TW201741130A - Optical laminate, liquid display device, adhesive composition and optical film - Google Patents

Abstract

The present invention provides an optical laminate and a liquid crystal display device including the same. The optical laminate comprises an optical film and an adhesive layer and a metal layer in this order, the metal layer is a metal wiring layer, the adhesive layer is formed of an adhesive composition containing a (meth) acrylic resin (A), an isocyanate crosslinking agent (B), a silane compound (C), and an ionic compound (D) represented by the formula: M<SP>+</SP> X<SP>-</SP>(M<SP>+</SP> represents an inorganic cation, X<SP>-</SP> represents a fluorine-containing anion), wherein, relative to 100 parts by weight of the (meth) acrylic resin (A), the adhesive composition contains the isocyanate crosslinking agent (B) 0.01 to 2.5 parts by weight, the silane compound (C) 0.01 to 10 parts by weight, and the ionic compound (D) 0.2 to 8 parts by weight.

Description

Optical laminate, liquid crystal display device, adhesive composition, and optical film

The present invention relates to an optical layered body of an image display device that constitutes a liquid crystal display device or the like, and a liquid crystal display device including the optical layered body.

An optical film typified by a polarizing plate in which a transparent resin film is bonded to one side or two layers of a polarizing plate is widely used as an optical member constituting an image display device such as a liquid crystal display device. The optical film of such a polarizing plate is often used by being bonded to another member (for example, a liquid crystal cell of a liquid crystal display device) via an adhesive layer (for example, refer to JP-A-2010-229321). Therefore, as an optical film, an optical film in which an adhesive layer of an adhesive layer is provided in advance on one surface thereof is known. Further, it is also known to contain an ionic compound in the adhesive layer in order to impart antistatic properties.

In recent years, the liquid crystal display device has been applied to a mobile device having a touch panel function typified by a smart phone, a tablet terminal, and a car navigation system. Such a touch input type liquid crystal display device The optical film with the adhesive layer attached thereto is a metal layer composed of, for example, a metal wiring, for example, a resin layer or a direct contact. However, in a combination of a metal layer composed of a metal material and an adhesive layer containing an ionic compound, the metal layer is corroded in a high-temperature and high-humidity environment. Pitting corrosion in corrosion, when the thickness of the metal layer is thin or when the metal layer is metal wiring, the line width is narrow, which is particularly problematic because it penetrates the metal layer.

An object of the present invention is to provide an optical layered body in which an optical film having an adhesive layer is laminated on a metal layer of a metal wiring layer, an optical layered body which can suppress corrosion of a metal layer, and a liquid crystal display device including the optical layered body.

The present invention provides an optical layered body shown below and a liquid crystal display device comprising the same, and an adhesive composition.

[1] An optical laminate comprising, in order, an optical film, an adhesive layer, and a metal layer; wherein the adhesive layer comprises a (meth)acrylic resin (A), an isocyanate crosslinking agent (B), The decane compound (C) and the ionic compound (D) represented by the following formula (I) are composed of an adhesive composition, M ⁺ X ^- (I) (in the formula (I), M ⁺ represents an inorganic cation, X ^- the anion containing a fluorine atom; the adhesive composition contains 0.01 to 2.5 parts by weight of the above isocyanate crosslinking agent (B), based on 100 parts by weight of the (meth)acrylic resin (A), 0.01 to 10 parts by weight of the aforementioned decane compound (C) and 0.2 to 8 parts by weight of the ionic compound (D).

[2] The optical layered product according to [1], wherein the inorganic cation is an alkali metal cation or an alkaline earth metal cation.

[3] The optical layered body according to [1] or [2] wherein the alkali metal cation is a lithium cation [Li ⁺ ], a potassium cation [K ⁺ ] or a sodium cation [Na ⁺ ].

[4] The optical layered body according to [1] or [2] wherein the alkali metal cation is a potassium cation [K ⁺ ].

[5] The optical layered product according to any one of [1], wherein the fluorine atom-containing anion is a fluorine atom-containing anion represented by the following formula (II): [Y(SO ₂ C) _m F _2m+1 ) _n ] ^- (II) (In the formula (II), Y represents a carbon atom or a nitrogen atom, Y represents a carbon atom, n is 3, Y represents a nitrogen atom, n is 2, and m represents 0 to 10 Integer).

[6] The optical layered product according to any one of [1], wherein the fluorine atom-containing anion is a bis(fluorosulfonyl)imide anion [(FSO ₂ ) ₂ N ^- ] or a double (Trifluoromethanesulfonyl) imine anion [(CF ₃ SO ₂ ) ₂ N ^- ].

[7] The optical layered product according to any one of [1] to [5] wherein the fluorine atom-containing anion is bis(fluorosulfonyl)imide anion [(FSO ₂ ) ₂ N ^- ].

[8] The optical layered product according to any one of [1], wherein the (meth)acrylic resin (A) contains an alkyl acrylate having a glass transition temperature of less than 0 ° C from a homopolymer. The constituent unit of (a1) and the constituent unit of the alkyl acrylate (a2) having a glass transition temperature of 0 ° C or higher from the homopolymer.

[9] The optical layered product according to [8], wherein the content of the constituent unit derived from the alkyl acrylate (a2) of the (meth)acrylic resin (A) is a (meth)acrylic resin ( In all of 100 parts by weight of all the constituent units of A), it is 10 parts by weight or more.

[10] The optical laminate according to [8], wherein the alkyl acrylate (a2) comprises methyl acrylate.

[11] The optical layered product according to any one of [1] to [10] wherein the (meth)acrylic resin (A) contains a constituent unit derived from a monomer having a hydroxyl group.

[12] The optical layered product according to any one of [1] to [11] wherein the (meth)acrylic resin (A) does not substantially contain a constituent unit derived from a monomer having a carboxyl group.

[13] The optical laminate according to any one of [1] to [12] wherein The adhesive composition does not substantially contain a triazole-based compound, a thiazole-based compound, an imidazole-based compound, an imidazoline-based compound, a quinoline-based compound, a pyridine-based compound, a pyrimidine-based compound, or an anthracene. A rust inhibitor in which a compound, an amine compound, a urea compound, sodium benzoate, a benzylthiol compound, di-butyl butyl sulfide, and diphenylarylene are grouped.

[14] The optical laminate according to any one of [1] to [13] wherein the metal layer comprises aluminum, copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and One or more types of the alloys of two or more kinds of metals selected from the above are included.

[15] The optical layered body according to any one of [1] to [14] wherein the metal layer contains an aluminum element.

[16] The optical layered body according to any one of [1] to [15] wherein the metal layer is a layer formed by sputtering.

[17] The optical layered product according to any one of [1] to [16] wherein the thickness of the metal layer is 3 μm or less.

[18] A liquid crystal display device comprising the optical layered body according to any one of [1] to [17].

[19] An adhesive composition containing 0.01 to 2.5 parts by weight of the isocyanate crosslinking agent (B) and 0.01 to 10 parts by weight based on 100 parts by weight of the (meth)acrylic resin (A). a decane compound (C) and 0.2 to 8 parts by weight of an ionic compound (D) represented by the following formula (I): M ⁺ X ^- (I) (in the formula (I), M ⁺ represents an inorganic cation, X ^- The anion composition containing a fluorine atom is used for forming an adhesive layer to be laminated on a metal layer.

According to the invention, it is possible to provide an optical layered body capable of suppressing corrosion of a metal layer and a liquid crystal display device including the same.

1‧‧‧Optical film with adhesive layer

2‧‧‧ polarizer

3‧‧‧1st resin film

4‧‧‧2nd resin film

5, 6, 7‧‧‧ Optical laminates

10‧‧‧Optical film

10a, 10b‧‧‧ polarizing plate

20‧‧‧Adhesive layer

30‧‧‧metal layer

40‧‧‧Substrate

50‧‧‧ resin layer

Fig. 1 is a schematic cross-sectional view showing an example of an optical layered body of the present invention.

Fig. 2 is a schematic cross-sectional view showing an example of a layer configuration of a polarizing plate.

Fig. 3 is a schematic cross-sectional view showing another example of the layer configuration of the polarizing plate.

Fig. 4 is a schematic cross-sectional view showing an example of a layer configuration of an optical layered body.

Fig. 5 is a schematic cross-sectional view showing another example of the layer constitution of the optical layered body.

Fig. 6 is a schematic cross-sectional view showing another example of the layer constitution of the optical layered body.

Fig. 7 is a schematic cross-sectional view showing another example of the layer constitution of the optical layered body.

<optical laminate>

Fig. 1 is a schematic cross-sectional view showing an example of an optical layered body of the present invention. As shown in FIG. 1, the optical layered body of the present invention includes the optical film 10, the adhesive layer 20, and the metal layer 30 in this order, and may further include a substrate 40. The optical layered body may be an optical film 1 having an adhesive layer of the adhesive layer 20 including the optical film 10 and the surface laminated on at least one side of the metal layer 30 formed on the substrate 40, The adhesive layer 20 is bonded to each other.

The adhesive layer 20 is usually laminated directly on the surface of the optical film 10. Further, the optical film 1 to which the adhesive layer is usually attached is such that the adhesive layer 20 is laminated on the metal layer 30 in such a manner as to directly contact the metal layer 30. According to the present invention, corrosion of the metal layer 30 can be effectively suppressed in such an optical layered body. Hereinafter, the property of corrosion of the metal layer 30 can be suppressed, which is also referred to as "metal corrosion resistance".

The optical film 10 may be an optical film having a single layer structure or an optical film having a multilayer structure. The adhesive layer 20 is composed of an adhesive composition containing a (meth)acrylic resin (A), an isocyanate crosslinking agent (B), a decane compound (C), and an ionic compound (D). The adhesive composition may further contain other ingredients. In the present specification, the term "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The same applies to "(meth) acrylate" and "(meth) acryl thiol".

[1] optical film

The optical film 10 provided in the optical layered product of the present invention is an optical member constituting the optical film 1 with an adhesive layer, and can be various optical films (having optical characteristics) that can be incorporated into an image display device such as a liquid crystal display device. Membrane). The optical film 10 may be an optical film having a single layer structure or an optical film having a multilayer structure. Specific examples of the optical film having a single-layer structure include an optical functional film such as a retardation film, a brightness enhancement film, an anti-glare film, an anti-reflection film, a diffusion film, and a light-concentrating film, in addition to the polarizer. Specific examples of the optical film having a multilayer structure include a polarizing plate and a phase difference plate. In the present specification, the polarizing plate refers to an area layer resin film or a resin layer of at least one side of the polarizing plate. The phase difference plate refers to an area layer resin film or a resin layer of at least one side of the retardation film. The optical film 10 is preferably a polarizing plate, a polarizing plate, a phase difference plate or a retardation film, and more preferably a polarizing plate or a polarizing plate.

[1-1] Polarizer

2 and 3 are schematic cross-sectional views showing an example of a layer configuration of a polarizing plate. The polarizing plate 10a shown in Fig. 2 is a polarizing plate which is bonded to one side of the first resin film 3 in the area layer on one side of the polarizing plate 2, and the polarizing plate 10b shown in Fig. 3 is attached to the polarizing plate. The other side of the surface of the second resin film 4 is laminated to the polarizing plate which is protected by both surfaces of the second resin film 4. The first and second resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer or an adhesive layer (not shown). The polarizing plates 10a and 10b may include other films and layers other than the first and second resin films 3 and 4.

The polarizing plates 10a and 10b shown in Figs. 2 and 3 are Examples of the layer configuration of the optical layered body used as the optical film are shown in Figs. 4 and 5, respectively. The optical layered body 5 shown in Fig. 4 is an example in which the polarizing plate 10a shown in Fig. 2 is used as an optical film, and the optical layered body 6 shown in Fig. 5 is a polarized light shown in Fig. 3. The plate 10b is used as an example of an optical film.

The polarizer 2 is provided with a film that absorbs linearly polarized light having a vibrating surface parallel to its absorption axis and penetrates a linearly polarizing property having a vibrating surface having a vertical absorption axis (parallel to the transmission axis), and can be used, for example, for a polyvinyl alcohol resin. The membrane adsorbs a film that is aligned to the dichroic pigment. As the dichroic dye, iodine or a dichroic organic dye can be used.

The polyvinyl alcohol-based resin can be obtained by saponifying a polyvinyl acetate-based resin. The polyvinyl acetate-based resin may, for example, be a copolymer of a monomer copolymerizable with vinyl acetate and vinyl acetate, in addition to polyvinyl acetate of a single polymer of vinyl acetate. As a monomer copolymerizable with vinyl acetate, for example, an unsaturated carboxylic acid, an olefin, a vinyl ether, an unsaturated sulfonic acid, a (meth) acrylamide having an ammonium group, or the like.

The degree of saponification of the polyvinyl alcohol-based resin is usually from 85 to 100 mol%, more preferably 98 mol% or more. The polyvinyl alcohol-based resin can be modified, and for example, an aldehyde-modified polyvinyl formal or polyvinyl acetal can be used. The average degree of polymerization of the polyvinyl alcohol-based resin is usually from 1,000 to 10,000, more preferably from 1,500 to 5,000. The average degree of polymerization of the polyvinyl alcohol-based resin can be determined in accordance with JIS K 6726.

