-containing copolymers such as methyldiethoxysilane-tetraethoxysilane copolymers and the like.

Most of the silane compounds (E) exemplified above are liquids. The content of the silane compound (E) in the adhesive composition is based on 100 parts by weight of the solid content of the (meth) acrylic resin (A) (when two or more kinds are used) 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and still more preferably 0.2 to 0.4 parts by weight. When the amount of the silane compound (E) is 0.01 parts by weight or more, the effect of improving the adhesion between the adhesive layer and the glass substrate is easily obtained. When the content is 10 parts by weight or less, bleeding of the silane compound (E) from the adhesive layer can be suppressed.

(6) Other ingredients

The adhesive composition may contain a crosslinking catalyst, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, light-scattering fine particles, and (meth) acrylic resin (A). Additives such as resin. In addition, an ultraviolet curable compound is blended in the adhesive composition to form an adhesive layer, and then it is irradiated with ultraviolet rays to harden to make a harder adhesive layer. Useful.

When the adhesive composition contains both the cross-linking agent (C) and the cross-linking catalyst, the adhesive layer can be prepared by short-term ripening. In addition, when a cross-linking catalyst is contained, it is possible to more effectively suppress floating or peeling at the interface between the adhesive layer and a member adjacent thereto, and foaming of the adhesive layer, and the reworkability is also improved. Examples of the crosslinking catalyst system include hexamethylenediamine, ethylenediamine, polyethylenimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isopropylidene Amine compounds such as phorone diamine, trimethylene diamine, polyamine resin, and melamine resin. When an amine-based compound is formulated as a crosslinking catalyst in the adhesive composition, an isocyanate-based compound is suitably used as the crosslinking agent (C).

The adhesive composition usually does not substantially contain a polymerization initiator. The content of the polymerization initiator in the adhesive composition is preferably 0.01 parts by weight or less, and more preferably 0 parts by weight, based on 100 parts by weight of the adhesive composition. Examples of the polymerization initiator system include a photopolymerization initiator that decomposes itself upon irradiation with light to generate radicals, and a thermal polymerization initiator that decomposes upon heating to generate radicals on its own.

In the adhesive composition of the present invention, the compound (B) is contained so as not to react with other components in the adhesive composition. Therefore, the adhesive composition of the present invention can have both high durability and heavy workability.

<Adhesive layer>

The adhesive layer of the present invention includes the adhesive composition of the present invention, and is typically composed of the adhesive composition of the present invention. Adhesive The layer system can be obtained by dissolving or dispersing each component constituting the above-mentioned adhesive composition in a solvent to prepare a solvent-containing adhesive composition, and then coating the base film and drying it. The adhesive layer system of the present invention is excellent in durability and reworkability, and also has an excellent ability to suppress an increase in peeling force of a release film laminated on the surface thereof. Even if the adhesive composition containing a solvent is applied and dried under a light environment, a high-temperature environment, or an environment containing oxygen, an adhesive layer with higher durability and reworkability can be easily formed. The double bond of the compound (B) contained in the adhesive composition is preferably a double bond contained in a methacrylfluorenyl group.

The base film is generally a plastic film, and typical examples thereof include a release film (separator) that has been subjected to a release treatment. The release film can be, for example, a polymer film formed on a surface of a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyarylate to form an adhesive layer. Silicone treatment plasma. In addition, an adhesive layer may be directly coated on the surface of the optical member to form an adhesive layer, and the film may be peeled off from the outer surface layer of the adhesive layer as an optical member with an adhesive layer as needed. When the adhesive layer is provided on the surface of the optical member, a surface activation treatment such as plasma treatment, corona treatment, etc. may be performed on the bonding surface of the optical member and / or the bonding surface of the adhesive layer as required.

The thickness of the adhesive layer is preferably 10 to 45 μm, more preferably 10 to 30 μm, and even more preferably 10 to 20 μm. When the thickness of the adhesive layer is 45 μm or less, the adhesiveness in a high-temperature and high-humidity environment is improved, and the possibility of floating or peeling between the member (such as a glass substrate) that adheres to the adhesive layer and the adhesive layer is reduced. Tendency and improved rework High tendency. In addition, when the thickness is 10 μm or more, if an optical member with an adhesive layer is applied to a liquid crystal display device, even if the size of the optical member is changed, the adhesive layer will follow the change of the size, so the periphery of the liquid crystal cell The difference between the brightness of the portion and the brightness of the center portion disappears, and there is a tendency that whitening and color unevenness are suppressed. Conventionally, the thickness of an adhesive layer attached to a liquid crystal cell is generally 25 μm. However, in the present invention, even if the thickness is 20 μm or less, it functions sufficiently as an adhesive layer.

The adhesive layer preferably has a gel fraction in the range of 30 to 85%. When the gel fraction is 30% or more, the durability under high temperature and high humidity is favorable, and the possibility of floating or peeling between the member (for example, a glass substrate) and the adhesive layer that adheres to the adhesive layer is reduced. And the reworkability tends to improve. On the other hand, when the gel fraction is 85% or less, when an optical member with an adhesive layer is applied to a liquid crystal display device, even if the size of the optical member changes, the adhesive layer will follow the change in size. Therefore, the difference between the brightness of the peripheral portion of the liquid crystal cell and the brightness of the center portion disappears, and whitening and color unevenness tend to be suppressed.

According to the adhesive composition of the present invention, after the adhesive layer having an adhesive layer having a release film (separator) on at least one side and a release film laminated on the outer surface of the adhesive layer, the optical member with the adhesive layer described later, When the peeling force of the peeling film after the heating test held at 70 ° C for 20 days is taken as P ₁ and the peeling force before the heating test is taken as P ₀ , the peeling force increase rate defined by the following formula is 200% or less, and May be 180% or less: Peeling force increase rate (%) = (P ₁ / P ₀ ) × 100

<Optical member with adhesive layer>

The adhesive layer of the present invention is suitable as an adhesive layer for attaching members (particularly, optical members) to each other. The optical member with an adhesive layer of the present invention is, for example, an adhesive member laminated on an optical member, or an optical member laminated on the outer surface of the adhesive layer to adhere other optical members.

