TW201823015A - 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 laminated body, liquid crystal display device, adhesive composition and optical film   

The present invention relates to an optical multilayer body constituting an image display device such as a liquid crystal display device and a liquid crystal display device including the optical multilayer body.

An optical film typified by a polarizing plate formed by laminating a transparent resin film on one or both sides of a polarizer 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 Japanese Patent Application Laid-Open No. 2010-229321]. Therefore, as an optical film, an optical film with an adhesive layer provided with an adhesive layer in advance on one side of the surface is known. It is also known to contain an ionic compound in the adhesive layer in order to impart antistatic properties.

In recent years, liquid crystal display devices have been used in mobile devices with touch panel functions typified by smart phones, tablet terminals, and car navigation systems. An optical film with an adhesive layer in such a touch input type liquid crystal display device is one in which the adhesive layer is disposed on a metal layer composed of, for example, metal wiring, such as through a resin layer, or by direct contact. However, in a combination of a metal layer made 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. Porosity during corrosion is particularly problematic because the thickness of the metal layer is thin or the line width is narrow when the metal layer is metal wiring.

An object of the present invention is to provide an optical laminated body in which an optical film with an adhesive layer is laminated on a metal layer such as a metal wiring layer, an optical laminated body capable of suppressing corrosion of a metal layer, and a liquid crystal display device including the optical laminated body.

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

[1] An optical laminate, which includes: an optical film, an adhesive layer, and a metal layer in order; wherein the aforementioned adhesive layer is composed of a (meth) acrylic resin (A), an isocyanate-based crosslinking agent (B), Silane compound (C) and the following formula (I) ions compound (D) is shown in the adhesive composition is constituted, M ⁺ X ^- (I) (in the formula (I), M ⁺ represents an inorganic cation, X ^- represents an anion containing a fluorine atom); with respect to the (meth) acrylic resin 100 parts by weight of (a), the aforementioned adhesive composition containing 0.01 to 2.5 parts by weight of the isocyanate-based crosslinking agent (B), 0.01 to 10 parts by weight of the aforementioned silane compound (C) and 0.2 to 8 parts by weight of the ionic compound (D).

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

[3] The optical laminate 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 laminate according to [1] or [2], wherein the alkali metal cation is a potassium cation [K ⁺ ].

[5] The optical laminate according to any one of [1] to [4], 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] of [1] to [5] The optical laminate of any one of claims, wherein the anion containing a fluorine atom is a bis (fluorosulfonyl acyl) imide anion ^{_{[(FSO 2) 2 N -}} ] or bis (trifluoromethane sulfonic acyl) imide anion _{[(CF 3 SO 2) 2} N -].

[7] of [1] to [5] The optical laminate of any one of claims, wherein the anion containing a fluorine atom is a bis (fluorosulfonyl acyl) imide anion ^{_{[(FSO 2) 2 N -}} ].

[8] The optical laminate according to any one of [1] to [7], wherein the (meth) acrylic resin (A) contains an alkyl acrylate having a glass transition temperature of less than 0 ° C derived from a homopolymer The structural unit of (a1) and the structural unit of the alkyl acrylate (a2) derived from a homopolymer having a glass transition temperature of 0 ° C or higher.

[9] The optical laminate according to [8], wherein the content of the constitutional unit derived from the alkyl acrylate (a2) in the (meth) acrylic resin (A) is the amount of A) It is 10 weight part or more among 100 weight part of all the structural units.

[10] The optical laminate according to [8] or [9], wherein the alkyl acrylate (a2) contains methyl acrylate.

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

[12] The optical laminate according to any one of [1] to [11], wherein the (meth) acrylic resin (A) does not substantially include a structural 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 include a member selected from the group consisting of triazole-based compounds, thiazole-based compounds, imidazole-based compounds, and imidazoline. ) Compounds, quinoline compounds, pyridine compounds, pyrimidine compounds, indole compounds, amine compounds, urea compounds, sodium benzoate, benzyl mercaptan compounds, di-2nd butyl A group of rust preventives for thioethers and diphenylsulfinium.

[14] The optical multilayer body according to any one of [1] to [13], wherein the metal layer includes a member selected from the group consisting of aluminum, copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and One or more kinds of alloys including alloys of two or more kinds of metals selected from these.

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

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

[17] The optical laminated body 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 including the optical multilayer body according to any one of [1] to [17].

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

According to the present invention, an optical multilayer body capable of suppressing corrosion of a metal layer and a liquid crystal display device including the optical multilayer body can be provided.

1‧‧‧ Optical film with adhesive layer

2‧‧‧ polarizer

3‧‧‧The first resin film

4‧‧‧ 2nd resin film

5, 6, 7‧‧‧‧ optical laminated body

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 multilayer body according to 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 laminate.

Fig. 5 is a schematic cross-sectional view showing another example of the layer configuration of the optical laminate.

Fig. 6 is a schematic cross-sectional view showing another example of the layer configuration of the optical laminate.

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

    <Optical laminated body>    

FIG. 1 is a schematic cross-sectional view showing an example of an optical multilayer body according to the present invention. As shown in FIG. 1, the optical laminate 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 laminated body may also be an optical film 1 with an adhesive layer including an optical film 10 and an adhesive layer 20 laminated on at least one side of the metal layer 30 formed on the substrate 40. It is made by bonding together through this adhesive layer 20.