Usually, a film made of a polyvinyl alcohol-based resin is used as a raw material film of the polarizer 2. Polyvinyl alcohol resin, can be used in the known side Film made by law. The thickness of the raw material film is usually from 1 to 150 μm, and is preferably 10 μm or more in consideration of easiness of stretching and the like.

The polarizer 2 is, for example, a step of performing a shaft stretching on the raw material film, a step of dyeing the film with a dichroic dye to adsorb the dichroic dye, a step of treating the film with a boric acid aqueous solution, and a step of washing the film, and finally drying the film. Manufacturing. The thickness of the polarizing plate 2 is usually 1 to 30 μm, and is preferably 20 μm or less, more preferably 15 μm or less, and still more preferably 10 μm or less from the viewpoint of thinning of the optical film 1 with an adhesive layer.

The polarizer 2 obtained by adsorbing a dichroic dye to a polyvinyl alcohol-based resin film is a single-layer stretching treatment and dichroism by using a single film of a polyvinyl alcohol-based resin film as a raw material film. a method of dyeing a dye and 2) applying a coating liquid (aqueous solution or the like) containing a polyvinyl alcohol-based resin to a base film, and drying the base film to obtain a base film having a polyvinyl alcohol-based resin layer This is obtained by performing a one-axis stretching together with the base film, and performing a dyeing treatment on the stretched polyvinyl alcohol-based resin layer by dichroic dye, and then peeling off the base film. As the base film, a film composed of a thermoplastic resin similar to the thermoplastic resin constituting the first and second resin films 3 and 4 described later can be used, and a polyester resin such as polyethylene terephthalate is preferable. A film composed of a polycarbonate resin such as a polycarbonate resin or triethyl fluorenyl cellulose, a cyclic polyolefin resin such as a decene-based resin, or a polystyrene resin. According to the method of the above 2), the production of the polarizer 2 of the film is facilitated, and the polarizer 2 having a thickness of, for example, 7 μm or less can be easily produced.

The first and second resin films 3 and 4 are each independently transparent The optical property is preferably an optically transparent thermoplastic resin such as a polyolefin resin (such as a polyethylene resin or a polypropylene resin) or a polyolefin resin having a cyclic polyolefin resin (such as a decene-based resin). Resin; cellulose resin (such as cellulose ester resin); polyester resin (polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, etc.); A carbonate resin; a (meth)acrylic resin; a polystyrene resin; a polyetheretherketone resin; a polyfluorene-based resin; or a film composed of such a mixture or a copolymer. In addition, each of the first and second resin films 3 and 4 is selected from the group consisting of a cyclic polyolefin resin, a polycarbonate resin, a cellulose resin, a polyester resin, and a (meth)acrylic resin. Preferably, the resin is preferably composed of a resin selected from the group consisting of a cellulose resin and a cyclic polyolefin resin.

The chain-like polyolefin resin may be a copolymer of two or more kinds of chain olefins, in addition to a homopolymer of a chain olefin such as a polyethylene resin or a polypropylene resin.

The cyclic polyolefin-based resin is a general term for a resin containing a norbornene, tetracyclododecene (alias: dimethicone) or a cyclic olefin represented by such a derivative as a polymerization unit. Specific examples of the cyclic polyolefin-based resin include a ring-opened (co)polymer of a cyclic olefin, a hydrogenated product thereof, an addition polymer of a cyclic olefin, a cyclic olefin, and a chain olefin such as ethylene or propylene. Or a copolymer of an aromatic compound having a vinyl group and such a modified (co)polymer modified with an unsaturated carboxylic acid or a derivative thereof. Among them, as the cyclic olefin, a norbornene-based resin having a norbornene-based monomer such as a norbornene or a polycyclic norbornene-based monomer is preferably used.

The cellulose resin is preferably a cellulose ester resin, that is, a partial or complete esterified product of cellulose, such as cellulose acetate, propionate, butyrate, or a mixed ester thereof. Among them, triethylenesulfonyl cellulose, diethylstilbene cellulose, cellulose acetate propionate, cellulose acetate butyrate or the like is preferably used.

The polyester resin is a resin other than the cellulose ester resin having an ester bond, and is generally composed of a polycondensate of a polyvalent carboxylic acid or a derivative thereof and a polyhydric alcohol. Specific examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polybutylene terephthalate. Ester, propylene naphthalate, dimethyl dimethyl terephthalate, cyclohexane dimethyl phthalate.

The polycarbonate resin is a polyester formed of carbonic acid and a diol or bisphenol. Among them, from the viewpoint of heat resistance, weather resistance, and acid resistance, it is preferred to use an aromatic carbonate having a diphenyl alkane in a molecular chain. As the polycarbonate, for example, is, for example, 2,2-bis(4-hydroxyphenyl)propane (alias: bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 1,1-double ( A bisphenol-derived polycarbonate such as 4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)isobutane or 1,1-bis(4-hydroxyphenyl)ethane.

The (meth)acrylic resin which can constitute the first and second resin films 3 and 4 may be a polymer mainly composed of a constituent unit derived from methacrylate (for example, containing 50% by weight or more), and is preferably a copolymer copolymerized with other copolymerization components. The (meth)acrylic resin contains two or more constituent units derived from methacrylate. As the methacrylate, for example, a C ₁ to C ₄ alkyl ester of a methacrylate such as methyl methacrylate, ethyl methacrylate or butyl methacrylate.

As the copolymerizable component copolymerizable with the methacrylate, an acrylate is exemplified. The acrylate is preferably a C ₁ to C ₈ alkyl acrylate such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate. Specific examples of the other copolymerization component are, for example, unsaturated acids such as (meth)acrylic acid; aromatic vinyl compounds such as styrene, halogenated styrene, α-methylstyrene, and vinyltoluene; (meth)acrylic acid; Vinyl cyanide such as nitrile; unsaturated acid anhydride such as maleic anhydride or methyl maleic anhydride; unsaturated quinone imide such as phenyl maleimide or cyclohexylmaleimide A compound other than the acrylate having one polymerizable carbon-carbon double bond in the molecule. A compound having two or more polymerizable carbon-carbon double bonds in the molecule may also be used as the copolymerization component. The copolymerization component may be used alone or in combination of two or more.

The (meth)acrylic resin may have a ring structure in the polymer main chain at the point of improving the durability of the film. The ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic quinone imine structure, or a lactone ring structure. Specific examples of the cyclic acid anhydride structure include, for example, a glutaric anhydride structure and a succinic anhydride structure, and specific examples of the cyclic quinone imine structure, for example, a pentaneimine structure and an amber quinone structure, and a lactone ring structure. For example, a butyrolactone ring structure and a valerolactone ring structure.

The (meth)acrylic resin may contain acrylic rubber particles from the viewpoints of film forming properties of the film and impact resistance of the film. The acrylic rubber particles are particles in which an elastic polymer mainly composed of an acrylate is an essential component, and for example, a single-layer structure consisting essentially of the elastic polymer or a layer of the elastic polymer is used. Multi-layer constructor. As an example of the elastic polymer, for example, a crosslinked elastic copolymer in which an alkyl acrylate is used as a main component and copolymerized with another vinyl monomer and a crosslinkable monomer copolymerizable therewith is used. The alkyl acrylate which is a main component of the elastic polymer may, for example, be a C ₁ to C ₈ alkyl acrylate such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate. The carbon number of the alkyl group is preferably 4 or more.

As the other vinyl monomer copolymerizable with the alkyl acrylate, for example, a compound having one polymerizable carbon-carbon double bond in the molecule, more specifically, a methacrylate such as methyl methacrylate, such as An aromatic vinyl compound of styrene, such as a vinyl cyanide of (meth)acrylonitrile. The crosslinkable monomer may, for example, be a crosslinkable compound having two or more polymerizable carbon-carbon double bonds in the molecule, and more specifically, for example, ethylene glycol di(meth)acrylate or butanediol (meth)acrylate of a polyhydric alcohol such as (meth)acrylate, an enester of (meth)acrylic acid such as allyl (meth)acrylate, or divinylbenzene.

The content of the acrylic rubber particles is preferably 5 parts by weight or more, and more preferably 10 parts by weight or more, based on 100 parts by weight of the (meth)acrylic resin. When the content of the acrylic rubber particles is too large, the surface hardness of the film is low, and when the film is subjected to surface treatment, the solvent resistance to the organic solvent in the surface treatment agent is low. Therefore, the content of the acrylic rubber particles is usually 80 parts by weight or less, and preferably 60 parts by weight or less, based on 100 parts by weight of the (meth)acrylic resin.

The first and second resin films 3 and 4 may contain a usual additive in the technical field of the present invention. Specific examples of the additive include, for example, an ultraviolet absorber, an infrared absorber, an organic dye, a pigment, an inorganic dye, an antioxidant, an antistatic agent, a surfactant, a lubricant, a dispersant, a heat stabilizer, and the like.

Examples of the ultraviolet absorber include a salicylate-based compound, a diphenylketone-based compound, a benzotriazole-based compound, and three (triazine) compound, cyano (meth) acrylate compound, nickel salt, and the like.

Each of the first and second resin films 3 and 4 may be a film having no extension, or may be a film extending in one axis or two axes. The two-axis extension may be a simultaneous two-axis extension in which two extension directions are simultaneously extended, and may be a second-axis extension extending in the other direction after extending in the specified direction. The first resin film 3 and/or the second resin film 4 may be a protective film that serves the task of protecting the polarizing film 2, and may have a protective film having an optical function as a retardation film to be described later. The retardation film is an optical film that exhibits optical anisotropy. For example, a film made of the above thermoplastic resin may be stretched (one-axis stretching or biaxial stretching), or a liquid crystal layer or the like may be formed on the thermoplastic resin film to form a retardation film to which an arbitrary retardation value is applied.

The first resin film 3 and the second resin film 4 may be a film composed of the same thermoplastic resin, or may be a film composed of a different thermoplastic resin. The first resin film 3 and the second resin film 4 may be the same or different in thickness, presence or absence of additives, phase difference characteristics, and the like.

The first resin film 3 and/or the second resin film 4 may have a hard coat layer, an antiglare layer, and an anti-reverse layer on the outer surface (the surface opposite to the polarizer 2). A surface treatment layer (coating layer) of a shot layer, a light diffusion layer, an antistatic layer, an antifouling layer, a conductive layer, or the like.

The thickness of each of the first resin film 3 and the second resin film 4 is usually 1 to 150 μm, more preferably 5 to 100 μm, still more preferably 5 to 60 μm. The thickness is 50 μm or less, and may be 30 μm or less. The thickness of the first and second resin films 3 and 4 is small, which is advantageous for thinning of the optical film 1 and the optical layered body with the adhesive layer, and further facilitates the liquid crystal including the optical film 1 or the optical laminate with the adhesive layer. Thinning of the display device.

In particular, in the case of a small-sized polarizing plate called a smart phone or a flat-type terminal, a thin film having a thickness of 30 μm or less is often used as the first resin film 3 and/or the second resin film 4 due to the thin film formation. The polarizing plate suppresses the weakening of the contraction force of the polarizer 2, and the durability is likely to be insufficient. According to the present invention, even when such a polarizing plate is used as the optical film 10, the optical film 1 and the optical layered body with the adhesive layer having good durability can be provided. The durability of the optical film 1 and the optical layered body with the adhesive layer refers to, for example, a high-temperature environment, a high-temperature and high-humidity environment, a high-temperature and low-temperature reversal environment, and the like, and the adhesion of the adhesive layer 20 and the adjacent film can be suppressed. The properties of defects such as floating, peeling of the interface of the member, and foaming of the adhesive layer 20.

Further, from the viewpoint of thinning of the polarizing plate, as in the polarizing plate 10a shown in FIG. 2, it is advantageous to arrange the resin film only on one surface of the polarizing plate 2. In this case, the adhesive layer 20 is directly bonded to the other surface of the polarizer 2 to form the optical film 1 with the adhesive layer (refer to FIG. 4). In the case of such a polarizing plate, due to the adhesive layer The ionic compound contained in 20 has a particularly remarkable problem of lowering the optical performance of the polarizing plate in a high-temperature and high-humidity environment. According to the present invention, even when such a polarizing plate is used as the optical film 10, the optical film 1 and the optical laminate having the adhesive layer having good optical durability (the property of suppressing deterioration of optical characteristics) can be provided. .

The first and second resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer or an adhesive layer. As the adhesive for forming the adhesive layer, a water-based adhesive or an active energy ray-curable adhesive can be used.

The water-based adhesive is, for example, an adhesive composed of a polyvinyl alcohol-based resin aqueous solution, an aqueous two-liquid amine ester-based emulsified adhesive, or the like. Among them, a water-based adhesive composed of a polyvinyl alcohol-based resin aqueous solution is suitably used. As the polyvinyl alcohol-based resin, in addition to the vinyl alcohol homopolymer obtained by subjecting polyvinyl acetate of a vinyl acetate homopolymer to saponification, vinyl acetate and other monomers copolymerizable therewith may be used. The copolymer is subjected to a saponification treatment to obtain a polyvinyl alcohol-based copolymer, or a modified polyvinyl alcohol-based polymer modified with the hydroxyl group. The aqueous binder may include a crosslinking agent such as an aldehyde compound, an epoxy compound, a melamine compound, a methylol compound, an isocyanate compound, an amine compound, or a polyvalent metal salt.

In the case of using a water-based adhesive, after the polarizer 2 is bonded to the first and second resin films 3 and 4, it is preferred to carry out a drying step in order to remove water contained in the aqueous binder. After the drying step, a ripening step of, for example, a ripening at about 20 to 45 ° C may be provided.