(1) First embodiment

An ideal embodiment of the optical component with an adhesive layer of the present invention includes a resin film and an adhesive layer laminated on at least one side thereof. Examples of the resin film include an optical film such as a polarizer, a protective film, and a retardation film, or a surface protective film used for the purpose of protecting the surface of the optical film belonging to the object to be protected from damage or contamination. .

The polarizer is a film having a function of extracting linearly polarized light from incident natural light. A preferred example is a polyvinyl alcohol-based resin film extending along one axis that adsorbs and aligns a dichroic dye such as iodine or a dichroic dye. The thickness of the polarizer is not particularly limited, but is usually 0.5 to 35 μm.

The protective film may be made of a resin having translucency (preferably optically transparent) such as a chain polyolefin resin (polypropylene resin, etc.), a cyclic polyolefin resin (norbornene resin, etc.) ) And other polyolefin resins; cellulose resins such as triethyl cellulose and diethyl cellulose; polyester resins; polycarbonate resins; (meth) acrylic resins; polystyrene resins Resin; polyetheretherketone resin; thermoplastic resin such as polyfluorene resin The composition of the film. In the protective film, a salicylate-based compound, a diphenyl ketone-based compound, a benzotriazole-based compound, a triazine-based compound, a cyanoacrylate-based compound, and a nickel salt-based compound can also be blended. And other UV absorbers. The thermoplastic resin constituting the protective film is preferably a cellulose resin or a (meth) acrylic resin.

Examples of the chain polyolefin resin include, in addition to homopolymers of chain olefins such as polyethylene resins and polypropylene resins, copolymers composed of two or more types of chain olefins.

The cyclic polyolefin resin is a general term for a resin polymerized by using a cyclic olefin as a polymerization unit. Specific examples of cyclic polyolefin resins include: ring-opened (co) polymers of cyclic olefins; addition polymers of cyclic olefins; and cyclic olefins with chain olefins such as ethylene and propylene. Copolymers (representative examples are random copolymers); graft polymers modified with these unsaturated carboxylic acids or derivatives thereof; and hydrides of the above. Among them, norbornene-based resins using a norbornene-based monomer such as norbornene or a polycyclic norbornene-based monomer as the cyclic olefin are more suitable.

Examples of the partially or completely esterified cellulose-based resin-based cellulose include cellulose acetate, propionate, butyrate, and mixed esters thereof. Among them, it is preferable to use triethyl cellulose, diethyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, and the like.

Polyester-based resins are resins other than the above-mentioned cellulose-based resins having an ester bond, and are generally composed of a polycondensate of a polycarboxylic acid or a derivative thereof and a polyhydric alcohol. Polycarboxylic acids or their derivatives can use dicarboxylic acids or their derivatives Examples of the derivative include terephthalic acid, isophthalic acid, dimethyl terephthalate, and dimethyl naphthalate. Polyols may be diols, and examples thereof include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol.

Specific examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polyterephthalic acid. Malonate, polytrimethylene naphthalate, cyclohexane dimethyl terephthalate, cyclohexane dimethyl polynaphthalate.

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

The (meth) acrylic resin may be a polymer having a methacrylate as a main monomer, and is preferably a copolymer copolymerized with a small amount of other comonomers. The (meth) acrylic resin is more preferably a copolymer of methyl methacrylate and methyl acrylate, and may also be copolymerized with a third functional group monomer.

Examples of the third functional single system include ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, and 2-ethyl methacrylate. Methacrylates other than methyl methacrylate such as hexyl ester, 2-hydroxyethyl methacrylate; such as ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, acrylic acid 2 -Ethylhexyl, 2-hydroxyacrylic acid Acrylates other than methyl acrylate, such as methyl ethyl acrylate; such as methyl 2- (hydroxymethyl) acrylate, methyl 2- (1-hydroxyethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, 2 -Hydroxyalkyl acrylates such as butyl (hydroxymethyl) acrylate; unsaturated acids such as methacrylic acid and acrylic acid; halogenated styrenes such as chlorostyrene and bromostyrene; such as vinyl toluene, α-formyl Substituted styrenes such as styrene; unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated acid anhydrides such as maleic anhydride and methyl maleic anhydride; such as phenyl maleic acid Unsaturated fluorene imines such as imines and cyclohexyl cis-butene difluorene imines and the like. The third functional group monomer may be used singly or in combination of two or more kinds.

The (meth) acrylic resin can be copolymerized with a polyfunctional monomer. Examples of the polyfunctional monosystem include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (Meth) acrylate, nonaethylene glycol di (meth) acrylate, tetradecane ethylene glycol di (meth) acrylate, etc. Esterification of acrylic acid; Esterification of propylene glycol or its oligomers with acrylic acid or methacrylic acid; such as neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylic acid Esters, butanediol di (meth) acrylates, etc. that esterify the hydroxyl groups of glycols with acrylic acid or methacrylic acid; bisphenol A, alkylene oxide adducts of bisphenol A, or the like Those whose two terminal hydroxyl groups of the halogen substituent are esterified with acrylic acid or methacrylic acid; those whose polyols such as trimethylolpropane and pentaerythritol are esterified with acrylic acid or methacrylic acid; Ring-opening addition to epoxy groups of propylene oxide or glycidyl methacrylate; for amber , Adipic acid, terephthalic Formic acid, phthalic acid, such dibasic acids of halogen substituted products, and such alkylene oxide adducts, etc., ring-open the epoxy group of propylene acrylate or propylene methacrylate. Additives; aryl (meth) acrylates; aromatic divinyl compounds such as divinylbenzene and the like. 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 be modified by further performing a reaction between functional groups of the copolymer. This reaction system includes, for example, a de-methanol condensation reaction in a polymer chain between a methyl group of methyl acrylate and a hydroxyl group of methyl 2- (hydroxymethyl) acrylate, and a carboxyl group of acrylic acid and 2- (hydroxymethyl). Dehydration condensation reaction in the polymer chain by the hydroxyl group of methyl acrylate and the like. The (meth) acrylic resin may have any one of a glutarimide derivative, a glutaric anhydride derivative, or a lactone ring structure.

The glass transition temperature of the (meth) acrylic resin is preferably 90 to 160 ° C, more preferably 110 to 160 ° C, and even more preferably 120 to 150 ° C.