The adhesive layer 20 is usually directly laminated on the surface of the optical film 10. Moreover, the optical film 1 with an adhesive layer is usually laminated on the metal layer 30 such that the adhesive layer 20 directly contacts the metal layer 30. According to the present invention, in such an optical laminate, the corrosion of the metal layer 30 can be effectively suppressed. Hereinafter, the property of suppressing the corrosion of the metal layer 30 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 multi-layer structure. The adhesive layer 20 is composed of an adhesive composition containing a (meth) acrylic resin (A), an isocyanate-based crosslinking agent (B), a silane compound (C), and an ionic compound (D). The adhesive composition may further contain other components. In this specification, "(meth) acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The same applies to "(meth) acrylate", "(meth) acrylfluorenyl", and the like.

    [1] Optical film    

The optical film 10 included in the optical multilayer body 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. Film). The optical film 10 may be an optical film having a single-layer structure or an optical film having a multi-layer 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-condensing film, in addition to the polarizer. Specific examples of the optical film having a multilayer structure include a polarizing plate and a retardation plate. In this specification, a polarizing plate refers to a resin film or a resin layer of an area layer on at least one side of a polarizer. The retardation plate refers to an area layer resin film or a resin layer on at least one side of the retardation film. The optical film 10 is preferably a polarizing plate, a polarizing plate, a retardation 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 examples of the layer configuration of a polarizing plate. The polarizing plate 10a shown in FIG. 2 is a polarizing plate in which the area layer on one side of the polarizer 2 is bonded to the single-sided protection of the first resin film 3, and the polarizing plate 10b shown in FIG. 3 is attached to the polarizer. The other side of 2 is further laminated and bonded to the polarizing plates protected on both sides 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 and 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.

Examples of the layer configuration of the optical laminate when the polarizing plates 10a and 10b shown in FIGS. 2 and 3 are used as an optical film are shown in FIGS. 4 and 5 respectively. The optical laminated body 5 shown in FIG. 4 is an example when the polarizing plate 10 a shown in FIG. 2 is used as an optical film, and the optical laminated body 6 shown in FIG. 5 is a polarized light shown in FIG. 3. An example when the plate 10b is used as an optical film.

The polarizer 2 is a film having a linearly polarizing property that absorbs linearly polarized light having a vibration plane parallel to its absorption axis and penetrates a vibrational plane having a vertical absorption axis (parallel to the transmission axis). For example, it can be used for polyvinyl alcohol resin The film adsorbs a film that aligns a dichroic pigment. As the dichroic pigment, iodine and a dichroic organic dye can be used.

The polyvinyl alcohol-based resin can be obtained by saponifying a polyvinyl acetate-based resin. Examples of the polyvinyl acetate-based resin include, in addition to polyvinyl acetate, a separate polymer of vinyl acetate, and copolymers of a monomer copolymerizable with vinyl acetate and vinyl acetate. Examples of the monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, (meth) acrylamide having an ammonium group, and the like.

The saponification degree of the polyvinyl alcohol resin is usually 85 to 100 mol%, and more preferably 98 mol% or more. The polyvinyl alcohol-based resin can be modified. For example, aldehyde-modified polyvinyl formal or polyvinyl acetal can be used. The average degree of polymerization of the polyvinyl alcohol resin is usually 1,000 to 10,000, and more preferably 1500 to 5,000. The average degree of polymerization of the polyvinyl alcohol-based resin can be obtained in accordance with JIS K 6726.

In general, a film made of a polyvinyl alcohol resin is used as a raw material film of the polarizer 2. The polyvinyl alcohol resin can be formed into a film by a conventional method. The thickness of the raw material film is usually 1 to 150 μm, and considering the ease of stretching, etc., it is preferably 10 μm or more.

The polarizer 2 is, for example, a step of uniaxially stretching the raw film, a step of dyeing the film with a dichroic pigment to adsorb the dichroic pigment, a step of treating the film with a boric acid aqueous solution, and a step of washing the film, and finally drying and Manufacturing. The thickness of the polarizer 2 is usually 1 to 30 μm. From the viewpoint of thinning the optical film 1 with an adhesive layer, the thickness is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less.