The above-mentioned active energy ray-curable adhesive refers to a hardening by irradiation of an active energy ray such as ultraviolet rays or electron beams. The agent is, for example, a curable composition containing a polymerizable compound and a photopolymerization initiator, a curable composition containing a photoreactive resin, a curable composition containing a binder resin and a photoreactive crosslinking agent, and the like. It is preferably an ultraviolet curable adhesive. The polymerizable compound is, for example, a photocurable epoxy monomer, a photocurable (meth)acrylic monomer, a photocurable monomer of a photocurable amine ester monomer, or an oligomer derived from a photopolymerizable monomer. Polymer. The photopolymerization initiator includes, for example, a substance which generates an active species such as a neutral radical, an anionic radical, or a cationic radical by irradiation with an active energy ray. As an active energy ray-curable adhesive containing a polymerizable compound and a photopolymerization initiator, a curable composition containing a photocurable epoxy-based monomer and a photo-cationic polymerization initiator, and photocurable (methyl) are used. A curable composition of the acrylic monomer and the photoradical polymerization initiator or a mixture of the curable compositions is preferred.

When the active energy ray-curable adhesive is used, after the polarizer 2 is bonded to the first and second resin films 3 and 4, a drying step is performed as needed, and then the active energy ray is cured by irradiation of the active energy ray. A hardening step followed by a hardening of the agent. The light source of the active energy ray is not particularly limited, and an ultraviolet ray having a light-emitting distribution of a wavelength of 400 nm or less is preferable, and specifically, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a black lamp, a microwave-excited mercury lamp, or the like can be used. Metal halide lamps, etc.

When the polarizer 2 is bonded to the first and second resin films 3 and 4, surface-activation treatment such as saponification treatment, corona treatment, or plasma treatment can be performed on at least one of the bonding surfaces. Bonding the tree to both sides of the polarizer 2 In the case of a lipid film, an adhesive for bonding the resin films may be the same kind of adhesive or a different type of adhesive.

The polarizing plates 10a, 10b may further comprise other films or layers. Specific examples thereof include a brightness enhancement film, an anti-glare film, an anti-reflection film, a diffusion film, a light-concentrating film, and an adhesive layer other than the adhesive layer 20, a coating layer, a protective film, and the like, in addition to the retardation film to be described later. The protective film is a film used for the purpose of protecting the surface of the optical film 10 such as a polarizing plate from damage or contamination. After the optical film 1 with the adhesive layer is bonded to, for example, the metal layer 30, it is usually peeled off.

The protective film is usually composed of a base film and an adhesive layer laminated thereon. The base film may be a thermoplastic resin such as a polyolefin resin such as a polyethylene resin or a polypropylene resin; a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; and polycarbonate. A resin; a (meth)acrylic resin or the like.

[1-2] phase difference plate

The retardation film to be included in the retardation film is an optical film which exhibits optical anisotropy as described above, and can be used for the above-exemplified thermoplastic resin of the first and second resin films 3 and 4, for example, a polyvinyl alcohol resin. a polyarylate resin, a polyamidene resin, a polyether oxime resin, a polyvinylidene fluoride/polymethyl methacrylate resin, a liquid crystal polyester resin, an ethylene-vinyl acetate copolymer saponified product, A resin film composed of a polyvinyl chloride resin or the like is stretched by a stretching film of about 1.01 to 6 times. In particular, a stretched film in which a polycarbonate resin film, a cyclic olefin resin film, a (meth)acrylic resin film, or a cellulose resin film is axially extended or biaxially stretched is preferable. And, in this book It is stated that the zero hysteresis film is also included in the retardation film (but the zero retardation film can also be used as a protective film). Further, a film called a one-axis retardation film, a wide viewing angle retardation film, a low photoelasticity retardation film, or the like may be applied as a retardation film.

Called zero retardation film, retardation value R _e means the plane and thickness direction retardation R _th are both -15 to 15nm film. This retardation film is suitably used for an IPS (in-plane switching) mode liquid crystal display device. The in-plane phase difference value R _e and the thickness direction phase difference value R _th are desirably -10 to 10 nm, more desirably -5 to 5 nm. Here, the in-plane phase difference value R _e and the thickness direction phase difference value R _th refer to a value of a wavelength of 590 nm.

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

R _th =[(n _x +n _y )/2-n _z ]×d. In the formula, n _x is a refractive index in the slow axis direction (x-axis direction) in the film plane, and n _y is a refractive index in the front fast axis direction (in the in-plane y-axis direction perpendicular to the x-axis) in the film plane, n _z is a refractive index in the thickness direction of the film (the z-axis direction of the vertical film surface), and d is the thickness of the film.

For the zero-hysteresis film, for example, a polyolefin resin such as a cellulose resin, a chain polyolefin resin, or a cyclic polyolefin resin, a polyethylene terephthalate or a (meth)acrylic resin can be used. A resin film formed. In particular, it is preferable to use a cellulose resin, a polyolefin resin, or a (meth)acrylic resin because the control of the retardation value is easy and easy to obtain.

Moreover, by the coating/alignment of the liquid crystalline compound A film which exhibits optical anisotropy or an optically anisotropic film by application of an inorganic layered compound can also be used as a retardation film. In such a retardation film, a rod-shaped liquid crystal sold by JX Nippon Mining & Energy Co., Ltd. under the trade name "NH FILM" is a film which is inclined and aligned, and is called a temperature-compensated retardation film. The disc-shaped liquid crystal sold by Fujifilm Co., Ltd. under the trade name "WV FILM" is a tilt-aligned film, and the full two-axis alignment type sold by Sumitomo Chemical Co., Ltd. under the trade name "VAC FILM". A film, a biaxial alignment type film sold under the trade name "new VAC FILM" by Sumitomo Chemical Co., Ltd., and the like.

The resin film laminated on at least one side of the retardation film may be, for example, the above-mentioned protective film.

[2] adhesive layer

The adhesive layer 20 disposed between the optical film 10 and the metal layer 30 is composed of a (meth)acrylic resin (A), an isocyanate crosslinking agent (B), a decane compound (C), and an ionic compound ( D) is composed of an adhesive composition. The ionic compound (D) in the adhesive composition is an ionic compound represented by the following formula (I): M ⁺ X ^- (I). In the formula (I), M ⁺ represents an inorganic cation, and X ^- represents an anion containing a fluorine atom.

The adhesive composition contains 0.01 to 2.5 parts by weight of an isocyanate crosslinking agent (B), 0.01 to 10 parts by weight of a decane compound (C), and 100 parts by weight of the (meth)acrylic resin (A). 0.2 to 8 parts by weight of the ionic compound (D).

Adhesive layer composed of the above adhesive composition 20, in the optical layered body comprising the adhesive layer 20 and the metal layer 30, the corrosion of the metal layer 30 can be suppressed, and the durability of the optical film 1 and the optical layered body with the adhesive layer can be improved. Further, according to the adhesive layer 20 composed of the above-described adhesive composition, the optical film 1 and the optical laminate having the adhesive layer can be formed by directly bonding the adhesive layer 20 to the polarizer 2, and can exhibit good results. Optical durability.

The thickness of the adhesive layer 20 is usually 2 to 40 μm, and it is preferably 5 to 5 from the viewpoints of the durability of the optical film 1 and the optical laminate to which the adhesive layer is attached, and the reworkability of the optical film 1 to which the adhesive layer is attached. 30 μm, more desirably 10 to 25 μm. When the thickness of the adhesive layer 20 is 10 μm or more, the followability of the adhesive layer 20 to the dimensional change of the optical film 10 is improved, and when it is 25 μm or less, the workability is improved.

The adhesive layer 20 is preferably one which exhibits a storage elastic modulus of 0.1 to 5 MPa in a temperature range of 23 to 80 °C. Thereby, the durability of the optical film 1 and the optical layered body with the adhesive layer can be more effectively improved. The phrase "the storage elastic modulus of 0.1 to 5 MPa in the temperature range of 23 to 80 ° C" means that the storage elastic modulus is a value within the above range at any temperature in the range. The storage elastic modulus is usually gradually decreased as the temperature rises, and when the storage elastic modulus at 23 ° C and 80 ° C is within the above range, the storage elastic modulus in the above range can be displayed in this temperature range. The storage elastic modulus of the adhesive layer 20 can be measured using a commercially available viscoelasticity measuring device such as a viscoelasticity measuring device "DYNAMIC ANALYZER RDA II" manufactured by REOMETERIC.

[2-1] (Meth)acrylic resin (A)

The (meth)acrylic resin (A) is a polymer or copolymer containing a constituent unit derived from a (meth)acrylic monomer as a main component (preferably containing 50% by weight or more). The (meth)acrylic monomer, for example, includes a monomer having a (meth)acryl fluorenyl group, and more preferably includes an alkyl (meth)acrylate. The alkyl group of the (meth)acrylic acid alkyl ester preferably has 1 to 14 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, and may be linear, branched or cyclic. As the (meth)acrylic acid alkyl ester, a (meth)acrylic acid alkyl ester containing a substituent of an alkyl acrylate having a substituent which is described later in the alkyl group-introducing substituent can also be used. The alkyl (meth)acrylate may be used alone or in combination of two or more.

Specific examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n- and iso-propyl (meth)acrylate, and (meth)acrylic acid. - and third-butyl ester, n- and iso-amyl (meth)acrylate, n- and iso-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, positive (meth)acrylate And iso-heptyl ester, n- and iso-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n- and iso-decyl (meth)acrylate, (meth)acrylic acid - and iso-decyl ester, isobornyl (meth)acrylate, n- and iso-dodecyl (meth)acrylate, stearyl (meth)acrylate, and the like.

The (meth)acrylic resin (A) is an alkyl acrylate having a Tg of 0 ° C or more and a constituent unit and a homopolymer of an alkyl acrylate (a1) having a glass transition temperature Tg of less than 0 ° C from a homopolymer. The constituent unit of (a2) is preferable. This is advantageous in improving the metal corrosion resistance and durability of the optical film 1 and the optical laminate having the adhesive layer. Homopolymer of alkyl acrylate As the Tg, for example, a literature value of a polymer handbook (Polymer Handbook, Wiley-Interscience) or the like can be used.

Specific examples of the alkyl acrylate (a1) include ethyl acrylate, n- and iso-propyl acrylate, n- and iso-butyl acrylate, n-amyl acrylate, n- and iso-hexyl acrylate, and acrylic acid. -heptyl ester, n- and iso-octyl acrylate, 2-ethylhexyl acrylate, n- and iso- decyl acrylate, n- and iso- decyl acrylate, n-dodecyl acrylate, etc. An alkyl acrylate having a carbon number of from 2 to about 12. As another specific example of the alkyl acrylate (a1), for example, an alkyl acrylate containing a substituent of an alkyl group in an alkyl acrylate of an alkyl group having an alkyl group of about 2 to 12 may be mentioned. The substituent of the alkyl acrylate having a substituent may be a group of a hydrogen atom of the substituted alkyl group, and specific examples thereof include a phenyl group, an alkoxy group, and a phenoxy group. The alkyl acrylate containing a substituent is specifically, for example, 2-methoxyethyl acrylate, ethoxymethyl acrylate, phenoxyethyl acrylate, phenoxy diethylene glycol acrylate, or the like. The alkyl group of the alkyl acrylate (a1) may have an alicyclic structure, and is preferably a linear or branched alkyl group.

The alkyl acrylate (a1) may be used alone or in combination of two or more. Among them, the alkyl acrylate (a1) is preferably one or more selected from the group consisting of ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. The alkyl acrylate (a1) is preferably composed of n-butyl acrylate from the viewpoint of the followability and reworkability of the adhesive layer 20 of the optical film 1 with the adhesive layer to the optical film 10.

The alkyl acrylate (a2) is an alkyl acrylate other than the alkyl acrylate (a1). Specific examples of the alkyl acrylate (a2) include methyl acrylate, Cyclohexyl acrylate, isobornyl acrylate, stearyl acrylate, tert-butyl acrylate, and the like.

The alkyl acrylate (a2) may be used alone or in combination of two or more. Among them, from the viewpoint of metal corrosion resistance and durability, the alkyl acrylate (a2) includes methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, and the like, and more preferably methyl acrylate.

The content of the constituent unit derived from the alkyl acrylate (a2) in the (meth)acrylic resin (A) is determined from the viewpoints of the metal corrosion resistance and durability of the optical film 1 and the optical laminate of the adhesive layer. The 100 parts by weight of all the constituent units of the (meth)acrylic resin (A) is preferably 10 parts by weight or more, more preferably 15 parts by weight or more, still more preferably 20 parts by weight or more, and particularly preferably 25 parts by weight or more. . In addition, the content of the constituent unit derived from the alkyl acrylate (a2) is preferably 70 parts by weight or less, more preferably 60 parts by weight or less, from the viewpoint of the followability and reworkability of the adhesive layer 20 with respect to the optical film 10. It is preferably 50 parts by weight or less.

The (meth)acrylic resin (A) may contain constituent units derived from monomers other than the alkyl acrylates (a1) and (a2). The (meth)acrylic resin (A) may contain only one type of constituent unit derived from another monomer, or may contain two or more types. Specific examples of other monomers are shown below.