The (meth) acrylic resin may contain an additive as needed. Examples of the additive system include a lubricant, an anti-caking agent, a heat stabilizer, an antioxidant, an antistatic agent, a light resistance agent, an impact resistance improver, and a surfactant.

From the viewpoints of film forming properties and impact resistance of the film, the (meth) acrylic resin may also contain acrylic rubber particles which are impact modifiers. The acrylic rubber particles refer to particles containing an elastic polymer whose main body is an acrylate as an essential component, and examples thereof are exemplified. For example, those having a single-layer structure consisting essentially of the elastic polymer, and those having a single-layer structure having the elastic polymer as a single layer. Examples of the elastic polymer include, for example, a crosslinked elastic copolymer mainly composed of an alkyl acrylate and copolymerized with other vinyl-based monomers and crosslinkable monomers that are copolymerizable therewith. The alkyl acrylate which is a main component of the elastic polymer includes, for example, those having an alkyl group having a carbon number of about 1 to 8 such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Acrylic acid having an alkyl group having 4 or more carbon atoms is suitably used. Examples of other vinyl-based monomers copolymerizable with the alkyl acrylate include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methyl groups such as methyl methacrylate Acrylates, aromatic vinyl compounds such as styrene, vinyl cyanide compounds such as acrylonitrile, and the like. Examples of the crosslinkable monomer include crosslinkable compounds having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, for example, ethylene glycol di (meth) acrylate and butanediol (Meth) acrylates of polyhydric alcohols such as di (meth) acrylates, alkenyl esters of (meth) acrylic acid such as allyl (meth) acrylate, divinylbenzene, and the like.

A laminate of a film made of a (meth) acrylic resin containing no rubber particles and a film made of a (meth) acrylic resin containing rubber particles can also be used as a protective film.

The retardation film is an optical film exhibiting optical anisotropy. In addition to the resin that can be used for the protective film, for example, a polyvinyl alcohol resin, a polyarylate resin, a polyimide resin, and a polyether may be used.碸 resin, polyfluorinated ethylene / polymethyl methacrylate resin, liquid crystal polymer A resin film made of an ester-based resin, an ethylene-vinyl acetate copolymer saponified product, or a polyvinyl chloride-based resin is stretched by about 1.01 to 6 times. Among these, a polycarbonate-based resin film, a cyclic polyolefin-based resin film, a (meth) acrylic-based resin film, or a cellulose-based resin film is preferably an uniaxially stretched or biaxially stretched stretched film. Moreover, in this specification, the retardation film also includes a zero retardation film (but a zero retardation film can also be used as a protective film). In addition, a film called a uniaxial retardation film, a wide viewing angle retardation film, a low photoelastic modulus retardation film, or the like may also be applied as a retardation film.

The zero-hysteresis film refers to a film in which both the in-plane retardation value R _e and the thickness direction retardation value R _th are -15 to 15 nm. The retardation film is suitable for a liquid crystal display device in an IPS mode. The in-plane retardation value R _e and the thickness direction retardation value R _th are both preferably -10 to 10 nm, and more preferably all -5 to 5 nm. R _e retardation value and the thickness direction Here, the term plane retardation value R _th value of the mean wavelength of 590nm.

The in-plane phase difference value R _e and the thickness direction phase difference value R _th are respectively defined by the following formulas: R _e = (n _x -n _y ) × d

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

In the formula, n _x is the refractive index in the slow axis direction (x-axis direction) in the film plane, n _y is the refractive index in the fast axis direction (y-axis direction perpendicular to the x-axis in the plane) in the film plane, n _z 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 a zero-lag film, for example, Resin, a polyolefin resin such as a chain polyolefin resin and a cyclic polyolefin resin, and a resin film composed of a polyethylene terephthalate or a (meth) acrylic resin. In particular, since it is easy to control and obtain a phase difference value, it is preferable to use a cellulose resin, a polyolefin resin, or a (meth) acrylic resin. For example, a one-sided or two-area layer (meth) acrylic resin layer of a retardation display layer composed of a resin different from a (meth) acrylic resin can also be used as a retardation film.

When an optical film such as a retardation film or a protective film is laminated with an adhesive layer and a glass substrate is bonded through the adhesive layer, if the moisture permeability of the optical film is small, the moisture in the adhesive layer is not easily removed, which may occur. The foaming and the like due to this moisture are particularly disadvantageous in durability under high temperature conditions. On the other hand, in the optical member with an adhesive layer of the present invention, when the optical film is used as the optical member, the optical film is measured at a temperature of 40 ° C and a relative humidity of 90% in accordance with the tea cup method specified in JIS Z 0208. When the water vapor transmission rate is 300 g / (m ² ‧24hr) or less, good durability can be exhibited. Examples of the optical film having low moisture permeability include the cyclic polyolefin resin film and the (meth) acrylic resin film disclosed above.

In addition, a film exhibiting optical anisotropy by application and alignment of a liquid crystalline compound, or a film exhibiting optical anisotropy by application of an inorganic layered compound can also be used as a retardation film. For such a retardation film, there is a film which is called a temperature-compensated retardation film and is obliquely aligned by a rod-shaped liquid crystal sold by JX Nippon Nissei Energy Co., Ltd. under the trade name "NH FILM". Disc-aligned film of disc-shaped liquid crystal sold by Fujifilm Corporation under the trade name of "WV FILM", Fully biaxially oriented membranes sold by Sumitomo Chemical Co., Ltd. under the trade name "VAC FILM", and biaxially oriented membranes also sold by Sumitomo Chemical Co., Ltd. under the trade name of "new VAC FILM" Wait.

On the other hand, the surface protective film is a film used for the purpose of protecting the surface of an optical film as a protected body from damage and contamination, such as a polarizer, a protective film, and a retardation film as an optical member for a liquid crystal display device. Various optical films, such as light-diffusing sheets, reflective sheets, and the like are usually circulated in a state where the surface protective film is bonded to the surface (when the adhesive layer is on one side, the surface opposite to the adhesive layer). . A general example of the use of the surface protective film is to peel and remove the optical film after bonding the optical film to a liquid crystal cell or the like.