The polarizer 2 formed of a dichroic pigment adsorbed and aligned on a polyvinyl alcohol-based resin film uses 1) a single film of a polyvinyl alcohol-based resin film as a raw material film, and the film is subjected to uniaxial stretching and dichroism. A method for dyeing a pigment and 2) applying a coating solution (aqueous solution, etc.) containing a polyvinyl alcohol resin to a substrate film and drying the substrate film to obtain a substrate film having a polyvinyl alcohol resin layer, and then It can be obtained by performing uniaxial stretching together with the base film, applying a dichroic dye to the stretched polyvinyl alcohol resin layer, and then peeling and removing the base film. As the base film, a film made of the same thermoplastic resin as the thermoplastic resin constituting the first and second resin films 3 and 4 described below can be used, and a polyester resin such as polyethylene terephthalate is more preferable. , A polycarbonate resin, a cellulose resin such as triethylfluorenyl cellulose, a cyclic polyolefin resin such as norbornene resin, a polystyrene resin, and the like. According to the method 2), the production of the thin film polarizer 2 is easy, 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 each have a light-transmitting property independently, and are preferably optically transparent thermoplastic resins, such as a chain polyolefin resin (polyethylene resin, polypropylene resin, etc.), and a ring. Polyolefin resins (such as norbornene resins); cellulose resins (cellulose ester resins, etc.); polyester resins (polyethylene terephthalate, polyethylene naphthalate) (Ethylene glycol, polybutylene terephthalate, etc.); polycarbonate resins; (meth) acrylic resins; polystyrene resins; polyetheretherketone resins; polyfluorene resins; or such Films made of mixtures, copolymers, etc. Among them, the first and second resin films 3 and 4 are each a group selected from the group consisting of a cyclic polyolefin resin, a polycarbonate resin, a cellulose resin, a polyester resin, and a (meth) acrylic resin. The resin composition is preferably composed of a resin selected from the group consisting of a cellulose resin and a cyclic polyolefin resin.

As the chain polyolefin resin, in addition to a homopolymer of a chain olefin such as a polyethylene resin and a polypropylene resin, a copolymer composed of two or more types of chain olefins may be mentioned.

The cyclic polyolefin resin is a general term for a resin including norbornene, tetracyclododecene (alias: dimethyl bridge octahydronaphthalene), or a cyclic olefin as a representative example thereof as a polymerization unit. Specific examples of cyclic polyolefin resins include ring-opened (co) polymers of cyclic olefins and their hydrides, addition polymers of cyclic olefins, cyclic olefins, and chain olefins such as ethylene and propylene. Or copolymers of aromatic compounds having a vinyl group, and such modified (co) polymers modified with an unsaturated carboxylic acid or a derivative thereof. Among them, as the cyclic olefin, a norbornene-based resin using a norbornene-based monomer such as norbornene or a polycyclic norbornene-based monomer is preferred.

The cellulose-based resin is preferably a cellulose ester-based resin, that is, a partial or complete esterification of cellulose, such as cellulose acetate, propionate, butyrate, and mixed esters thereof. Among them, triethyl cellulose, diethyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, etc. are preferably used.

The polyester resin is a resin other than the above-mentioned cellulose ester resin having an ester bond, and is generally composed of a polycondensate of a polycarboxylic acid or a derivative thereof and a polyhydric alcohol. Specific examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polytrimethylene terephthalate. Ester, polynaphthalate, polycyclohexane dimethyl terephthalate, cyclohexane dimethyl polynaphthalate.

Polycarbonate resins are polyesters made of carbonic acid and diols or bisphenols. Among them, it is preferable to use an aromatic carbonate having a diphenylalkane in the molecular chain from the viewpoints of heat resistance, weather resistance, and acid resistance. As the polycarbonate, for example, 2,2-bis (4-hydroxyphenyl) propane (alias: bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis ( Polycarbonates derived from bisphenols such as 4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) isobutane, and 1,1-bis (4-hydroxyphenyl) ethane.

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

As a copolymerization component copolymerizable with a methacrylate, an acrylate is mentioned, for example. 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 other copolymerization components are, for example, unsaturated acids such as (meth) acrylic acid; aromatic vinyl compounds such as styrene, halogenated styrene, α-methylstyrene, and vinyl toluene; (meth) propylene Vinyl cyanide, such as nitrile; Unsaturated anhydride, such as maleic anhydride, methyl maleic anhydride; Unsaturated hydrazone, such as phenylmaleimide, cyclohexylmaleimide, etc. Compounds other than 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 be used as a copolymerization component. A copolymerization component may be used individually by 1 type, and may use 2 or more types together.

The (meth) acrylic resin may have a ring structure in the polymer main chain in order to improve the durability of the film. The ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic amidine structure, and a lactone ring structure. As specific examples of the cyclic anhydride structure, for example, glutaric anhydride structure and succinic anhydride structure, and as specific examples of the cyclic amidine structure, for example, glutarimide structure, succinimide structure, and 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 and impact resistance of the film. The acrylic rubber particles refer to particles having an elastic polymer mainly composed of acrylate as an essential component. For example, a single-layer structure consisting essentially of the elastic polymer or one layer of the elastic polymer is used. Multi-layer constructor. Examples of the elastic polymer include, for example, a crosslinked elastic copolymer containing an alkyl acrylate as a main component and copolymerized with other vinyl monomers and crosslinkable monomers copolymerizable therewith. Examples of the alkyl acrylate to be the main component of the elastic polymer include C ₁ to C ₈ alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. The carbon number of the alkyl group is preferably 4 or more.

Examples of other vinyl monomers that can be copolymerized with alkyl acrylates include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methyl methacrylate, such as Aromatic vinyl compounds of styrene, vinyl cyanides such as (meth) acrylonitrile, and the like. Examples of the crosslinkable monomer include a crosslinkable compound having two or more polymerizable carbon-carbon double bonds in the molecule, and more specifically, ethylene glycol di (meth) acrylate and butanediol di (Meth) acrylates of polyhydric alcohols such as (meth) acrylates, (meth) acrylic alkenes such as allyl (meth) acrylate, divinylbenzene, and the like.