1) Monomers with polar functional groups

The monomer having a polar functional group is, for example, a (meth) acrylate having a substituent such as a hydroxyl group, a carboxyl group, a substituted or unsubstituted amino group, or a heterocyclic group such as an epoxy group. Specifically, for example, 2-hydroxyethyl (meth)acrylate, (methyl) 3-hydroxypropyl acrylate, 4-hydroxybutyl (meth)acrylate, 2-(2-hydroxyethoxy)ethyl (meth)acrylate, 2-chloro-2-hydroxypropyl (meth)acrylate a monomer having a hydroxyl group such as 3-chloro-2-hydroxypropyl (meth)acrylate or diethylene glycol mono(meth)acrylate; acryloylmorpholine, vinyl caprolactam, N- Vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofuran methyl (meth)acrylate, caprolactone modified tetrahydrofuran methyl acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, Monomer having a heterocyclic group such as glycidyl methacrylate, 2,5-dihydrofuran or the like; aminoethyl (meth) acrylate or N,N-dimethylamino (meth) acrylate a monomer having a substituted or unsubstituted amino group such as ethyl ester or dimethylaminopropyl (meth)acrylate; or a carboxyl group-containing monomer such as (meth)acrylic acid or carboxyethyl (meth)acrylate. Among them, a monomer having a hydroxyl group is preferred, and a (meth) acrylate having a hydroxyl group is more preferable in terms of reactivity of the (meth)acrylic resin (A) and the crosslinking agent.

The monomer having the above other polar functional groups may be contained together with the (meth) acrylate having a hydroxyl group, and from the viewpoint of preventing the peeling force of the release film which can be deposited on the outer surface of the adhesive layer 20 from being substantially It is preferred to include a monomer having an amine group. Further, from the viewpoint of improving the corrosion resistance to ITO, it is preferred that the monomer having a carboxyl group is not substantially contained. The term "substantially not included" herein means 0.1 part by weight or less based on 100 parts by weight of all the constituent units constituting the (meth)acrylic resin (A).

2) Acrylamide monomer

For example, N-methylol acrylamide, N-(2-hydroxyethyl) acrylamide, N-(3-hydroxypropyl) acrylamide, N-(4-hydroxybutyl) acrylamide, N -(5- Hydroxypentyl) acrylamide, N-(6-hydroxyhexyl) acrylamide, N,N-dimethyl decylamine, N,N-diethyl acrylamide, N-isopropyl acrylamide , N-(3-dimethylaminopropyl) acrylamide, N-(1,1-dimethyl-3-oxobutyl)propenamide, N-[2-(2- side Oxy-1-imidazolidinyl)ethyl]propenylamine, 2-propenylamino-2-methyl-1-propanesulfonic acid, N-(methoxymethyl)propenylamine, N- (ethoxymethyl) acrylamide, N-(propyloxymethyl) acrylamide, N-(1-methylethoxymethyl) acrylamide, N-(1-methylpropoxy) Methyl) acrylamide, N-(2-methylpropoxymethyl) acrylamide [alias: N-(isobutoxymethyl) acrylamide], N-(butoxymethyl) Acrylamide, N-(1,1-dimethylethoxymethyl)propenylamine, N-(2-methoxyethyl)propenylamine, N-(2-ethoxyethyl Acrylamide, N-(2-propoxyethyl)propenylamine, N-[2-(1-methylethoxy)ethyl]propenylamine, N-[2-(1-A Propyloxy)ethyl]propenylamine, N-[2-(2-methylpropoxy)ethyl]propenylamine [alias: N-(isobutoxyethyl) acrylamide], N-(2-butoxy B ) Acrylamide, N- [2- (1,1- dimethylethoxy) ethyl] acrylamide and the like. Among them, N-(methoxymethyl)propenylamine, N-(ethoxymethyl)propenylamine, N-(propoxymethyl)propenylamine, N-(butoxymethyl) are used. Acrylamide and N-(2-methylpropoxymethyl)propenylamine are preferred.

3) methacrylate, also known as ester of methacrylic acid

For example, a linear alkyl ester of methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate or lauryl methacrylate; Methyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate, etc. Branched alkyl ester of acrylic acid; isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, cyclododecyl methacrylate, methylcyclohexyl methacrylate, methacrylic acid An alicyclic alkyl ester of methacrylic acid such as trimethylcyclohexyl ester, t-butylcyclohexyl methacrylate or cyclohexyl phenyl methacrylate; 2-methoxyethyl methacrylate, methyl An alkoxyalkyl methacrylate such as ethoxymethyl acrylate; an arylalkyl methacrylate such as benzyl methacrylate; 2-hydroxyethyl methacrylate or 3-hydroxy propyl methacrylate; Ester, 4-hydroxybutyl methacrylate, 2-(2-hydroxyethoxy)ethyl methacrylate, 2-chloro-2-hydroxypropyl methacrylate, 3-chloro-2-hydroxy methacrylate An alkyl ester of methacrylic acid having a hydroxyl group such as propyl ester or diethylene glycol monomethacrylate; aminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, methacrylic acid An alkyl ester of methacrylic acid having a substituted or unsubstituted amine group such as dimethylaminopropyl ester; 2-phenoxyethyl methacrylate , 2-(2-phenoxyethoxy)ethyl methacrylate, ethylene oxide modified nonylphenol ester of (meth)acrylic acid, 2-(o-phenylphenoxy) methacrylate An ester of methacrylic acid having a phenoxyethyl group such as an ethyl ester.

4) Methacrylamide amide monomer

For example, it corresponds to the methacrylamide-based monomer of the acrylamide-based monomer described in the above 1).

5) Styrene monomer

Such as styrene; such as methyl styrene, dimethyl styrene, trimethyl Alkyl styrene of styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene; Halogenated styrene such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodine styrene; nitrostyrene; ethoxylated styrene; methoxystyrene; divinylbenzene.

6) Vinyl monomer

For example, vinyl acetate, vinyl butyrate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, etc.; vinyl halide such as ethylene chloride or ethylene bromide; vinyl chloride a halogenated vinylene; a nitrogen-containing aromatic vinyl such as vinylpyridine, vinylpyrrolidone or vinylcarbazole; a conjugated diene monomer such as butadiene, isoprene or chloroprene; An unsaturated nitrile such as acrylonitrile or methacrylonitrile.

7) Monomers having a complex number of (meth) acrylonitrile groups in the molecule

For example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethylene glycol II (Methyl) acrylate, diethylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, tripropylene glycol di(meth) acrylate, etc. have two molecules in the molecule (methyl) a monomer having an acrylonitrile group; a monomer having three (meth) acrylonitrile groups in the molecule such as trimethylolpropane tri(meth)acrylate.

As described above, the (meth)acrylic resin (A) is composed of a constituent unit derived from an alkyl (meth)acrylate from the viewpoints of durability and metal corrosion resistance of the optical film 1 and the optical laminate having the adhesive layer. Outside, to pack It is preferred to contain a constituent unit derived from a monomer having a polar functional group. The monomer having a polar functional group is preferably a (meth) acrylate monomer having a polar functional group, and more preferably a monomer having a hydroxyl group. The content of the constituent unit derived from the monomer having a polar functional group is preferably from 0.1 to 10 parts by weight, more preferably from 0.25 to 5, based on 100 parts by weight of all the constituent units constituting the (meth)acrylic resin (A). It is more preferably 0.5 to 5 parts by weight in parts by weight.

Further, the (meth)acrylic resin (A) is derived from a methacrylate (ester of methacrylic acid), a methacrylamide-based monomer, etc. from the viewpoint of the reworkability of the optical film 1 with an adhesive layer. The content of the constituent unit of the methacrylic monomer is preferably small. Specifically, the content of the constituent unit is preferably 10 parts by weight based on 100 parts by weight of all constituent units constituting the (meth)acrylic resin (A). The amount is preferably 5 parts by weight or less, more preferably substantially no such structural unit (0.1 part by weight or less).

The (meth)acrylic resin (A) has a weight average molecular weight Mw of 1,000 to 2.5 million on a discharge curve of a gel permeation chromatography (GPC), and has a single peak, and has a range of Mw of 1,000 to 2.5 million. It is more preferable to have a single peak and a constituent unit derived from the alkyl acrylates (a1) and (a2). The adhesive layer 20 using the (meth)acrylic resin (A) as a matrix polymer is advantageous in improving the durability of the optical film 1 and the optical laminate of the adhesive layer. When the number of peaks in the range of the above Mw is 2 or more, sufficient durability may not be obtained.

The number of peaks of the GPC discharge curve in the range of Mw 1000 to 2.5 million was determined based on the GPC measurement conditions described in the items of the examples. Obtain the discharge curve. In the above range of the obtained discharge curve, "having a single peak" means that there is only one maximum value in the range of Mw 1000 to 2.5 million. In the present specification, the GPC discharge curve is defined as a peak with an S/N ratio of 30 or more.

The (meth)acrylic resin (A) is preferably in the range of 500,000 to 2,500,000 in terms of Mw in terms of GPC conversion, and more preferably in the range of 600,000 to 2,000,000. When the Mw is 500,000 or more, it is advantageous in improving the metal corrosion resistance and durability of the optical film 1 and the optical layered body with the adhesive layer, and also tends to improve the reworkability of the optical film 1 with the adhesive layer. Further, when the Mw is 2.5 million or less, the followability of the adhesive layer 20 to the dimensional change of the optical film 10 is improved. The molecular weight distribution expressed by the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn is usually 2 to 10. The Mw and Mn of the (meth)acrylic resin (A) can be determined by the GPC measurement conditions described in the items of the examples.

When the (meth)acrylic resin (A) is dissolved in ethyl acetate as a solution having a concentration of 20% by weight, the viscosity at 25 ° C is preferably 20 Pa ‧ or less, more preferably 0.1 to 7 Pa s. The viscosity in such a range is advantageous in improving the durability of the optical film 1 and the optical layered body to which the adhesive layer is attached, and the reworkability of the optical film 1 to which the adhesive layer is attached. The above viscosity can be measured by a Brookfield viscometer.

The (meth)acrylic resin (A) preferably has a glass transition temperature Tg of from -60 to -10 ° C as measured by a differential scanning calorimeter (DSC), and more preferably from -55 to -15 ° C. Such a range of Tg is advantageous for the metal corrosion resistance and durability of the optical film 1 and the optical laminate with the adhesive layer. high.

The adhesive composition may contain two or more (meth)acrylic resins belonging to the (meth)acrylic resin (A). Further, the adhesive composition may contain another (meth)acrylic resin different from the (meth)acrylic resin (A). However, the content of the (meth)acrylic resin (A) is based on the total (meth)acrylic resin from the viewpoint of the metal corrosion resistance and durability of the optical film 1 and the optical laminate having the adhesive layer. In general, it is preferably 70% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, and the adhesive composition is particularly useful as a matrix polymer containing only (meth)acrylic resin (A). ideal.

The (meth)acrylic resin (A) or another (meth)acrylic resin which can be used in combination as needed can be, for example, a conventional method such as a solution polymerization method, an overall polymerization method, a suspension polymerization method, or an emulsion polymerization method. Manufacturing. A polymerization initiator is usually used for the production of the (meth)acrylic resin. The polymerization initiator is used in an amount of about 0.001 to 5 parts by weight based on 100 parts by weight of the total of all the monomers used in the production of the (meth)acrylic resin. Further, the (meth)acrylic resin can be produced, for example, by a method of polymerizing an active energy ray such as ultraviolet rays.

As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, or the like can be used. As a photoinitiator, 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-propyl) ketone, etc. are mentioned, for example. As a thermal polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1) -carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) , dimethyl-2,2'-even An azo compound of nitrogen bis(2-methylpropionate), 2,2'-azobis(2-hydroxymethylpropionitrile); such as lauryl peroxide, tert-butyl peroxide, peroxidation Benzoquinone, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, tert-butyl peroxy neodecanoate, new peroxidation Tertiary valerate, an organic peroxide of (3,5,5-trimethylhexyl) peroxide; an inorganic peroxide such as potassium persulfate, ammonium persulfate or hydrogen peroxide. Further, a redox initiator such as a peroxide and a reducing agent may be used as a polymerization initiator.

As a method for producing a (meth)acrylic resin, among the methods described above, a solution polymerization method is preferred. In an example of the solution polymerization method, a monomer to be used is mixed with an organic solvent, and a thermal polymerization initiator is added under a nitrogen atmosphere, and is stirred at about 40 to 90 ° C, preferably at about 50 to 80 ° C for about 3 to 15 hours. In order to control the reaction, a monomer or a thermal polymerization initiator may be continuously or intermittently added during the polymerization, or may be added in a state of being dissolved in an organic solvent. As the organic solvent, for example, an aromatic hydrocarbon such as toluene or xylene; an ester such as ethyl acetate or butyl acetate; an aliphatic alcohol such as propanol or isopropanol; such as acetone or methyl ethyl; A ketone such as a ketone or a methyl isobutyl ketone.

[2-2] Isocyanate crosslinking agent (B)

The adhesive composition contains an isocyanate crosslinking agent (B). By using the isocyanate crosslinking agent (B) as a crosslinking agent, the metal corrosion resistance and durability of the optical film 1 and the optical laminate of the adhesive layer can be improved. The isocyanate-based crosslinking agent (B) may be used alone or in combination of two or more.