Examples of the base material of the surface protective film include polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; polyvinyl fluoride, polyvinylidene fluoride, and polyvinyl fluoride Fluorinated polyolefin resins such as polyfluoroethylene; polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / m-benzene Polyester resins such as ethylene diformate copolymers; Polyamides such as nylon 6, nylon 6,6; polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol Copolymers, polyvinyl alcohol, vinyl polymers such as vinylylon; cellulose resins such as triethyl cellulose, diethyl cellulose, and cellophane; polymethyl methacrylate (Meth) acrylic resins such as esters, polyethyl methacrylate, polyethyl acrylate, polybutyl acrylate; other thermoplastic resins such as polystyrene, polycarbonate, polyarylate, and polyimide Of the film. Adhesive agent of the present invention in which the resin film is a surface protection film The optical member of the layer is one in which an adhesive layer is provided on the substrate.

The optical member with an adhesive layer according to this aspect is preferably attached to the release film on the surface of the adhesive layer and temporarily protected until the time of use. The optical member with an adhesive layer of this embodiment attached to the release film can be formed by applying an adhesive composition on the release film to form an adhesive layer, and then laminating the resin film on the obtained adhesive layer. It is manufactured by a method or a method of coating an adhesive composition on a resin film to form an adhesive layer and bonding a release film on the adhesive surface.

(2) Second embodiment

Other desirable embodiments of the optical member with an adhesive layer of the present invention are those comprising a laminated body of a resin film and an adhesive layer laminated on at least one side thereof. The laminated body of the resin film is preferably a laminated body of an optical film selected from optical films such as a polarizer, a protective film, and a retardation film. A typical example of the laminated body of an optical film is a polarizing plate. In the optical member with an adhesive layer of this embodiment, it is also preferable that a release film is attached to the surface of the adhesive layer and temporarily protected until use.

The polarizing plate includes, for example, a linear polarizing plate having a property of absorbing linearly polarized light having a vibration surface of a certain direction incident on a film surface and transmitting linearly polarized light having a vibrating surface perpendicular to the polarizing plate; A polarized light separating plate having linearly polarized light having a vibrating surface in a certain direction incident on the film surface and having the property of penetrating linearly polarized light with a vibrating surface perpendicular to the polarizing plate; an elliptical polarized light obtained by laminating a retardation film on a linearly polarizing plate Board, etc.

The linear polarizer generally has a configuration in which the protective film is bonded to one or both sides of the polarizer. When a protective film is laminated on both sides of the polarizer, an adhesive layer is formed on at least one surface of the protective film. When the protective film is laminated on only one side of the polarizer, an adhesive layer can be formed on the surface of the polarizer (the surface on which the protective film is not attached). An elliptically polarizing plate is obtained by laminating a retardation film on a linearly polarizing plate. The linearly polarizing plate generally has the same structure as described above. When the adhesive is laminated on the elliptically polarizing plate, the adhesive layer is usually laminated on the retardation film side.

A specific example of an optical member with an adhesive layer when the optical member is a polarizing plate will be described with reference to the drawings. The example shown in FIG. 1 is a polarizing plate 10 in which a protective film 3 having a surface-treated layer 2 is attached to one surface of the polarizer 1 with a surface opposite to the surface-treated layer 2. An adhesive layer 20 is provided on the surface of the polarizer 1 on the side opposite to the protective film 3 to constitute a polarizing plate (optical member with an adhesive layer) 25 with an adhesive layer. The adhesive layer 20 may be bonded to a glass substrate 30 on a surface opposite to the polarizing plate 10. The glass substrate 30 will be described later.

In the example shown in FIG. 2, the first protective film 3 having the surface-treated layer 2 is attached to one surface of the polarizer 1 with a surface on the side opposite to the surface-treated layer 2, and to the other surface of the polarizer 1. The second protective film 4 is attached to form a polarizing plate 10. An adhesive layer 20 is provided on the outer surface of the second protective film 4 to constitute a polarizing plate 25 with an adhesive layer.

In the example shown in FIG. 3, the protective film 3 having the surface-treated layer 2 is attached to one surface of the polarizer 1 with a surface opposite to the surface-treated layer 2, and the other surface of the polarizer 1 passes through the interlayer. Adhesive 8 The retardation film 7 is attached to form a polarizing plate 10. An adhesive layer 20 is provided on the outer surface of the retardation film 7 to constitute a polarizing plate 25 with an adhesive layer.

In the example shown in FIG. 4, the first protective film 3 having the surface-treated layer 2 is attached to one surface of the polarizer 1 with the surface opposite to the surface-treated layer 2 and to the other surface of the polarizer 1. A second protective film 4 is attached, and a retardation film 7 is attached to an outer surface of the second protective film 4 through an interlayer adhesive 8 to form a polarizing plate 10. An adhesive layer 20 is provided on the outer surface of the retardation film 7 to constitute a polarizing plate 25 with an adhesive layer.

The surface treatment layer 2 formed on the surface of the protective film 3 may be a hard coat layer, an anti-glare layer, an anti-reflection layer, an anti-static layer, or the like. Among these, plural layers may be provided.

As the examples shown in FIGS. 3 and 4, when the polarizing plate 10 includes the retardation film 7, a suitable example of the retardation film 7 may be a quarter-wave plate if the liquid crystal display device is a small or medium-sized liquid crystal display device. In this case, generally, the absorption axis of the polarizer 1 and the slow axis of the retardation film 7 are arranged to intersect at about 45 degrees, but depending on the characteristics of the liquid crystal cell, the angle may also be somewhat from 45 degrees The deviation. On the other hand, in the case of a large-scale liquid crystal display device such as a television, a phase difference film 7 having various phase difference values is used in accordance with the characteristics of the liquid crystal cell for the purpose of phase difference compensation or viewing angle compensation of the liquid crystal cell. In this case, generally, the absorption axis of the polarizer 1 and the slow axis of the retardation film 7 are arranged in a relationship of approximately vertical or approximately parallel. When the retardation film 7 is constituted by a 1/4 wavelength plate, a uniaxial or biaxial stretching film is suitably used. Moreover, when the retardation film 7 is provided for the purpose of phase difference compensation or viewing angle compensation of a liquid crystal cell, as far as the retardation film 7 is concerned, It is possible to use a uniaxial or biaxial stretching film, or a film that is also aligned in the thickness direction in addition to the uniaxial or biaxial stretching, or a film that is fixed by applying a phase difference display substance such as liquid crystal on a support film and fixed orientation. Compensation film.