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 a 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 more 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 ordinary additives in the technical field of the present invention. Specific examples of the additives include, for example, ultraviolet absorbers, infrared absorbers, organic dyes, pigments, inorganic pigments, antioxidants, antistatic agents, surfactants, lubricants, dispersants, and thermal stabilizers.

Examples of the ultraviolet absorber include a salicylate-based compound, a diphenyl ketone-based compound, a benzotriazole-based compound, and (triazine) compounds, cyano (meth) acrylate compounds, nickel salts, and the like.

The first and second resin films 3 and 4 may be non-stretched films, or may be uniaxially or biaxially stretched films. Biaxial extension can be simultaneous biaxial extension in two extension directions, or successive biaxial extension 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 is responsible for protecting the polarizer 2 and may be a protective film having an optical function of a retardation film as described later. The retardation film is an optical film showing optical anisotropy. For example, a film made of the thermoplastic resin (e.g., uniaxial or biaxial stretching) or a liquid crystal layer formed on the thermoplastic resin film can be used to form a retardation film having an arbitrary retardation value.

The first resin film 3 and the second resin film 4 may be films made of the same thermoplastic resin or films made of different thermoplastic resins. The first resin film 3 and the second resin film 4 may be the same as or different from each other in thickness, presence or absence and type of additives, retardation characteristics, and the like.

The first resin film 3 and / or the second resin film 4 may be provided with a hard coat layer, an anti-glare layer, an anti-reflection layer, a light diffusion layer, an anti-static layer, and an anti-glare layer on the outer surface (the surface opposite to the polarizer 2). Surface treatment layer (coating layer) such as a stain layer, a conductive layer, and the like.

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

In particular, for small and medium-sized polarizers called smart phones and tablet terminals, thin films with a thickness of 30 μm or less are often used as the first resin film 3 and / or the second resin film 4 due to thin film requirements. The polarizing plate has a weak contraction force for suppressing the polarizer 2 and is liable to become insufficient in durability. According to the present invention, even when such a polarizing plate is used as the optical film 10, it is possible to provide an optical film 1 with an adhesive layer and an optical laminate having excellent durability. The durability of the optical film 1 with the adhesive layer and the optical laminated body refers to, for example, a high-temperature environment, a high-temperature and high-humidity environment, and a high-temperature and low-temperature environment where the adhesive layer 20 and the optical adjacent to it can be suppressed. Defects such as floating, peeling of the interface of the member, and blistering of the adhesive layer 20.

From the viewpoint of thinning the polarizing plate, the polarizing plate 10 a shown in FIG. 2 is advantageous in that a resin film is arranged on only one side of the polarizing plate 2. In this case, the adhesive layer 20 is usually directly adhered to the other surface of the polarizer 2 to form an optical film 1 with an adhesive layer (see FIG. 4). In the case of a polarizing plate having such a configuration, the problem of a reduction in the optical performance of the polarizing plate in a high-temperature and high-humidity environment becomes particularly significant due to the ionic compound contained in the adhesive layer 20. According to the present invention, even in the case where such a polarizing plate is used as the optical film 10, it is possible to provide an optical film 1 with an adhesive layer and an optical laminate having excellent optical durability (property capable of suppressing deterioration of optical characteristics). .

The first and second resin films 3 and 4 can be bonded to the polarizer 2 through an adhesive layer and 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.

Examples of the water-based adhesive include an adhesive composed of a polyvinyl alcohol-based resin aqueous solution, and a water-based two-liquid amine ester-based emulsification adhesive. Among these, a water-based adhesive composed of a polyvinyl alcohol-based resin aqueous solution is suitably used. As the polyvinyl alcohol resin, in addition to a vinyl alcohol homopolymer obtained by saponifying a polyvinyl acetate homopolymer of polyvinyl acetate, vinyl acetate and other monomers copolymerizable therewith may also be used. The polyvinyl alcohol-based copolymer obtained by saponifying the copolymer, or the modified polyvinyl alcohol-based polymer in which the hydroxyl group is partially modified. The water-based adhesive may include a crosslinking agent such as an aldehyde compound, an epoxy compound, a melamine-based compound, a methylol compound, an isocyanate compound, an amine compound, or a polyvalent metal salt.

In the case of using a water-based adhesive, it is preferable to perform a drying step in order to remove the water contained in the water-based adhesive after the polarizer 2 is bonded to the first and second resin films 3 and 4. After the drying step, a ripening step such as ripening at about 20 to 45 ° C. may be provided.