The isocyanate crosslinking agent (B) is a compound having at least two isocyanate groups (-NCO) in the molecule, specifically, for example, tolyl diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylene Diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, stilbene diisocyanate, triphenylmethane triisocyanate, and the like. Further, the isocyanate crosslinking agent (B) may be a polyol compound adduct of the isocyanate compound (for example, an adduct of glycerol or trimethylolpropane), an isocyanurate compound, or a condensation product. An amine ester prepolymer of a diuret type compound, an addition reaction with a polyether polyol, a polyester polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol, or the like A derivative of a isocyanate compound or the like. Among the above, in particular, a polyol compound adduct of tolyl diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate or the isocyanate compound is preferred, and the optical film 1 and the optical layer from the adhesive layer are preferable. From the viewpoint of durability of the laminate, it is more preferable to use xylylene diisocyanate or a polyol compound adduct thereof.

The content of the isocyanate-based crosslinking agent (B) is preferably from 0.01 to 2.5 parts by weight, more preferably from 0.1 to 2 parts by weight (for example, 1 part by weight, per 100 parts by weight of the (meth)acrylic resin (A). the following). When the content of the isocyanate-based crosslinking agent (B) is within this range, the optical film 1 and the optical layered body of the pressure-sensitive adhesive layer are both excellent in metal corrosion resistance and durability.

The adhesive composition may be used together with the isocyanate crosslinking agent (B), and other crosslinking agents may be used, for example, an epoxy compound, an aziridine compound, a metal clamp compound, a peroxide, or the like. From From the viewpoint of the metal corrosion resistance and durability of the optical film 1 and the optical laminate of the adhesive layer, the adhesive composition preferably contains only the isocyanate crosslinking agent (B), and particularly contains no peroxide. . The term "substantially not included" means that the content of the (meth)acrylic resin (A) is 0.01 parts by weight or less based on 100 parts by weight.

[2-3] decane compound (C)

The adhesive composition contains a decane compound (C). Thereby, the adhesiveness of the adhesive layer 20, the metal layer 30, the glass substrate, etc. can be improved. Two or more kinds of decane compounds (C) can also be used.

As the decane compound (C), for example, vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, 3-glycidoxypropyltrimethoxy Decane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylethoxydimethyl decane , 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropene oxime Oxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, and the like.

The decane compound (C) may also contain a polyoxyxene oligomer type. When the polyoxyl oligomer is represented by a combination of monomers, it is as follows.

3-mercaptopropyltrimethoxydecane-tetramethoxydecane oligomer, 3-mercaptopropyltrimethoxydecane-tetraethoxydecane oligomer, a mercaptopropyl group-containing oligomer such as 3-mercaptopropyltriethoxydecane-tetramethoxydecane oligomer or 3-mercaptopropyltriethoxydecane-tetraethoxydecane oligomer; Mercaptomethyltrimethoxydecane-tetramethoxydecane oligomer, mercaptomethyltrimethoxydecane-tetraethoxydecane oligomer, mercaptomethyltriethoxydecane-tetramethoxynonane oligomerization a mercaptomethyl-containing oligomer such as a mercaptomethyltriethoxydecane-tetraethoxydecane oligomer; 3-glycidoxypropyltrimethoxydecane-tetramethoxynonane Polymer, 3-glycidoxypropyltrimethoxydecane-tetraethoxydecane oligomer, 3-glycidoxypropyltriethoxydecane-tetramethoxydecane oligomer, 3-glycidoxypropyltriethoxydecane-tetraethoxydecane oligomer, 3-glycidoxypropylmethyldimethoxydecane-tetramethoxydecane oligomer, 3-glycidoxypropylmethyldimethoxydecane-tetraethoxydecane oligomer, 3-glycidoxypropylmethyldiethoxydecane-tetramethoxynonane oligomerization 3-glycidoxypropylmethyldiethyl Yl Silane - tetraethyl orthosilicate oligomer or the like containing 3-glycidoxypropyl oligomers; 3-methylpropenyloxypropyltrimethoxydecane-tetramethoxydecane oligomer, 3-methacryloxypropyltrimethoxydecane-tetraethoxydecane oligomer, 3- Methyl propylene methoxy propyl triethoxy decane - tetramethoxy decane oligomer, 3-methyl propylene methoxy propyl triethoxy decane - tetraethoxy decane oligomer, 3- Methyl propylene methoxy propyl methyl dimethoxy decane - tetramethoxy decane oligomer, 3-methyl propylene methoxy propyl methyl dimethoxy decane - tetraethoxy decane oligomerization , 3-methylpropenyloxypropylmethyldiethoxydecane-tetramethoxydecane oligomer, 3-methylpropenyloxypropylmethyldiethoxydecane-tetraethoxy A methacryloxypropyl group-containing oligomer such as a decane oligomer; a 3-propenyloxypropyltrimethoxydecane-tetramethoxydecane oligomer, 3-propenyloxypropane Trimethoxy decane-tetraethoxy decane oligomer, 3-propenyl methoxypropyl triethoxy decane-tetramethoxy decane oligomer, 3-propenyl methoxy propyl triethoxy矽-tetraethoxy decane oligomer, 3-propenyloxypropylmethyldimethoxydecane-tetramethoxydecane oligomer, 3-propenylmethoxypropylmethyldimethoxydecane-tetraethoxydecane oligomer, 3-propenyloxypropylmethyldiethoxydecane-tetramethoxydecane oligomer, 3-propenyloxypropylmethyldiethoxydecane-tetraethoxydecane oligomer, etc. An acryloxypropyl group-containing oligomer; a vinyl trimethoxy decane-tetramethoxy decane oligomer, a vinyl trimethoxy decane-tetraethoxy decane oligomer, a vinyl triethoxy group Base decane-tetramethoxy decane oligomer, vinyl triethoxy decane-tetraethoxy decane oligomer, vinyl methyl dimethoxy decane-tetramethoxy decane oligomer, vinyl Methyldimethoxydecane-tetraethoxydecane oligomer, vinylmethyldimethoxymethoxynonane-tetramethoxydecane oligomer, vinylmethyldiethoxydecane-tetraethoxy a vinyl group-containing oligomer such as a decane oligomer or the like; 3-aminopropyltrimethoxydecane-tetramethoxydecane oligomer, 3-aminopropyltrimethoxydecane-tetraethoxy Decane oligo , 3-aminopropyltriethoxydecane-tetramethoxydecane oligomer, 3-aminopropyltriethoxydecane-tetraethoxydecane oligomer, 3-aminopropyl Methyldimethoxydecane-tetramethoxydecane oligomer, 3-aminopropylmethyldimethoxydecane-tetraethoxydecane oligomer, 3-aminopropylmethyldiethyl Oxydecane-tetramethoxynonane oligomer, An amine group-containing oligomer or the like such as a 3-aminopropylmethyldiethoxydecane-tetraethoxydecane oligomer.

The content of the decane compound (C) in the adhesive composition is 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, more preferably 0.05, based on 100 parts by weight of the (meth)acrylic resin (A). It is more preferably from 0.1 to 1 part by weight to 2 parts by weight. When the amount of the decane compound (C) is 0.01 parts by weight or more, the adhesion improving effect of the adhesive layer 20, the metal layer 30, the glass substrate, or the like is easily obtained. When the content is 10 parts by weight or less, bleeding of the decane compound (C) from the adhesive layer 20 can be suppressed.

[2-4] Ionic compound (D)

The adhesive composition contains an ionic compound (D). The ionic compound (D) is an ionic compound represented by the following formula (I): M ⁺ X ^- (I) (in the formula (I), M ⁺ represents an inorganic cation, and X ^- represents an anion containing a fluorine atom) . By using the ionic compound (D), not only the adhesive layer 20 can be imparted with a good antistatic function, but also good metal corrosion resistance and optical durability can be imparted. The adhesive composition may contain one or more ionic compounds (D).

In the above formula (I), M ⁺ represents an inorganic cation. Specific examples of the inorganic cation include an alkali metal ion such as a lithium cation [Li ⁺ ], a sodium cation [Na ⁺ ], a potassium cation [K ⁺ ], a phosphonium cation [Cs ⁺ ], a ^phosphonium cation [Be ²⁺ ], and a magnesium cation. [Mg ²⁺ ], alkaline earth metal ions such as calcium cation [Ca ²⁺ ], and the like. Among them, from the viewpoint of metal corrosion resistance of the optical film 1 and the optical laminate having the adhesive layer, it is preferable to use lithium cation [Li ⁺ ], sodium cation [Na ⁺ ], potassium cation [K ⁺ ], and From the viewpoint of the durability of the optical film 1 and the optical laminate of the adhesive layer, it is more preferable to use potassium cation [K ⁺ ].

In the above formula (I), X ^- represents an anion containing a fluorine atom. An anion containing a fluorine atom tends to give an ionic compound (D) which is excellent in antistatic function. Any of an inorganic anion and an organic anion can be used as the anion containing a fluorine atom. Specific examples of the inorganic anion which can constitute the ionic compound (D) include tetrafluoroborate anion [BF ₄ ^- ], hexafluorophosphate anion [PF ₆ ^- ], hexafluoroarsenate anion [AsF ₆ ^- ], and six Fluoroantimonate anion [SbF ₆ ^- ], hexafluoroantimonate anion [NbF ₆ ^- ], hexafluoroantimonate anion [TaF ₆ ^- ], bis(fluorosulfonyl)imide anion [(FSO ₂ ) ₂ N ^- ], (poly) hydrogen fluoride fluoride anion [F(HF) _n ^- ] (n is about 1 to 3) and the like.

Specific examples of the organic anion which can constitute the ionic compound (D) include a trifluoroacetate anion [CF ₃ COO ^- ], a trifluoromethanesulfonate anion [CF ₃ SO ₃ ^- ], and a bis(trifluoromethanesulfonyl) group. Imine anion [(CF ₃ SO ₂ ) ₂ N ^- ], tris(trifluoromethanesulfonyl)methyl (methanide) anion [(CF ₃ SO ₂ ) ₃ C ^- ], perfluorobutanesulfonate anion [C ₄ F ₉ SO ₃ ^- ], bis(pentafluoroethanesulfonyl)imide anion [(C ₂ F ₅ SO ₂ ) ₂ N ^- ], perfluorobutyrate anion [C ₃ F ₇ COO ^- ], (trifluoromethane sulfonic acyl) (carbonyl trifluoromethanesulfonyl) imide anion _{[(CF 3 SO 2) (} CF 3 CO) N -], -1,3- perfluoropropane disulfonate anion ^[- O ₃ S(CF ₂ ) ₃ SO ₃ ^- ], tetraarylborate anion (for example, tetrakis(pentafluorophenyl)borate anion, etc.), dicyandiamide anion [(CN) ₂ N ^- ] and the following formula (III): The imine anions and the like are shown.

The anion containing a fluorine atom is preferably from the following formula (II) from the viewpoints of antistatic function, metal corrosion resistance and durability of the optical film 1 and the optical layered body to which the adhesive layer is attached: [Y(SO ₂ C) _m F _2m+1 ) _n ] ^- (II) (In the formula (II), Y represents a carbon atom or a nitrogen atom, Y represents a carbon atom, n is 3, Y represents a nitrogen atom, n is 2, and m represents 0 to 10 An integer of the fluorine atom shown by the integer). Specific examples of the fluorine atom-containing anion represented by the formula (II) include a bis(fluorosulfonyl)imide anion, a bis(trifluoromethanesulfonyl)imide anion, and a tris(trifluoromethanesulfonyl) group. A methyl anion, bis(pentafluoroethanesulfonyl) imide anion, and the like. Among them, the use of bis(fluorosulfonyl)imide anion [FSI ^- ] or bis(trifluoromethanesulfonyl) imide anion [TFSI ^- ] ionic compound (D) is particularly advantageous for improving the adhesive layer The anti-static function, metal corrosion resistance and durability of the optical film 1 and the optical laminate. Y is preferably a nitrogen atom, and m is preferably an integer of 0 to 4, more preferably an integer of 0 to 1, and particularly preferably 0.

Preferred examples of the ionic compound (D) represented by the above formula (I) are as follows.

Bis(fluorosulfonyl)imide lithium

Bis(trifluoromethanesulfonyl)imide lithium

Bis(pentafluoroethanesulfonyl)imide lithium

Tris(trifluoromethanesulfonyl)methyllithium

Bis(fluorosulfonyl)imide sodium

Bis(trifluoromethanesulfonyl)imide sodium

Bis(pentafluoroethanesulfonyl)imide sodium

Tris(trifluoromethanesulfonyl)methyl sodium

Bis(fluorosulfonyl)imide potassium

Bis(trifluoromethanesulfonyl)imide potassium

Bis(pentafluoroethanesulfonyl)imide potassium

Tris(trifluoromethanesulfonyl)methyl potassium

The content of the ionic compound (D) in the adhesive composition is preferably 0.2 to 8 parts by weight, more preferably 0.2 to 7 parts by weight, based on 100 parts by weight of the (meth)acrylic resin (A), and 0.3 to 5 parts by weight. The parts by weight are more desirable, and 0.5 to 3 parts by weight are particularly desirable. The content of the ionic compound (D) is 0.2 parts by weight or more, which is advantageous for improving the antistatic function, and when it is 8 parts by weight or less, it is advantageous for the metal corrosion resistance and durability of the optical film 1 and the optical layered body to which the adhesive layer is attached.