The interlayer adhesive 8 in FIGS. 3 and 4 is generally a general (meth) acrylic adhesive, but of course, the adhesive layer of the present invention may be used. In the large-scale liquid crystal display device described above, an adhesive may be used instead of the interlayer adhesive 8 when the absorption axis of the polarizer 1 and the slow axis of the retardation film 7 are arranged in an approximately vertical or approximately parallel relationship. Examples of the adhesive include a water-based adhesive composed of an aqueous solution or an aqueous dispersion and exhibiting adhesive force by evaporating water belonging to a solvent; an ultraviolet-curable adhesive that exhibits adhesive force by being cured by ultraviolet irradiation; . Lamination of the polarizer 1 and the protective films 3 and 4 is usually performed using an adhesive.

(3) Third embodiment

Another preferable embodiment of the optical member with an adhesive layer of the present invention resides in the optical member with an adhesive layer of the first or second embodiment described above, and is further formed on the outer surface of the adhesive layer. Laminated with other optical components. The other optical member is suitable as a glass substrate. In FIGS. 1 to 4, the state in which the polarizing plate with an adhesive layer of the second embodiment is bonded to the glass substrate 30 is shown in combination.

Examples of the glass substrate 30 include a glass substrate for a liquid crystal cell, anti-glare glass, and glass for sunglasses. Examples of the material of the glass substrate 30 include soda-lime glass, low-alkali glass, and alkali-free glass. Among them, the glass substrate is preferably a glass substrate with a liquid crystal cell.

For a liquid crystal cell, a polarizing plate is usually laminated on both sides thereof via an adhesive layer. Among these polarizing plates, only the polarizing plate disposed on the front side (viewing side) of the liquid crystal cell can be the polarized light with the adhesive layer of the present invention The plate may be a polarizing plate with an adhesive layer of the present invention, or both of them may be polarizing plates with an adhesive layer of the present invention. The driving method of the liquid crystal cell may be any conventionally known method. The polarizing plate arranged on the back side (backlight side) usually does not include 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.

Optical members with an adhesive layer, such as a polarizing plate with an adhesive layer, are suitable for use in a liquid crystal display device. Liquid crystal display devices are, for example, suitable for use as personal computers including notebooks, desktops, and PDAs (personal digital assistants); various portable devices such as smart phones and tablet terminals; televisions; car displays; electronics Dictionary; digital cameras; digital video cameras; electronic desktop computers; liquid crystal display devices for clocks, etc.

[Example]

Hereinafter, the present invention will be described more specifically by showing examples and comparative examples, but the present invention is not limited to these examples. Hereinafter, "parts" and "%" indicating the amount or content used are based on weight unless otherwise specified.

In the following examples, the weight average molecular weight Mw and the number average molecular weight Mn of the (meth) acrylic resin are based on a GPC device. In this example, four "TSKgel XL" manufactured by Tosoh Co., Ltd. and one "Shodex GPC KF-802" sold by Showa Denki Co., Ltd. manufactured by Showa Denko Co., Ltd. were used in series as a column. Tetrahydrofuran was used as the eluent, and the measurement was performed by converting standard polystyrene under the conditions of a sample concentration of 5 mg / mL, a sample introduction amount of 100 μL, a temperature of 40 ° C., and a flow rate of 1 mL / minute.

<Production Example 1: Production of (meth) acrylic resin 1 for adhesive layer>

In a reaction vessel including a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirrer, 120 parts of ethyl acetate was placed, and the air in the apparatus was replaced with nitrogen to make it oxygen-free, and then the internal temperature was raised to 75 ° C. After adding 0.05 parts of azobisisobutyronitrile (polymerization initiator) dissolved in 5 parts of ethyl acetate to the entire amount, it was dropped into the reaction system over 2 hours while maintaining the internal temperature at 74 to 76 ° C. A mixed solution of 65.7 parts of butyl acrylate, 30.0 parts of methyl acrylate, 4.0 parts of 2-hydroxyethyl acrylate, and 0.3 parts of 2-carboxyethyl acrylate. Furthermore, the reaction was completed by holding at an internal temperature of 74 to 76 ° C for 5 hours. Finally, ethyl acetate was added to adjust the concentration of the (meth) acrylic resin to 40% to prepare an ethyl acetate solution of the (meth) acrylic resin 1. The obtained (meth) acrylic resin 1 had a weight average molecular weight Mw of 680,000 and a Mw / Mn of 4.9.

<Production Example 2: Production of (meth) acrylic resin 2 for adhesive layer>

In a reaction vessel including a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirrer, 120 parts of ethyl acetate was placed, and the air in the apparatus was replaced with nitrogen to make it oxygen-free, and then the internal temperature was raised to 75 ° C. After adding 0.05 parts of azobisisobutyronitrile (polymerization initiator) dissolved in 5 parts of ethyl acetate to the entire amount, it was dropped into the reaction system over 2 hours while maintaining the internal temperature at 74 to 76 ° C. A mixed solution of 50.7 parts of butyl acrylate, 45.0 parts of methyl acrylate, 4.0 parts of 2-hydroxyethyl acrylate, and 0.3 parts of 2-carboxyethyl acrylate. Furthermore, the reaction was completed by holding at an internal temperature of 74 to 76 ° C for 5 hours. Finally, ethyl acetate was added to adjust the concentration of the (meth) acrylic resin to 40% to prepare an ethyl acetate solution of the (meth) acrylic resin 2. The obtained (meth) acrylic resin 2 had a weight average molecular weight Mw of 650,000 and a Mw / Mn of 4.2.

<Production Example 3: Production of (meth) acrylic resin 3 for adhesive layer>

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, 81.8 parts of ethyl acetate, 72.2 parts of butyl acrylate, 20.0 parts of methyl acrylate, 6.0 parts of 2-hydroxyethyl acrylate, and 1.8 parts of acrylic acid were placed. After the solution was mixed, the air in the apparatus was replaced with nitrogen to be free of oxygen, and then the internal temperature was raised to 55 ° C. Then, a solution of 0.14 parts of azobisisobutyronitrile (polymerization initiator) dissolved in 10 parts of ethyl acetate was added in the entire amount. One hour after the starter was added, while the ethyl acetate was continuously added to the reaction vessel at a rate of 17.3 parts / hour so that the concentration of the (meth) acrylic resin was 35%, the internal temperature was 54 to 56 ° C. Incubate for 12 hours, Finally, ethyl acetate was added to adjust the concentration of the (meth) acrylic resin to 20% to obtain a solution of the (meth) acrylic resin 3. The obtained (meth) acrylic resin 3 had a weight average molecular weight Mw of 1.44 million and a molecular weight distribution Mw / Mn of 4.6.