The above-mentioned active energy ray-curable adhesive refers to an adhesive that is cured by irradiating active energy rays such as ultraviolet rays and electron rays, and includes, for example, a curable composition containing a polymerizable compound and a photopolymerization initiator, and a photoreaction A curable composition of a flexible resin, a curable composition containing a binder resin and a photoreactive cross-linking agent, and the like. A UV-curable adhesive is more preferable. Examples of the polymerizable compound include a photocurable epoxy-based monomer, a photocurable (meth) acrylic monomer, a photocurable monomer of a photocurable amine ester monomer, and an oligo derived from the photopolymerizable monomer. Polymer. The photopolymerization initiator includes, for example, a substance that generates active species such as neutral radicals, anionic radicals, and cationic radicals upon irradiation with active energy rays. As the active energy ray-curable adhesive containing a polymerizable compound and a photopolymerization initiator, a photocurable (meth) -containing curable composition containing a photocurable epoxy-based monomer and a photocationic polymerization initiator is used. A curable composition of an acrylic monomer and a photoradical polymerization initiator, or a mixture of such curable compositions is preferred.

In the case of using an active energy ray-curable adhesive, after the polarizer 2 is bonded to the first and second resin films 3 and 4, a drying step is performed as required, and then the active energy ray is hardened by irradiating the active energy ray. A hardening step followed by hardening of the agent. There is no particular limitation on the source of the active energy ray. Ultraviolet rays with a light emission distribution below 400 nm are ideal. Specifically, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black lights, microwave-excited mercury lamps, Metal halide lamps, etc.

When the polarizer 2 and the first and second resin films 3 and 4 are bonded, a surface activation treatment such as saponification treatment, corona treatment, or plasma treatment may be performed on the bonding surface of at least one of these. When a resin film is bonded to both sides of the polarizer 2, the adhesive for bonding these resin films may be the same kind of adhesive or different kinds of adhesives.

The polarizing plates 10a and 10b may further include 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-condensing film, and an adhesive layer, a coating layer, a protective film, and the like other than the retardation film 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 being damaged or contaminated. After the optical film 1 with an adhesive layer is attached to, for example, the metal layer 30, it is usually peeled and removed.

The protective film is usually composed of a base film and an adhesive layer laminated on the base film. The base film can be made of thermoplastic resins such as polyolefin resins such as polyethylene resins and polypropylene resins; polyester resins such as polyethylene terephthalate, polyethylene naphthalate; polycarbonate Based resin; (meth) acrylic based resin.

    [1-2] Phase difference plate    

The retardation film included in the retardation plate is an optical film exhibiting optical anisotropy as described above. In addition to the thermoplastic resins exemplified above for the first and second resin films 3 and 4, for example, polyvinyl alcohol resins , Polyarylate resin, polyimide resin, polyether fluorene resin, polyvinylidene fluoride / polymethyl methacrylate resin, liquid crystal polyester resin, ethylene-vinyl acetate copolymer saponification, A resin film made of a polyvinyl chloride resin or the like is a stretched film obtained by stretching about 1.01 to 6 times. Among these, a polycarbonate resin film, a cyclic olefin resin film, a (meth) acrylic resin film, or a cellulose resin film is preferably an uniaxially or biaxially stretched stretched film. Moreover, in this specification, a zero retardation film is also included in a retardation film (however, a zero retardation film can also be used as a protective film). In addition, a film called a uniaxial retardation film, a wide viewing angle retardation film, a low photoelasticity retardation film, or the like may also be applied as the retardation film.

The zero-hysteresis film refers to a film in which both the in-plane retardation value R _e and the thickness direction retardation value R _th are -15 to 15 nm. This retardation film is suitable for use in an IPS (In-Plane Switching) mode liquid crystal display device. The in-plane retardation value R _e and the thickness direction retardation value R _th are preferably -10 to 10 nm, and more preferably -5 to 5 nm. Here, the in-plane retardation value R _e and the thickness direction retardation value R _th are values having 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 formulas: R _e = (n _x -n _y ) × d

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

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

Further, a film that exhibits optical anisotropy by coating / alignment of a liquid crystalline compound or a film that exhibits optical anisotropy by application of an inorganic layered compound can also be used as a retardation film. For such retardation films, there are those known as temperature-compensated retardation films, and rod-shaped liquid crystals sold by JX Nippon Steel and Nissho Energy Co., Ltd. under the trade name of "NH FILM" are obliquely aligned films. The disc-shaped liquid crystals sold under the brand name of “WV FILM” by Fujifilm (stock) are obliquely aligned films. The fully biaxially-aligned type is sold by Sumitomo Chemical (stock) under the brand name of “VAC FILM” Membranes, biaxially oriented membranes, etc. that are also sold under the brand name "new VAC FILM" by Sumitomo Chemical Co., Ltd.

The resin film laminated on at least one surface 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-based crosslinking agent (B), a silane compound (C), and an ionic compound ( D) An adhesive composition. In the adhesive compositions in an ionic compound (D) based the following formula (I): M ⁺ X ^- ionic compound (I) shown below. In formula (I), M ⁺ represents an inorganic cation, and X ⁻ represents an anion containing a fluorine atom.

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

According to the adhesive layer 20 composed of the above-mentioned adhesive composition, in the optical laminated body including the adhesive layer 20 and the metal layer 30, the corrosion of the metal layer 30 can be suppressed, and the optical film 1 with the adhesive layer can be improved. And the durability of optical laminates. In addition, according to the adhesive layer 20 composed of the above-mentioned adhesive composition, the optical film 1 and the optical laminate with the adhesive layer formed thereon can be displayed well even if the adhesive layer 20 is directly bonded to the polarizer 2. Optical durability.