The adhesive composition can be used together with the ionic compound (D) represented by the above formula (I), and an antistatic agent other than the above, from the optical film 1 of the adhesive layer and the metal corrosion resistance of the optical laminate. In view of the above, the adhesive composition preferably contains the ionic compound (D) represented by the above formula (I) as an antistatic agent.

[2-5] Other ingredients

The adhesive composition may contain one or more solvents, a crosslinking catalyst, an ultraviolet absorber, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, and a light scattering property. Additives such as microparticles. Further, an ultraviolet curable compound is blended in the adhesive composition to form an adhesive layer, which is then cured by irradiation with ultraviolet rays, and is used to form a harder adhesive layer. As a crosslinking catalyst, for example, hexamethylenediamine, ethylidene diamine, polyethylenimine, hexamethylenetetramine, diethylidenetriamine, triethylidenetetraamine, and isophora An amine compound such as a ketone diamine, a trimethylene diamine, a polyamine resin, or a melamine resin.

The adhesive composition may contain a metal corrosion-resistant rust inhibitor which can improve the optical film 1 and the optical laminate of the adhesive layer. Examples of the rust preventive agent include a triazole compound such as a benzotriazole compound or another triazole compound; a thiazole compound such as a benzothiazole compound or another thiazole compound; a benzyl imidazole compound and other imidazole. An imidazole compound such as a compound; an imidazoline compound; a quinoline compound; a pyridine compound; a pyrimidine compound; an anthraquinone compound; an amine compound; a urea compound; a sodium benzoate; a benzylthiol compound; Di-second butyl sulfide; and diphenylarylene.

However, according to the present invention, even if the rust preventive agent is not contained, sufficient metal corrosion resistance can be obtained, and therefore, the content of the rust preventive agent is preferably as small as possible, and in particular, the adhesive composition is substantially not contained as an anti-defense agent. The triazole-based compound of the rust agent is more preferable, and it is more preferable that the rust preventive agent selected from the above compound group is not substantially contained. The term “substantially not included here” means The (meth)acrylic resin (A) is 0.01 parts by weight or less based on 100 parts by weight.

[3] Metal layer and substrate

The metal layer 30 may, for example, be composed of an alloy selected from the group consisting of aluminum, copper, silver, gold, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and an alloy containing two or more metals selected from the group. The one or more layers are preferably a layer containing a metal element selected from the group consisting of aluminum, copper, silver, and gold from the viewpoint of conductivity, and more preferably a layer containing aluminum from the viewpoint of conductivity and cost. More preferably, it is a layer containing an aluminum element as a main component. The term "included as a main component" means that the metal component constituting the metal layer 30 is 30% by weight or more and 50% by weight or more of all the metal components.

The metal layer 30 may be a metal oxide layer such as ITO. The optical film with an adhesive layer of the present invention has a good corrosion resistance particularly to a metal monomer or an alloy, and the metal layer 30 contains the above-mentioned metal element. It is preferable that the metal monomer and/or the two or more alloys containing the above metal element are formed. However, the optical laminate may have a transparent electrode layer made of a metal oxide such as ITO together with the metal layer 30.

The form (for example, thickness) and the preparation method of the metal layer 30 are not particularly limited, and may be a metal foil, a vacuum deposition method, a sputtering method, an ion plating method, an inkjet printing method, or a gravure printing method. The formation is preferably a metal layer formed by a sputtering method, an inkjet printing method, or a gravure printing method, and more preferably a metal layer formed by a sputtering method. a metal layer formed by sputtering and a metal foil, the former having a tendency to be poor in corrosion resistance, according to the light according to the present invention The laminated body has good metal corrosion resistance even for the metal layer formed by sputtering. The thickness of the metal layer 30 is usually 3 μm or less, more preferably 1 μm or less, and still more preferably 0.8 μm or less. Further, the thickness of the metal layer 30 is usually 0.01 μm or more. In addition, when the metal layer 30 is a metal wiring layer, the metal wiring of the metal wiring layer has a line width of usually 10 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less. Further, the line width of the metal wiring is usually 0.01 μm or more, preferably 0.1 μm or more, and more preferably 0.5 μm or more. Even in the metal layer 30 composed of the metal layer 30 of such a thin film or the metal wiring of the thin line, the optical layered body of the present invention exhibits good metal corrosion resistance. In particular, the metal wiring may have a thickness of 3 μm or less and a line width of 10 μm or less, or a thickness of 3 μm or less and a line width of 10 μm or less, and may be formed by sputtering, and corrosion, particularly pitting corrosion, may be suppressed.

The metal layer 30 may be, for example, a metal wiring layer (ie, an electrode layer) of a touch input element included in the touch input type liquid crystal display device. In this case, the metal layer 30 is typically patterned into a designated shape. In the case of laminating the adhesive layer 20 on the patterned metal layer 30, the adhesive layer 20 may have a portion that does not contact the metal layer 30. The metal layer 30 may be a continuous film containing the above metal or alloy.

Further, the metal layer 30 may have a single layer structure or a multilayer structure of two or more layers. As the metal layer of the multilayer structure, for example, a metal-containing layer (metal mesh or the like) having a three-layer structure represented by molybdenum/aluminum/molybdenum is used.

As shown in FIG. 1, for example, the metal layer 30 of the metal wiring layer is usually formed on the substrate 40. In this case, the optical body of the present invention The laminate includes the substrate 40. The formation of the metal layer 30 on the substrate 40 can be performed by, for example, sputtering. The substrate 40 may be a transparent substrate constituting a liquid crystal cell including a touch input element. The substrate 40 is preferably a glass substrate. As a material of the glass substrate, for example, soda lime glass, low alkali glass, alkali-free glass, or the like. The metal layer 30 may be formed on the entire surface of the substrate 40 or may be formed on a part thereof. When the patterned metal layer 30 is formed on the substrate 40, the metal layer 30 is formed on a part of the surface of the substrate 40, and a part of the adhesive layer 20 is directly in contact with the substrate 40 made of glass, for example. The adhesive layer 20 of the optical laminate of the invention has good adhesion to glass, and the optical laminate and the liquid crystal display device including the optical laminate are also excellent in durability.

[4] Composition and manufacturing method of optical laminate

In one embodiment, the optical laminate of the present invention, as shown in Figs. 4 and 5, includes an optical film 1 with an adhesive layer and a metal layer 30 laminated on the adhesive layer 20. In the optical laminates 5 and 6 as shown in Figs. 4 and 5, the optical film 1 with the adhesive layer is laminated on the metal layer 30 so that the adhesive layer 20 directly contacts the metal layer 30. According to the present invention, even when such an adhesive layer 20 directly contacts the optical layered body of the metal layer 30, corrosion of the metal layer 30 can be effectively suppressed.

Fig. 6 is a schematic cross-sectional view showing another example of the layer constitution of the optical layered body of the present invention. In another embodiment, the optical laminate of the present invention, such as the optical laminate 7 shown in FIG. 6, the adhesive layer 20 of the optical film 1 with the adhesive layer, is laminated on the metal via the resin layer 50. Layer 30. The adhesive layer 20 is in direct contact with the resin layer 50. Even in such an optical layered body 7, corrosion of the metal layer 30 can be effectively suppressed. The resin layer 50 disposed between the adhesive layer 20 and the metal layer 30 may be, for example, a cured layer of a curable resin. As the curable resin capable of forming the resin layer 50, those skilled in the art can be used, for example, those described in JP-A-2009-217037.

The metal layer 30 may be a metal wiring layer. An example of the case where the metal layer 30 is a metal wiring layer is shown in FIG. In the optical laminate shown in Fig. 7, the resin layer 50 can be omitted.

The optical laminate 1 is interposed between the optical film 10 including the optical film 10 and the adhesive layer 20 on the surface of at least one side of the optical layer 10, for example, on the metal layer 30 formed on the substrate 40. The adhesive layer 20 is bonded and produced.

The optical film 1 having the adhesive layer as described above includes the optical film 10 and an adhesive layer 20 (Fig. 1) laminated on at least one side thereof. The adhesive layer 20 can be adhered to the two-layer layer of the optical film 10. Usually, the adhesive layer 20 is directly laminated on the surface of the optical film 10. When the adhesive layer 20 is provided on the surface of the optical film 10, an undercoat layer is formed on the bonding surface of the optical film 10 and/or the bonding surface of the adhesive layer 20, and a surface activation treatment is performed, for example, plasma treatment, Corona treatment and the like are preferred, and corona treatment is more desirable.

The optical film 10 is a single-sided protective polarizing plate as shown in Fig. 2, and the adhesive layer 20 is usually preferably laminated directly on the polarizing plate surface, that is, the surface opposite to the first resin film 3 of the polarizing plate 2. . In the case where the optical film 10 is a polarizing plate protected by both surfaces as shown in FIG. 3, the adhesive layer 20 may be laminated on the outer surface of any of the first and second resin films 3 and 4, or may be Laminated on the outside of both.

An antistatic layer may be additionally provided between the optical film 10 and the adhesive layer 20. The adhesive layer 20 of the present invention can provide good antistatic property by a single adhesive layer, and can be formed into a thin film or laminated body of an optical laminate. In the simplified aspect of the step, it is preferable to have no antistatic layer between the optical film 10 and the adhesive layer 20.

The optical film 1 to which the adhesive layer is attached may also include a release film (release film) laminated on the outer surface of the adhesive layer 20. The release film is usually peeled off and removed when the adhesive layer 20 is used (for example, when the metal layer 30 is laminated). The release film may be, for example, a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or polyarylate, and the surface on which the adhesive layer 20 is formed is subjected to polymerization. A release processor such as oxygen treatment.

The optical film 1 with an adhesive layer can dissolve or disperse each component constituting the above-mentioned adhesive composition in a solvent as a solvent-containing adhesive composition, and then apply it to the surface of the optical film 10 and dry it. The adhesive layer 20 is formed. Further, the optical film 1 with an adhesive layer may be formed on the release-treated surface of the release film, and the adhesive layer 20 may be formed in the same manner as described above, and the adhesive layer 20 may be laminated (transferred) to the optical film 10. The surface comes.

An optical layered body can be obtained by bonding the optical film 1 with an adhesive layer to the metal layer 30 (or the above resin layer) via the adhesive layer 20. After the optical film 1 with the adhesive layer is bonded to the metal layer 30 to form an optical laminate, if there is any defect, the optical film 1 with the adhesive layer is peeled off from the metal layer 30, and the other adhesive is re-attached. Layer optical film 1 It is attached to the metal layer 30 and has the necessity of so-called heavy work. In the optical layered body of the present invention, the surface of the metal layer 30 from which the optical film 1 having the adhesive layer is peeled off from the metal layer 30 is less likely to cause turbidity, residual glue, or the like, and is excellent in reworkability. According to the optical layered body of the present invention, when the surface of the adhesive layer 20 is bonded to the metal layer 30 instead of the glass substrate or the ITO layer, good reworkability can be exhibited.

<Liquid crystal display device>

The liquid crystal display device of the present invention comprises the optical layered body of the present invention described above. With regard to the liquid crystal display device of the present invention, corrosion of the metal layer 30 can be suppressed, and good durability can be exhibited.

The liquid crystal display device of the present invention is preferably a touch input type liquid crystal display device having a touch panel function. The touch input type liquid crystal display device includes a touch input element including a liquid crystal cell and a backlight. The configuration of the touch panel may be any one of an external unit (Out-cell) type, an on-cell type, an in-cell type, and the like, and the operation mode of the touch panel. It may be any conventionally known method such as a resistive film method or a capacitive method (surface type capacitance method or projection type capacitance method). The optical laminate of the present invention may be disposed on the viewing side of the touch input element (liquid crystal cell), may be disposed on the backlight side, or may be disposed on both sides. The driving method of the liquid crystal cell may be any one of conventional methods such as TN mode, VA mode, IPS mode, multi-zone mode, and OCB mode. In the liquid crystal display device of the present invention, the substrate 40 included in the optical layered body may be a substrate (typically a glass substrate) included in the liquid crystal cell.

[Examples]

Hereinafter, the present invention will be more specifically described by showing examples and comparative examples, but the present invention is not limited to the examples. Hereinafter, the amount used, the amount of the content, and the % are indicated, and the weight basis is not indicated unless otherwise noted.

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

In a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, and a stirrer, a solution obtained by mixing a monomer having a composition shown in Table 1 (the numerical value in Table 1 is a part by weight) and 81.8 parts of ethyl acetate was added. After replacing the air in the reaction vessel with nitrogen, the internal temperature was raised to 60 °C. Then, a solution of 0.12 parts of azobisisobutyronitrile dissolved in 10 parts of ethyl acetate was added. After maintaining at the same temperature for 1 hour, while maintaining the internal temperature at 54 to 56 ° C, ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts/hour to adjust the concentration of the polymer to about 35%. Ethyl acetate was added from the start of the addition of ethyl acetate until the temperature was maintained at 54 to 56 ° C for 12 hours, and the concentration of the polymer was adjusted to 20% to obtain ethyl acetate of the (meth)acrylic resin (A-1). Solution. The weight average molecular weight Mw of the (meth)acrylic resin (A-1) was 1.39 million, and the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn was 5.32. In the gel permeation chromatography (GPC) discharge curve, the composition of Mw 1.39 million shows a single peak, and there are no other peaks in the range of Mw 1000 to 2.5 million.