<Production Example 4: Production of (meth) acrylic resin 4 for adhesive layer>

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, 81.8 parts of ethyl acetate, 91.0 parts of butyl acrylate, 5.0 parts of methyl acrylate, 4.0 parts of 2-hydroxyethyl acrylate, and 2-carboxy acrylate were placed. The mixed solution of 0.3 parts of ethyl ester was heated up to 55 ° C while replacing the air in the apparatus with nitrogen to make it oxygen-free. Then, a solution of 0.14 parts of azobisisobutyronitrile (polymerization initiator) dissolved in 10 parts of ethyl acetate was added in the entire amount. One hour after the starter was added, while the ethyl acetate was continuously added to the reaction vessel at a rate of 17.3 parts / hour so that the concentration of the (meth) acrylic resin was 35%, the internal temperature was 54 to 56 ° C. After the temperature was maintained for 12 hours, ethyl acetate was finally added to adjust the concentration of the (meth) acrylic resin to 20% to obtain a solution of the (meth) acrylic resin 4. The obtained (meth) acrylic resin 4 had a weight average molecular weight Mw of 1.44 million and a molecular weight distribution Mw / Mn of 4.6.

In addition, when the amount of each monomer used in the production of the (meth) acrylic resin 4 is converted to 100 parts by weight based on the total amount thereof, it is 90.7 parts of butyl acrylate, 5.0 parts of methyl acrylate, 4.0 parts of 2-hydroxyethyl acrylate, and 0.3 parts of 2-carboxyethyl acrylate.

<Examples 1 to 10, Comparative Examples 1 to 5>

(1) Preparation of adhesive composition

To 100 parts of the solid content of the (meth) acrylic resin (A) obtained in Production Examples 1 to 4 above, the compound (B) and the crosslinking agent (C) shown in Table 2 were mixed in the amounts shown in Table 2 respectively. ), The ionic compound (D) and the silane compound (E), and further, ethyl acetate is added, and when the (meth) acrylic resin 1 or 2 is used, the solid content concentration becomes 28%. In the case of the (meth) acrylic resin 3 or 4, the solid content concentration is adjusted to 14% to prepare a solution of the adhesive composition.

In Table 2, the details of each of the compounded components indicated by abbreviations are as follows.

[Compound (B)]

Refer to Table 3 below.

[Crosslinking agent (C)]

C1: Ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate (solid content concentration 75%), "CORONATE L" obtained from Japan Polyurethane Co., Ltd .; C2: hexamethylene diisocyanate Isocyanurate, a liquid with an active ingredient of about 100%, "CORONATE HXR" obtained from Japan Polyurethane Co., Ltd.

[Ionic compound (D)]

AS1: N-octyl-4-methylpyridinium hexafluorophosphate (melting point 44 ° C), AS2: grade 4 ammonium bis (trifluoromethanesulfonyl) phosphonium imine (melting point 34 ° C).

[Silane compound (E)]

S1: 3-glycidoxypropyltrimethoxysilane (liquid), "KBM403" obtained from Shin-Etsu Chemical Industry Co., Ltd.

(2) Production of adhesive layer

Each adhesive composition prepared in the above (1) was applied to a separator made of polyethylene terephthalate subjected to a release treatment using an applicator [obtained from "LINTEC Corporation" PLR-382051 "], the release-treated surface was dried to a thickness of 20 µm, and dried at 100 ° C for 1 minute to prepare an adhesive layer (adhesive sheet).

(3) Production of a protective film made of (meth) acrylic resin

A copolymer of methyl methacrylate / methyl acrylate (weight ratio of 96/4) was prepared as a (meth) acrylic resin. In addition, elastomer particles having the following three-layer structure were prepared as rubber particles. The innermost layer was a hard polymer polymerized by using methyl methacrylate and a small amount of allyl methacrylate, and the intermediate layer was made of butyl acrylate. A soft elastomer formed by polymerizing styrene and a small amount of allyl methacrylate as the main component, and a hard polymer polymerized by using a small amount of ethyl acrylate in methyl methacrylate. The average particle diameter up to the elastomer of the intermediate layer was 240 nm.

A benzotriazole-based ultraviolet absorber is added to particles prepared by the weight ratio of the former / the latter = 70/30 of the aforementioned (meth) acrylic resin and rubber particles, and melt-kneaded by a biaxial extruder. At the same time, 100 parts of the particles were mixed and added with 0.05 parts of stearic acid as a lubricant to make particles of a resin composition. The pellets were put into a 65 mm φ uniaxial extruder, extruded through a T-die set at a temperature of 275 ° C, and both sides of the extruded film-like molten resin were set to a mirror surface having a temperature of 45 ° C. The two polishing rollers were sandwiched and cooled, and a protective film made of (meth) acrylic resin with a thickness of 75 μm was produced.

(4) Fabrication of polarizing plate with adhesive layer

A protective film made of (meth) acrylic resin produced in (3) above was bonded to one side of a polarizer having a thickness of 23 μm by iodine adsorption and alignment with a polyvinyl alcohol film extending on one axis, through an adhesive. And a 50 μm-thick retardation made of a cyclic polyolefin resin is bonded on the other side Film to make a polarizing plate. Then, on the outer surface of the retardation film, the surface of the adhesive layer produced in (2) above on the opposite side of the separator was bonded by a laminator, and then cured at 23 ° C and 65% relative humidity for 7 days. A polarizing plate with an adhesive layer was obtained.

(5) Evaluation of durability

After peeling off the separator from the polarizer with the adhesive layer prepared in the above (4), the adhesive layer was attached to both sides of a glass substrate for a liquid crystal cell ("Eagle XG" by Corning Corporation) so that it intersected. Cross Nicol, making samples for evaluation. Using this sample, the following three types of durability tests were performed.