The thickness of the adhesive layer 20 is usually 2 to 40 μm. From the viewpoints of the durability of the optical film 1 and the optical laminate with the adhesive layer, and the reworkability of the optical film 1 with the adhesive layer, it is more preferably 5 to 30 μm, more preferably 10 to 25 μm. In addition, 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, reworkability is improved.

The adhesive layer 20 preferably 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 an optical laminated body with an adhesive layer can be improved more effectively. The so-called "displaying a storage elastic modulus in a temperature range of 23 to 80 ° C from 0.1 to 5 MPa" means any temperature in this range, and the storage elastic modulus is a value within the above range. The storage elastic modulus generally decreases with increasing temperature. If the storage elastic modulus at 23 ° C and 80 ° C is within the above range, the storage elastic modulus within 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, for example, 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 having a structural unit derived from a (meth) acrylic monomer as a main component (preferably containing 50% by weight or more). The (meth) acrylic monomer includes, for example, a monomer having a (meth) acrylfluorene group, and preferably includes an alkyl (meth) acrylate. The alkyl group of the alkyl (meth) acrylate preferably has a carbon number of 1 to 14, more preferably 1 to 12, and even more preferably 1 to 8, and may be linear, branched, or cyclic. As the alkyl (meth) acrylate, a substituent-containing alkyl (meth) acrylate containing a substituent-containing alkyl acrylate introduced into a substituent as described later can also be used. The alkyl (meth) acrylate may be used alone or in combination of two or more.

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

The (meth) acrylic resin (A) contains a structural unit containing an alkyl acrylate (a1) having a glass transition temperature Tg of less than 0 ° C derived from the homopolymer and an alkyl acrylate having a Tg of the homopolymer of 0 ° C or higher The constituent unit of (a2) is preferable. This is beneficial to improve the metal corrosion resistance and durability of the optical film 1 and the optical laminate with the adhesive layer. The Tg of the homopolymer of the alkyl acrylate can be, for example, a literature value such as the Polymer Handbook (Wiley-Interscience).

Specific examples of the alkyl acrylate (a1) include ethyl acrylate, n- and iso-propyl acrylate, n- and iso-butyl acrylate, n-pentyl acrylate, n- and iso-hexyl acrylate, and n-acrylate -Heptyl, n- and iso-octyl acrylate, 2-ethylhexyl acrylate, n- and iso-nonyl acrylate, n- and iso-decyl acrylate, and n-dodecyl acrylate Alkyl acrylate having a carbon number of about 2 to 12. As another specific example of the alkyl acrylate (a1), for example, an alkyl acrylate containing a substituent may be used as the alkyl group-inducing substituent in the alkyl acrylate having an alkyl group having about 2 to 12 carbon atoms. The substituent of the alkyl acrylate containing a substituent may be a group substituted for a hydrogen atom of an alkyl group, and specific examples thereof include a phenyl group, an alkoxy group, and a phenoxy group. Specific examples of the alkyl acrylate containing a substituent include 2-methoxyethyl acrylate, ethoxymethyl acrylate, phenoxyethyl acrylate, and phenoxydiethylene glycol acrylate. 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) preferably contains one or two or more selected from the group consisting of ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl 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, it is preferable that the alkyl acrylate (a1) contains n-butyl acrylate.

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, and tert-butyl acrylate.

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

The content of the structural unit derived from the alkyl acrylate (a2) in the (meth) acrylic resin (A) is in terms of the metal corrosion resistance and durability of the optical film 1 and the optical laminate with the adhesive layer Out of 100 parts by weight of all the constituent units of the (meth) acrylic resin (A), it is more 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 even more preferably 25 parts by weight or more. . From the viewpoint of the followability and reworkability of the adhesive layer 20 to the optical film 10, the content of the constituent units derived from the alkyl acrylate (a2) is preferably 70 parts by weight or less, more preferably 60 parts by weight or less, and more preferably It is preferably 50 parts by weight or less.

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

    1) Monomers with polar functional groups    

Examples of the monomer having a polar functional group include (meth) acrylates having a substituent such as a hydroxyl group, a carboxyl group, a substituted or unsubstituted heterocyclic group such as an amine group, and an epoxy group. Specifically, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- (2-hydroxyethoxy) (meth) acrylate (Hydroxy) ethyl ester, 2-chloro-2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, etc. Monomers; allyl morpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, vinyl pyridine, tetrahydrofuran methyl (meth) acrylate, tetrahydrofuran methyl acrylate modified Monomers having a heterocyclic group such as 3,4-epoxycyclohexyl methyl (meth) acrylate, propylene oxide (meth) acrylate, 2,5-dihydrofuran; (meth) acrylic acid Monomers with substituted or unsubstituted amino groups, such as aminoethyl esters, N, N-dimethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylate; (methyl ) A monomer having a carboxyl group such as acrylic acid or carboxyethyl (meth) acrylate. Among these, a monomer having a hydroxyl group is preferable, and a (meth) acrylic acid ester having a hydroxyl group is more preferable in terms of the reactivity of the (meth) acrylic resin (A) and the crosslinking agent.