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

An ethyl acetate solution of the (meth)acrylic resin (A-2) was obtained in the same manner as in Production Example 1 except that the composition of the monomer was as shown in Table 1. Degree: 20%). The (meth)acrylic resin (A-2) had a weight average molecular weight Mw of 1.41 million and Mw/Mn of 4.71. In the GPC discharge curve, the composition of Mw 1.39 million shows a single peak, and there are no other peaks in the range of Mw 1000 to 2.5 million.

In the above-mentioned production example, the weight average molecular weight Mw and the number average molecular weight Mn are sold by the "TSKgel XL" manufactured by Tosoh Co., Ltd. and the "Shin Kwong Trading Co., Ltd." manufactured by Showa Denko Electric Co., Ltd. in the GPC device. A total of 5 Shodex GPC KF-802" were arranged in series as a column, using tetrahydrofuran as the eluent, the sample concentration was 5 mg/mL, the sample introduction amount was 100 μL, and the temperature was 40 ° C, and the flow rate was 1 mL/min. Under the conditions, it was determined by converting standard polystyrene. The conditions for obtaining the GPC discharge curve are also the same.

The glass transition temperature Tg was measured using a differential scanning calorimeter (DSC) "EXSTAR DSC600" manufactured by SII Nanotechnology Co., Ltd. under a nitrogen atmosphere at a temperature ranging from -80 to 50 ° C and a temperature rising temperature of 10 ° C /min. .

The composition of the monomer of each production example (the numerical value in Table 1 is a part by weight) and the number of peaks in the range of Mw of 1,000 to 2.5 million on the discharge curve of GPC (shown as "number of GPC peaks in Table 1") are summarized in Table 1.

The abbreviation of the column of "monomer composition" in Table 1 means the following monomers.

BA: butyl acrylate (glass transition temperature of homopolymer: -54 ° C)

MA: methyl acrylate (glass transition temperature of homopolymer: 10 ° C)

HEA: 2-hydroxyethyl acrylate

<Examples 1 to 3, Comparative Example 1> (1) Modulation of adhesive composition

The ethyl acetate solution (resin concentration: 20%) of the (meth)acrylic resin obtained in the above production example, and the solid content of the solution was 100 parts, and the amount (parts by weight) shown in Table 2 was mixed as shown in Table 2. The isocyanate-based crosslinking agent (B), the decane compound (C), and the ionic compound (D) were further added with ethyl acetate to have a solid content concentration of 14% to obtain an adhesive composition. The blending amount of each of the blending components shown in Table 2 is the weight fraction of the active component contained in the case where the product to be used contains a solvent or the like.

The details of the respective components shown in the abbreviation in Table 2 are as follows.

(isocyanate crosslinking agent)

B-1: Ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate (solid content: 75%), trade name "TAKENATE D-110N" obtained from Mitsui Chemicals Co., Ltd.

(decane compound)

C-1: 3-glycidoxypropyltrimethoxydecane, trade name "KBM403" obtained from Shin-Etsu Chemical Co., Ltd.

(ionic compound)

D-1: bis(fluorosulfonyl)imide potassium

D-2: bis(trifluoromethanesulfonyl)imide lithium

D-3: N-octyl-4-methylpyridinium hexafluorophosphate

(2) Production of adhesive layer

Each of the adhesive compositions prepared in the above (1) is applied to a release film comprising a release-treated polyethylene terephthalate using an applicator [LINTEC Corporation] The release surface of "PLR-382051"] 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 optical film (P-1) with adhesive layer

A polyvinyl alcohol film (Kuraray Vinylon VF-PE #6000, manufactured by Kuraray Co., Ltd.) having an average polymerization degree of about 2400, a saponification degree of 99.9 mol%, and a thickness of 60 μm was immersed in pure water at 37 ° C. It was immersed in an aqueous solution containing iodine and potassium iodide (iodine/potassium iodide/water (weight ratio) = 0.04/1.5/100) at 30 °C. Then, it was immersed in an aqueous solution containing potassium iodide and boric acid at 56.5 ° C (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100). The film was washed with pure water at 10 ° C, and then dried at 85 ° C to obtain a polarizer having an iodine-adsorbed orientation of polyvinyl alcohol having a thickness of about 23 μm. The extension was carried out mainly in the steps of iodine dyeing and boric acid treatment, and the total stretching ratio was 5.3 times.

A transparent protective film made of a triethylenesulfonated cellulose film having a thickness of 25 μm was bonded to one surface of the obtained polarizer via an adhesive composed of an aqueous solution of a polyvinyl alcohol resin [Konica Minolta Optical ( The product name of the stock system is "KC2UA"]. Then, a film of a cyclic polyolefin resin having a thickness of 23 μm was bonded to the surface of the polarizing plate opposite to the triacetyl cellulose film of the polarizer via an adhesive composed of an aqueous solution of a polyvinyl alcohol resin. A zero-phase retardation film [trade name "ZEONOR" manufactured by Japan ZEON Co., Ltd.] was used to prepare a polarizing plate. Then, after the corona discharge treatment for improving the adhesion is performed on the surface of the zero retardation film on the side opposite to the surface in contact with the polarizer, the adhesive layer prepared in the above (2) is bonded by a laminator. After the surface on the opposite side of the film (adhesive layer), the film was aged for 7 days under the conditions of a temperature of 23 ° C and a relative humidity of 65% to obtain an optical film (P-1) with an adhesive layer.

(4) Production of optical film (P-2) with adhesive layer

A polyvinyl alcohol film [Kuraray Vinylon VF-PE #3000" manufactured by Kuraray Co., Ltd. having an average polymerization degree of about 2400, a saponification degree of 99.9 mol%, and a thickness of 30 μm was immersed in pure water at 37 ° C. It was immersed in an aqueous solution containing iodine and potassium iodide (iodine/potassium iodide/water (weight ratio) = 0.04/1.5/100) at 30 °C. Then, it was immersed in an aqueous solution containing potassium iodide and boric acid at 56.5 ° C (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100). The film was washed with pure water at 10 ° C, and then dried at 85 ° C to obtain a polarizer having an iodine-adsorbed orientation of polyvinyl alcohol having a thickness of about 12 μm. The extension was carried out mainly in the steps of iodine dyeing and boric acid treatment, and the total stretching ratio was 5.3 times.

A transparent protective film made of a triethylenesulfonated cellulose film having a thickness of 25 μm was bonded to one surface of the obtained polarizer via an adhesive composed of an aqueous solution of a polyvinyl alcohol resin [Konica Minolta Optical ( The product name "KC2UA" made by the company is made of polarizing plates. Then, on the surface opposite to the bonding surface of the protective film of the polarizer, the surface (adhesive layer) on the opposite side of the release film of the adhesive layer prepared in the above (2) is bonded by a laminator at a temperature of 23 After curing at 7 °C under conditions of °C and relative humidity of 65%, an adhesive layer was obtained. Optical film (P-2).

(5) Evaluation of metal corrosion resistance of optical film with adhesive layer

The optical film (P-1) with the adhesive layer prepared in the above (3) was cut into a test piece having a size of 20 mm × 50 mm, and attached to the metal layer side of the glass substrate with the metal layer via the adhesive layer. . The glass substrate with a metal layer is a glass substrate (manufactured by GEOMATEC Co., Ltd.) in which a metal aluminum layer having a thickness of about 500 nm is deposited by sputtering on the surface of the alkali-free glass. The obtained optical laminate was stored in an oven at a temperature of 60 ° C and a relative humidity of 90% for 500 hours, and then the metal layer of the portion to which the optical film of the adhesive layer was attached was placed against the light from the back surface of the glass substrate. The surface of the polarizing plate was observed by a magnifying glass, and the pitting corrosion (the occurrence of a hole having a diameter of 0.1 mm or more and penetrating light) was evaluated by the following criteria. The results are shown in Table 3.

4: the number of pitting corrosion occurring on the surface of the metal layer is 2 or less, 3: the number of pitting corrosion occurring on the surface of the metal layer is 3 to 5, 2: the number of pitting corrosion occurring on the surface of the metal layer is 6 More than one, 1: most of the surface of the surface of the metal layer is crusted and white turbidity occurs.

(6) Durability evaluation of optical film with adhesive layer

The optical film (P-1) with the adhesive layer prepared in the above (3) is cut to a length of 200 mm × 150 mm so that the direction of the axis of extension of the polarizing plate is long, and the release film is peeled off to expose the adhesive layer. Bonded to a glass substrate. The test piece to which the obtained glass substrate was attached (the optical film with the adhesive layer attached to the glass substrate) was pressurized in an autoclave at a temperature of 50 ° C and a pressure of 5 kg/cm ² (490.3 kPa) for 20 minutes. As the glass substrate, an alkali-free glass manufactured by Corning Incorporated, trade name "Eagle XG" was used. The following three kinds of durability tests were carried out on the obtained optical laminate.

[Durability Test]

‧ 750 hours of heat resistance test under dry conditions at 85 ° C; ‧ heat and humidity test for 750 hours at 60 ° C and 90% relative humidity; ‧ 30 minutes under dry conditions at 85 ° C, then - The drying cycle was maintained at 40 ° C for 1 minute for 1 cycle, and 400 cycles of the thermal shock (HS) test were repeated.

The optical laminates after the respective tests were visually observed to visually observe the presence or absence of changes in the appearance of the adhesive layer such as floating, peeling, and foaming, and the durability was evaluated according to the following evaluation criteria. The results are shown in Table 3.

4: It is completely impossible to recognize the change in appearance such as floating, peeling, and foaming.

3: It is almost impossible to recognize the change in appearance such as floating, peeling, and foaming.

2: A slight change in the appearance of floating, peeling, foaming, etc.

1: Significantly confirm the appearance change of floating, peeling, foaming, etc.

(7) Evaluation of the reworkability of the optical film with the adhesive layer

The optical film (P-1) with the adhesive layer prepared in the above (3) was cut into a test piece of 25 mm × 150 mm. After peeling off the release film from the test piece, the adhesive layer was attached to the glass substrate. The obtained test piece attached to the glass substrate (optical film to which the adhesive layer of the glass substrate was attached) was pressurized in an autoclave at a temperature of 50 ° C and a pressure of 5 kg/cm ² (490.3 kPa) for 20 minutes. Then, after holding in an oven at a temperature of 50 ° C for 48 hours, and then in an environment of a temperature of 23 ° C and a relative humidity of 50%, the optical film and the adhesive layer were peeled off from the test piece at a speed of 300 mm/min in a 180° direction. . The state of the surface of the glass substrate after peeling was observed, and it evaluated by the following evaluation criteria. The results are shown in Table 3.

4: No turbidity was observed on the surface of the glass substrate. 3: The surface of the glass substrate was almost incapable of confirming turbidity. 2: The surface of the glass substrate was confirmed to be turbid. 1. The surface of the glass substrate was confirmed to have a residue of the adhesive layer.

(8) Evaluation of fading property of optical film with adhesive layer

The optical film (P-2) with the adhesive layer prepared in the above (4) was cut into a size of 30 mm × 30 mm, and the release film was peeled off, and the exposed adhesive layer was bonded to the glass substrate. As the glass substrate, an alkali-free glass manufactured by Corning Incorporated, trade name "Eagle XG" was used. For the obtained optical layered body, a spectrophotometer with an integrating sphere [product name "V7100" manufactured by JASCO Corporation] was used, and the MD transmittance and the TD transmittance in the wavelength range of 380 to 780 nm were measured, and each was calculated. The transmittance and the degree of polarization of the wavelength are then measured by the 2D field of view (C light source) of JIS Z8701:1999 "Color display method - XYZ color system and X ₁₀ Y ₁₀ Z ₁₀ color system" Correction was performed to obtain the opacity-corrected monomer transmittance (Ty) and the opacity-corrected polarization (Py) before the endurance test. Further, the optical laminate is provided on the side of the triacetyl cellulose film of the polarizing plate as a detector side, and is provided on a spectrophotometer with an integrating sphere so that light is incident from the glass substrate side.

The monomer transmittance and the degree of polarization are defined by the following formula: monomer transmittance (λ) = 0.5 × (Tp (λ) + Tc (λ))

The degree of polarization (λ) = 100 × ((Tp(λ) - Tc(λ)) / (Tp(λ) + Tc(λ)))). Tp(λ) is the transmittance (%) of the optical laminate measured by the linear polarization of the incident wavelength λ (nm) and Parallel Nicol, and Tc(λ) is the incident wavelength λ. The transmittance (%) of the optical laminate measured by the linear polarization of (nm) and the relationship of Cross Nicol.

Then, the optical laminate was allowed to stand in a hot and humid environment at a temperature of 80 ° C and a relative humidity of 90% for 24 hours, and then left in a temperature of 23 ° C and a relative humidity of 60% for 24 hours, by the same method as before the endurance test. Find the Ty and Py after the endurance test. Then, Py and Ty before the test were subtracted from the Py and Ty after the test, and the amount of change before and after the endurance test was calculated, and the amount of change in the degree of polarization (ΔPy) and the amount of change in the monomer transmittance (ΔTy) were obtained. . ΔPy is shown in Table 3.