[Durability test]

‧Heat resistance test for 1000 hours at a temperature of 80 ℃; ‧Heat and heat resistance test for 1000 hours under an environment of temperature of 60 ℃ and relative humidity of 90%; It was maintained at 40 ° C. for 30 minutes as one cycle, and the heat shock (HS) test was repeated for 500 cycles.

The samples after each test were visually observed, and the durability was evaluated according to the evaluation criteria described below. The results are shown in Table 4.

A: I ca n’t see any changes in appearance such as floating, peeling, and foaming.

B: Almost no change in appearance such as floating, peeling, and foaming

C: Slight changes in appearance such as floating, peeling, and foaming

D: Significant changes in appearance such as floating, peeling, and foaming

(6) Evaluation of heavy industry

The polarizing plate with an adhesive layer produced in the above (4) was cut into a test piece of 25 mm × 150 mm. Then, the separator was peeled from the test piece, and the adhesive layer was attached to a glass substrate for a liquid crystal cell ["Eagle XG" manufactured by Corning Corporation] at a temperature of 50 ° C and a pressure of 5 kg / cm ² (490.3 kPa). Autoclave treatment was carried out for 20 minutes. Then, hold it in an oven at a temperature of 50 ° C for 50 hours, and then place the polarizer and the adhesive layer together at 300 mm / minute from the test piece attached to the glass substrate under the environment of a temperature of 23 ° C and a relative humidity of 50%. The peeling test was performed at a speed of 180 degrees (a direction parallel to the glass substrate surface when the polarizing plate was peeled and turned upside down). The state of the surface of the glass substrate after the peeling test was visually observed, and reworkability was evaluated according to the following evaluation criteria. The results are shown in Table 4.

A: It is impossible to see the blur and adhesive residue on the surface of the glass substrate

B: It is almost impossible to see the blur and adhesive on the surface of the glass substrate

C: Although the glue on the surface of the glass substrate can hardly be seen, the blur can be seen

D: Residual glue can be seen on the surface of the glass substrate

(7) Measurement of gel fraction of the adhesive layer

After the adhesive layer (adhesive sheet) prepared in the above (2) was left at room temperature for 1 day and after being left for 8 days, the gel fraction was measured. Results are shown in Table 4. The gel fraction was measured according to the following [a] to [d].

[a] An adhesive layer having an area of about 8 cm × about 8 cm is bonded to a metal mesh (whose weight is Wm) made of SUS304 and about 10 cm × about 10 cm.

[b] Weigh the paste obtained in [a] above, whose weight is Ws, and then fold it 4 times to cover the adhesive layer. After fixing it with a stapler, weigh it and weigh it is Wb.

[c] The net fixed with the stapler [b] above was placed in a glass container, 60 ml of ethyl acetate was added and impregnated, and the glass container was stored at room temperature for 3 days.

[d] Take the net out of the glass container, and measure it after drying at 120 ° C for 24 hours. Its weight is Wa. Calculate the gel fraction according to the following formula: Gel fraction (wt%) = [{Wa- (Wb- Ws) -Wm} / (Ws-Wm)] × 100

(8) Evaluation of antistatic property of polarizing plate with adhesive layer

When the separator of the polarizing plate with an adhesive layer produced in the above (4) was peeled off, the surface resistance value of the adhesive layer was measured using a surface intrinsic resistance measuring device ["Hirest-up MCP-HT450" manufactured by Mitsubishi Chemical Corporation]. Assess antistatic properties. When the surface resistance value is 10 ¹¹ Ω / □ or less, good antistatic properties can be obtained. The evaluation of the antistatic property was performed immediately after the curing of the polarizer with the adhesive layer was completed. The results are shown in Table 4.

(9) Measurement of peeling force of separator (release film)

The polarizing plate with an adhesive layer produced in the above (4) was cut into a test piece of 25 mm × 150 mm. Then, at a temperature of 23 ℃, relative humidity of 50%, the separator is peeled from the test piece at a speed of 300mm / min to a direction of 180 degrees, peel test, peel force was measured in the partition P _0. The peeling force P ₁ of the peeling film after the heating test held at 70 ° C. for 20 days was also measured under the same conditions, and the peeling force increase rate was calculated according to the following formula: peeling force increase rate (%) = (P ₁ / P ₀ ) × 100; the results are shown in Table 4.

<Production Example 5: Production of (meth) acrylic resin 5 for adhesive layer>

In a reaction vessel including a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirrer, 120 parts of ethyl acetate was placed, and the air in the apparatus was replaced with nitrogen to make it oxygen-free, and then the internal temperature was raised to 75 ° C. After adding 0.05 parts of azobisisobutyronitrile (polymerization initiator) dissolved in 5 parts of ethyl acetate to the entire amount, it was dropped into the reaction system over 2 hours while maintaining the internal temperature at 74 to 76 ° C. A mixed solution of 50.6 parts of butyl acrylate, 40.0 parts of methyl acrylate, 4.0 parts of 2-phenoxyethyl acrylate, 4.0 parts of 2-hydroxyethyl acrylate, and 1.4 parts of acrylic acid. Furthermore, the reaction was completed by holding at an internal temperature of 74 to 76 ° C for 5 hours. Finally, ethyl acetate was added to adjust the concentration of the (meth) acrylic resin to 40% to prepare an ethyl acetate solution of the (meth) acrylic resin 5. The obtained (meth) acrylic resin 5 had a weight average molecular weight Mw of 700,000 and a Mw / Mn of 5.8.

<Production Example 6: Production of (meth) acrylic resin 6 for adhesive layer>

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, 81.8 parts of ethyl acetate, 35.0 parts of methyl acrylate, 6.0 parts of 2-phenoxyethyl acrylate, and 2.0 parts of 2-hydroxyethyl acrylate were placed. The mixed solution of 1.0 part of acrylic acid and acrylic acid was heated up to 55 ° C. while replacing the air in the apparatus with nitrogen to make it oxygen-free. Then, a solution of 0.14 parts of azobisisobutyronitrile (polymerization initiator) in 10 parts of ethyl acetate was dissolved. Add in full. One hour after the starter was added, while the ethyl acetate was continuously added to the reaction vessel at a rate of 17.3 parts / hour so that the concentration of the (meth) acrylic resin was 35%, the internal temperature was 54 to 56 ° C. After incubation for 12 hours, ethyl acetate was added at the end to adjust the concentration of the (meth) acrylic resin to 20% to obtain a solution of the (meth) acrylic resin 6. The obtained (meth) acrylic resin 6 had a weight average molecular weight Mw of 1.54 million and a molecular weight distribution Mw / Mn of 5.8.