The monomer having the above-mentioned other polar functional group may be contained together with the (meth) acrylate having a hydroxyl group. From the viewpoint of preventing the release force of the release film that can be laminated on the outer surface of the adhesive layer 20 from being excessively increased, It is desirable to include a monomer having an amine group. Further, from the viewpoint of improving the corrosion resistance to ITO, it is preferable to substantially not contain a monomer having a carboxyl group. The term "substantially not included" herein means that the total weight of all constituent units constituting the (meth) acrylic resin (A) is 0.1 part by weight or less.

    2) acrylamide-based monomer    

For example, N-hydroxymethyl acrylamide, N- (2-hydroxyethyl) acrylamide, N- (3-hydroxypropyl) acrylamide, N- (4-hydroxybutyl) acrylamide, N -(5-hydroxypentyl) acrylamide, N- (6-hydroxyhexyl) acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropyl Acrylamide, N- (3-dimethylaminopropyl) acrylamide, N- (1,1-dimethyl-3-butoxybutyl) acrylamide, N- [2- (2-Pentoxy-1-imidazolidinyl) ethyl] acrylamidonium, 2-propenylaminoamino-2-methyl-1-propanesulfonic acid, N- (methoxymethyl) propenehydrazone Amine, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (1-methylethoxymethyl) acrylamide, N- (1- Methylpropoxymethyl) acrylamide, N- (2-methylpropoxymethyl) acrylamide [alias: N- (isobutoxymethyl) acrylamide], N- (butyl Oxymethyl) acrylamide, N- (1,1-dimethylethoxymethyl) acrylamide, N- (2-methoxyethyl) acrylamide, N- (2-ethyl (Oxyethyl) acrylamide, N- (2-propoxyethyl) acrylamide, N- [2- (1-methylethoxy) ethyl] acrylamide, N- [2- (1-methylpropane (Yl) ethyl] acrylamide, N- [2- (2-methylpropoxy) ethyl] acrylamide [alias: N- (isobutoxyethyl) acrylamide], N- ( 2-butoxyethyl) acrylamide, N- [2- (1,1-dimethylethoxy) ethyl] acrylamide, and the like. Among them, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (butoxymethyl) ) Acrylamide and N- (2-methylpropoxymethyl) acrylamide are preferred.

    3) Methacrylic acid ester    

For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, lauryl methacrylate and the like are linear alkyl methacrylates; Branched alkyl methacrylates such as isobutyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate; isobornyl methacrylate, cyclohexyl methacrylate, methyl Dicyclopentyl acrylate, cyclododecyl methacrylate, methyl cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, third butyl cyclohexyl methacrylate, cyclohexyl methacrylate Alicyclic alkyl esters of methacrylic acid such as phenyl esters; alkoxyalkyl esters of methacrylic acid such as 2-methoxyethyl methacrylate and ethoxymethyl methacrylate; benzoyl methacrylate Aryl methacrylates such as esters; 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2- (2-hydroxyethoxy methacrylate) ) Ethyl ester, 2-chloro-2-hydroxypropyl methacrylate, 3-chloro-2-hydroxy methacrylate Alkyl esters of methacrylic acid having a hydroxyl group such as esters, diethylene glycol monomethacrylate; aminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, dimethacrylate Alkyl esters of methacrylic acid having substituted or unsubstituted amine groups such as methylaminopropyl ester; 2-phenoxyethyl methacrylate, 2- (2-phenoxyethoxy) ethyl methacrylate Esters, ethylene oxide modified nonylphenol esters of (meth) acrylic acid, esters of methacrylic acid having phenoxyethyl groups such as 2- (o-phenylphenoxy) ethyl methacrylate, etc. .

    4) Methacrylamide-based monomer    

For example, a methacrylamide-based monomer corresponding to the acrylamide-based monomer described in 1) above.

    5) styrene monomer    

For example, styrene; such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexyl Alkylstyrenes such as styrene, heptylstyrene, octylstyrene, etc .; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene, etc .; nitrostyrene ; Ethyl styrene; methoxystyrene; divinylbenzene and the like.

    6) vinyl monomer    

For example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, and other fatty acid vinyl esters; vinyl chloride, vinyl bromide, and other halogenated ethylene; vinyl chloride Halogenated vinylidene; nitrogen-containing aromatic vinyl such as vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc .; conjugated diene monomers such as butadiene, isoprene, chloroprene, etc .; Unsaturated nitriles such as acrylonitrile and methacrylonitrile.

    7) Monomers with multiple (meth) acrylfluorene 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 di (Meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, etc. have two (methyl) ) Monomers of acryl fluorenyl group; monomers having three (meth) acryl fluorenyl groups in the molecule such as trimethylolpropane tri (meth) acrylate and the like.

As described above, the (meth) acrylic resin (A), from the viewpoint of the durability and metal corrosion resistance of the optical film 1 and the optical laminated body with the adhesive layer, is the constituent unit derived from the alkyl (meth) acrylate In addition, it is preferable to include a structural unit derived from a monomer having a polar functional group. The monomer having a polar functional group is more preferably a (meth) acrylate-based 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 and more preferably from 0.25 to 5 out of 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.