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

In a reaction vessel equipped with a cooling tube, a nitrogen gas introduction tube, a thermometer, and a stirrer, a solution obtained by mixing a monomer having a composition shown in Table 4 (the numerical value in Table 4 is a part by weight) and 81.8 parts of ethyl acetate was added. After replacing the air in the reaction vessel with nitrogen, the internal temperature was raised to 60 °C. Then, a solution of 0.12 parts of azobisisobutyronitrile dissolved in 10 parts of ethyl acetate was added. After maintaining at the same temperature for 1 hour, while maintaining the internal temperature at 54 to 56 ° C, ethyl acetate was continuously added to the reaction vessel at an addition rate of 17.3 parts / hr to adjust the concentration of the polymer to about 35%. Ethyl acetate was added from the start of the addition of ethyl acetate until the temperature was maintained at 54 to 56 ° C for 12 hours, and the concentration of the polymer was adjusted to 20% to obtain ethyl acetate of the (meth)acrylic resin (A-1). Solution. The weight average molecular weight Mw of the (meth)acrylic resin (A-1) was 1.39 million, and the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn was 5.32. In the gel permeation chromatography (GPC) discharge curve, the composition of Mw 1.39 million showed a single peak, and in the range of Mw 1000 to 2.5 million, no other peaks were observed.

In the above-mentioned production example, the weight average molecular weight Mw and the number average molecular weight Mn are "Shodex" sold by Tosoh Corporation's "TSKgel XL" and "Showa Electric Co., Ltd." A total of five GPC KF-802" were arranged in series as a column, using tetrahydrofuran as the eluent, the sample concentration was 5 mg/mL, the sample introduction amount was 100 μL, and the temperature was 40 ° C, and the flow rate was 1 mL/min. Next, measured by conversion of standard polystyrene. The conditions for obtaining the GPC discharge curve are also the same.

The glass transition temperature Tg was measured using a differential scanning calorimeter (DSC) "EXSTAR DSC600" manufactured by SII Nanotechnology Co., Ltd. under a nitrogen atmosphere at a temperature ranging from -80 to 50 ° C and a temperature rising temperature of 10 ° C /min. .

The composition of the monomer of each production example (the numerical value in Table 4 is a part by weight) and the number of peaks in the range of Mw of 1,000 to 2.5 million on the discharge curve of GPC (shown as "number of GPC peaks in Table 4") are summarized in Table 4.

The abbreviation of the column of "monomer composition" in Table 4 means the following monomers.

BA: butyl acrylate (glass transition temperature of homopolymer: -54 ° C)

MA: methyl acrylate (glass transition temperature of homopolymer: 10 ° C)

HEA: 2-hydroxyethyl acrylate

<Examples 4 to 5, Comparative Examples 2 to 3> (1) Modulation of adhesive composition

In the ethyl acetate solution (resin concentration: 20%) of the (meth)acrylic resin obtained in the above production example, 100 parts of the solid content of the solution were mixed according to the amounts (parts by weight) shown in Table 5, respectively. The isocyanate-based crosslinking agent (B), the decane compound (C) and the ionic compound (D) were further added with ethyl acetate to have a solid content concentration of 14% to obtain an adhesive composition. The blending amount of each of the blending components shown in Table 5 is the weight fraction of the active component contained in the case where the product to be used contains a solvent or the like.

The details of each of the blending components shown in Table 5 are abbreviated as follows.

(isocyanate crosslinking agent)

B-1: Ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate (solid content: 75%), trade name "TAKENATE D-110N" obtained from Mitsui Chemicals Co., Ltd.

(decane compound)

C-1: 3-glycidoxypropyltrimethoxydecane, trade name "KBM403" obtained from Shin-Etsu Chemical Co., Ltd.

(ionic compound)

D-1: bis(fluorosulfonyl)imide potassium

D-2: bis(trifluoromethanesulfonyl)imide lithium

D-3: N-octyl-4-methylpyridinium hexafluorophosphate

D-4: Lithium iodide

(2) Production of adhesive layer

Each of the adhesive compositions prepared in the above (1) was applied to a release film comprising a release-treated polyethylene terephthalate using an applicator [PLR-382051 obtained by LINTEC Co., Ltd. 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 optical film (P-1) with adhesive layer

A polyvinyl alcohol film having an average polymerization degree of about 2,400, a saponification degree of 99.9 mol%, and a thickness of 60 μm [Kuraray Vinylon VF-PE #6000, manufactured by Kuraray Co., Ltd.] was immersed in pure water at 37 ° C, It was immersed in an aqueous solution containing iodine and potassium iodide (iodine/potassium iodide/water (weight ratio) = 0.04/1.5/100) at 30 °C. Then, it was immersed in an aqueous solution containing potassium iodide and boric acid at 56.5 ° C (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100). The film was washed with pure water at 10 ° C, and then dried at 85 ° C to obtain a polarizer having an iodine-adsorbed orientation of polyvinyl alcohol having a thickness of about 23 μm. The extension was carried out mainly in the steps of iodine dyeing and boric acid treatment, and the total stretching ratio was 5.3 times.

A transparent protective film made of a triethylenesulfonated cellulose film having a thickness of 25 μm was bonded to one surface of the obtained polarizer via an adhesive composed of an aqueous solution of a polyvinyl alcohol resin [Konica Minolta Optical ( The product name of the stock system is "KC2UA"]. Then, a film made of a cyclic polyolefin resin having a thickness of 23 μm is bonded to a surface of the polarizing plate opposite to the triacetyl cellulose film of the polarizer via an adhesive composed of an aqueous solution of a polyvinyl alcohol resin. A retardation film [trade name "ZEONOR" manufactured by ZEON Co., Ltd., Japan] was used to produce a polarizing plate. Then, after the corona discharge treatment for improving the adhesion is performed on the surface of the zero retardation film on the side opposite to the surface in contact with the polarizer, the adhesive layer prepared in the above (2) is bonded by a laminator. After the surface on the opposite side of the film (adhesive layer), the film was aged for 7 days under the conditions of a temperature of 23 ° C and a relative humidity of 65% to obtain an optical film (P-1) with an adhesive layer.

(5) Evaluation of metal corrosion resistance of optical film with adhesive layer <Comparative Example 2>

The optical film (P-1) with the adhesive layer prepared in the above (3) was cut into a test piece having a size of 20 mm × 50 mm, and attached to the metal layer side of the glass substrate with the metal layer via the adhesive layer. . The glass substrate with a metal layer is a glass substrate (manufactured by GEOMATEC Co., Ltd.) in which a metal aluminum layer having a thickness of about 500 nm is deposited by sputtering on the surface of the alkali-free glass. The obtained optical laminate was stored in an oven at a temperature of 60 ° C and a relative humidity of 90% for 500 hours, and then the metal layer of the portion to which the optical film of the adhesive layer was attached was placed against the light from the back surface of the glass substrate. The surface of the polarizing plate was observed by a magnifying glass, and the pitting corrosion (the occurrence of a hole having a diameter of 0.1 mm or more and penetrating light) was evaluated by the following criteria. The results are shown in Table 6.

<Examples 4 to 5, Comparative Example 3>

The optical film (P-1) with the adhesive layer prepared in the above (3) was cut into a test piece having a size of 20 mm × 50 mm, and attached to the metal layer side of the glass substrate with the metal layer via the adhesive layer. . The glass substrate with a metal layer is a glass substrate in which a silver alloy (an alloy containing silver as a main component, an alloy of palladium and copper, or APC) having a thickness of about 500 nm is deposited on the surface of the alkali-free glass by sputtering. The obtained optical laminate was stored in an oven at a temperature of 60 ° C and a relative humidity of 90% for 500 hours, and then the metal layer of the portion to which the optical film of the adhesive layer was attached was placed against the light from the back surface of the glass substrate. The surface of the polarizing plate was observed by a magnifying glass, and the pitting corrosion (the occurrence of a hole having a diameter of 0.1 mm or more and penetrating light) was evaluated by the following criteria. The results are shown in Table 6.

4: the number of pitting corrosion occurring on the surface of the metal layer is 2 or less, 3: the number of pitting corrosion occurring on the surface of the metal layer is 3 to 5, 2: The number of pitting corrosion occurring on the surface of the metal layer was 6 or more, and 1: the majority of the surface of the surface of the metal layer was cavitation and white turbidity occurred.

1‧‧‧Optical film with adhesive layer

10‧‧‧Optical film

20‧‧‧Adhesive layer

30‧‧‧metal layer

40‧‧‧Substrate

Claims (20)

An optical laminate comprising, in order, an optical film, an adhesive layer and a metal layer; wherein the metal layer is a metal wiring layer and comprises a layer selected from the group consisting of copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, One or more types of lead and an alloy containing two or more kinds of metals selected from the above; the adhesive layer contains (meth)acrylic resin (A), isocyanate crosslinking agent (B), a decane compound (C) and the following formula (I): M ⁺ X ^- (I) (in the formula (I), M ⁺ represents an inorganic cation, and X ^- represents an anion containing a fluorine atom), an ionic compound (D) ) is composed of an adhesive composition. The optical laminate according to claim 1, wherein the adhesive composition contains 0.01 to 2.5 parts by weight of the aforementioned isocyanate crosslinking relative to 100 parts by weight of the (meth)acrylic resin (A). The agent (B), 0.01 to 10 parts by weight of the aforementioned decane compound (C) and 0.2 to 8 parts by weight of the aforementioned ionic compound (D). The optical laminate according to claim 1 or 2, wherein the metal wiring layer has a line width of 10 μm or less. The optical layered body according to claim 1 or 2, wherein the inorganic cation is an alkali metal ion or an alkaline earth metal ion. The optical layered body according to claim 4, wherein the alkali metal ion is a lithium cation, a potassium cation or a sodium cation. The optical laminate according to claim 4, wherein the alkali is The metal ion is a potassium cation. The optical layered body according to claim 1 or 2, wherein the fluorine atom-containing anion is represented by the following formula (II): [Y(SO ₂ C _m F _2m+1 ) _n ] ^- (II) ( In the formula (II), Y represents a carbon atom or a nitrogen atom, Y represents a carbon atom, n is 3, Y represents a nitrogen atom, and when n is 2, m represents an integer of 0 to 10, the fluorine atom-containing anion. The optical layered body according to claim 1 or 2, wherein the fluorine atom-containing anion is a bis(fluorosulfonyl) quinone imine anion or a bis(trifluoromethanesulfonyl) quinone imine. The optical layered body according to claim 1 or 2, wherein the fluorine atom-containing anion is a bis(fluorosulfonyl) quinone imine. The optical layered product according to claim 1, wherein the (meth)acrylic resin (A) contains a constituent unit of an alkyl acrylate (a1) having a glass transition temperature of less than 0 ° C from a homopolymer. And a constituent unit of the alkyl acrylate (a2) having a glass transition temperature of 0 ° C or higher from the homopolymer. The optical layered product according to claim 10, wherein the content of the constituent unit derived from the alkyl acrylate (a2) of the (meth)acrylic resin (A) is a (meth)acrylic resin. 10 parts by weight or more of 100 parts by weight of all the constituent units of (A). The optical layered body according to claim 10, wherein the aforementioned alkyl acrylate (a2) comprises methyl acrylate. An optical laminate according to claim 1 or 2, wherein the front The (meth)acrylic resin (A) contains a constituent unit derived from a monomer having a hydroxyl group. The optical layered product according to claim 1 or 2, wherein the (meth)acrylic resin (A) does not substantially contain a constituent unit derived from a monomer having a carboxyl group. The optical layered body according to claim 1 or 2, wherein the adhesive composition does not substantially contain a compound selected from the group consisting of a triazole compound, a thiazole compound, an imidazole compound, and an imidazoline compound. Quinoline compound, pyridine compound, pyrimidine compound, oxime compound, amine compound, urea compound, sodium benzoate, benzyl sulfonium compound, di-butyl butyl sulfide and diphenyl A group of rust inhibitors. The optical laminate according to claim 1 or 2, wherein the metal layer is a layer formed by sputtering. The optical layered body according to claim 1 or 2, wherein the metal layer has a thickness of 3 μm or less. A liquid crystal display device comprising the optical laminate as described in claim 1 or 2. An adhesive composition containing 0.01 to 2.5 parts by weight of an isocyanate crosslinking agent (B) and 0.01 to 10 parts by weight of decane based on 100 parts by weight of the above (meth)acrylic resin (A). Compound (C) and 0.2 to 8 parts by weight of the following formula (I): M ⁺ X ^- (I) (in the formula (I), M ⁺ represents an inorganic cation, and X ^- represents an anion having a fluorine atom) The ionic compound (D) is an adhesive composition for forming an adhesive layer on the metal layer; the metal layer is a metal wiring layer and comprises a material selected from the group consisting of copper, silver, iron, tin, zinc, nickel, One or more types of molybdenum, chromium, tungsten, lead, and an alloy containing two or more kinds of metals selected from the above. An optical film with an adhesive layer comprising an optical film and an adhesive layer laminated on at least one side of the optical film, and adhered to the adhesive layer for the metal layer via the adhesive layer An optical film; wherein the metal layer is a metal wiring layer, and comprises an alloy selected from the group consisting of copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and a metal containing two or more metals selected from the group consisting of The adhesive layer is contained in an amount of 0.01 to 2.5 parts by weight based on 100 parts by weight of the (meth)acrylic resin (A), and isocyanate crosslinking agent (B), 0.01. To 10 parts by weight of the decane compound (C) and 0.2 to 8 parts by weight of the following formula (I): M ⁺ X ^- (I) (in the formula (I), M ⁺ represents an inorganic cation, and X ^- represents a fluorine atom An anion) is formed by an adhesive composition of the ionic compound (D).