<Examples 11 to 22, Comparative Examples 6 to 7>

(1) Preparation of adhesive composition

For 100 parts of the solid content of the (meth) acrylic resin (A) obtained in Production Examples 5 to 6, the compounds (B) and the cross-linking agent (C) shown in Table 5 were mixed in the amounts shown in Table 5 respectively. ), An ionic compound (D) and a silane compound (E), and further, ethyl acetate was added. When using (meth) acrylic resin 5, the solid content concentration was 28%. In the case of acrylic resin 6, the solid content concentration is set to 14% to prepare a solution of the adhesive composition.

In Table 5, the details of the compound (B) represented by abbreviations of EO6 to EO9 are shown in Table 6 below. The details of the abbreviations EO3, EO5, C1, AS1 and S1 are as described above.

(2) Production of polarizing plate with adhesive layer and evaluation of durability and reworkability

An adhesive layer (adhesive sheet) was prepared by using each of the adhesive compositions prepared in the above (1) in the same procedure as described in the above (2) of <Examples 1 to 10 and Comparative Examples 1 to 5>. This adhesive layer and the protective film made of a (meth) acrylic resin produced in (3) of the above (Examples 1 to 10 and Comparative Examples 1 to 5) were used to make the same as the above (Examples 1 to 10). In the same order as described in (4) of Comparative Examples 1 to 5>, a polarizing plate with an adhesive layer was produced. For the obtained polarizing plate with an adhesive layer, according to the above-mentioned <Examples 1 to 10 and Comparative Example 1 (5) and (6) to 5> to evaluate durability and weight Workability. The results are shown in Table 7.

Claims (15)

An adhesive composition comprising: 100 parts by weight of a (meth) acrylic resin (A); and a compound (B) containing at least one double bond and at least one alkylenedioxy in a molecule. 0.15 to 8 parts by weight; the aforementioned compound (B) includes the compound (B-1) represented by the following formula (B-1), 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 alkylene dioxy group. The aforementioned Q ⁰ is selected from the following Q ⁰¹ , Q At least one of the bases shown in ⁰³ and Q ⁰⁴ , In Q ⁰¹ , Q ² represents an alkyl, aryl or aralkyl group having 1 to 4 carbon atoms which may be substituted by an alkoxy group having 1 to 3 carbon atoms, and L represents a single bond or an alkylene group having 1 to 4 carbon atoms. Group, i represents an integer of 7 to 50, the carbon number of the aryl group which can be Q ² is 6 to 20, and the carbon number of the aralkyl group is 7 to 20; in Q ⁰³ , y and z each independently represent 1 to An integer of 40, y + z is an integer of 1 to 40. In Q ⁰⁴ , e, f, and g each independently represent an integer of 1 to 20, and e + f + g is an integer of 1 to 30. An adhesive composition comprising: 100 parts by weight of a (meth) acrylic resin (A); and a compound (B) containing at least one double bond and at least one alkylene dioxy group in a molecule of 0.15 to 8 Parts by weight; the aforementioned compound (B) is composed only of the compound (B-1) represented by the following formula (B-1), and the molecular weight of the aforementioned compound (B) is 400 or more, 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 alkylene dioxy group; the aforementioned Q ⁰ is a group represented by the following Q ⁰² , In Q ⁰² , j represents an integer from 1 to 40. The adhesive composition according to item 1 or 2 of the scope of patent application, wherein the molecular weight of the compound (B) is 3,000 or less. The adhesive composition according to item 1 or 2 of the scope of patent application, wherein the alkylene dioxy group is a linear or branched alkylene dioxy group having 1 to 3 carbon atoms. The adhesive composition according to item 1 or 2 of the scope of the patent application, wherein the above-mentioned alkylene dioxy group is an ethylene dioxy group. The adhesive composition according to item 1 of the scope of patent application, wherein the compound (B-1) is a compound (B-1a) represented by the following formula (B-1a): In the formula, Q ¹ represents a hydrogen atom or a methyl group, L represents a single bond or an alkylene group having 1 to 4 carbon atoms, i represents an integer of 7 to 50, and Q ² represents an alkoxy group having 1 to 3 carbon atoms. Alkyl, aryl or aralkyl having 1 to 4 carbons. The adhesive composition according to item 1 or 2 of the scope of patent application, wherein the weight average molecular weight Mw of the (meth) acrylic resin (A) is from 500,000 to 1.7 million. The adhesive composition according to item 1 or 2 of the scope of patent application, further comprising: a cross-linking agent (C); wherein the content of the cross-linking agent (C) is relative to that of the (meth) acrylic resin ( A) 100 parts by weight and 0.1 to 5 parts by weight. The adhesive composition according to item 1 or 2 of the scope of patent application, further comprising: an ionic compound (D); wherein the content of the ionic compound (D) is relative to the (meth) acrylic resin ( A) 100 parts by weight and 0.3 to 5 parts by weight. An adhesive layer includes the adhesive composition according to any one of claims 1 to 9 of the scope of patent application. An optical member with an adhesive layer includes an optical member and an adhesive layer as described in item 10 of the scope of the patent application, which is laminated on the optical member. The optical component with an adhesive layer according to item 11 of the scope of the patent application, wherein the optical component includes a polarizer. According to the eleventh or twelfth aspect of the patent application scope, the optical member with an adhesive layer further includes a release film laminated on the outer surface of the aforementioned adhesive layer. According to the optical component with an adhesive layer described in item 13 of the scope of the patent application, wherein the peeling force of the peeling film after the heat test at 70 ° C for 20 days is P ₁ , and the peeling force before the heat test is At P ₀ , the peeling force increase rate defined by the following formula is 200% or less: the peeling force increase rate (%) = (P ₁ / P ₀ ) × 100. According to the eleventh or twelfth aspect of the patent application scope, the optical member with an adhesive layer further includes: a glass substrate laminated on the outer surface of the aforementioned adhesive layer.