Further, from the viewpoint of reworkability of the optical film 1 with the adhesive layer, the (meth) acrylic resin (A) is derived from a methacrylate (methacrylic acid ester), a methacrylamide-based monomer, or the like The content of the constituent units of the methacrylic monomer is preferably less. Specifically, the content of the constituent units is preferably 10 parts by weight based on 100 parts by weight of all constituent units constituting the (meth) acrylic resin (A). 5 parts by weight or less, more preferably 5 parts by weight or less, and more preferably, the constituent unit is not substantially contained (0.1 parts by weight or less).

The (meth) acrylic resin (A) has a weight average molecular weight on the discharge curve of a gel permeation chromatograph (GPC) in the range of Mw 10 to 2.5 million, and preferably has a single peak, and in the range of Mw 1000 to 2.5 million It is more preferable that it has a single peak and contains a structural unit derived from the alkyl acrylates (a1) and (a2). The adhesive layer 20 using such a (meth) acrylic resin (A) as a matrix polymer is advantageous in improving the durability of the optical film 1 and the optical laminate with the adhesive layer. In the case where the number of peaks in the above-mentioned range of Mw is 2 or more, there is a tendency that sufficient durability cannot be obtained.

The number of peaks of the GPC discharge curve in the range of Mw1000 to 2.5 million was determined, and the discharge curve was obtained according to the GPC measurement conditions described in the item of the example. In the above range of the obtained discharge curve, the so-called "having a single peak" means that the range of Mw1000 to 2.5 million has only one maximum value. In this specification, a peak is defined as a G / C discharge curve with an S / N ratio of 30 or more.

According to the (meth) acrylic resin (A), the Mw of polystyrene according to the GPC conversion standard is preferably in the range of 500,000 to 2.5 million, and more preferably in the range of 600,000 to 2 million. When Mw is 500,000 or more, it is beneficial to improve the metal corrosion resistance and durability of the optical film 1 and the optical laminate with the adhesive layer, and it also tends to improve the reworkability of the optical film 1 with the adhesive layer. When 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 represented by the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn is usually 2 to 10. Mw and Mn of the (meth) acrylic resin (A) can be determined according to 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, a viscosity at 25 ° C. of 20 Pa · s or less is preferable, and 0.1 to 7 Pa · s is more preferable. A viscosity in such a range is advantageous for improving the durability of the optical film 1 and the optical laminate with the adhesive layer, and the reworkability of the optical film 1 with the adhesive layer. The above viscosity can be measured by a Brookfield viscometer.

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

The adhesive composition may contain two or more types of (meth) acrylic resins that belong to the (meth) acrylic resin (A). Moreover, the adhesive composition may contain other (meth) acrylic resin other than (meth) acrylic resin (A). However, from the viewpoint of the metal corrosion resistance and durability of the optical film 1 and the optical laminate with the adhesive layer, the content of the (meth) acrylic resin (A) is the same as that of the entire (meth) acrylic resin. In the total, it is more preferably 70% by weight or more, more preferably 80% by weight or more, and even more preferably 90% by weight or more. The adhesive composition is particularly one containing only (meth) acrylic resin (A) as a matrix polymer. ideal.

The (meth) acrylic resin (A) or other (meth) acrylic resin that can be used in combination as required can be obtained by a known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method. Manufacturing. For the production of (meth) acrylic resins, a polymerization initiator is usually used. The polymerization initiator is used in an amount of about 0.001 to 5 parts by weight based on 100 parts by weight of the total of all the monomers used in the production of the (meth) acrylic resin. The (meth) acrylic resin can also be produced by, for example, 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. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone. As the thermal polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1) -Nitrile), 2,2'-Azobis (2,4-dimethylvaleronitrile), 2,2'-Azobis (2,4-dimethyl-4-methoxyvaleronitrile) Azo compounds such as dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis (2-hydroxymethylpropionitrile); such as laurel peroxide Base, third butyl peroxide, benzoylperoxide, third butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, peroxidation Tertiary butyl neodecanoate, tertiary butyl peroxypivalate, organic peroxides (3,5,5-trimethylhexyl) peroxide; such as potassium persulfate, ammonium persulfate, persulfate Inorganic peroxides such as hydrogen oxide. Further, a redox-based initiator used in combination with a peroxide and a reducing agent can also 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. An example of the solution polymerization method is to mix the monomers used with an organic solvent, add a thermal polymerization initiator under a nitrogen atmosphere, and stir at about 40 to 90 ° C, preferably 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 added continuously or intermittently during the polymerization, or may be added in a state of being dissolved in an organic solvent. As the organic solvent, for example, aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropyl alcohol; such as acetone and methyl ethyl Ketones such as methyl ketone and methyl isobutyl ketone.

    [2-2] Isocyanate-based crosslinking agent (B)    

The adhesive composition contains an isocyanate-based crosslinking agent (B). By using the isocyanate-based crosslinking agent (B) as the crosslinking agent, it is possible to improve the metal corrosion resistance and durability of the optical film 1 and the optical laminate with the adhesive layer. The isocyanate-based crosslinking agent (B) may be used singly or in combination of two or more kinds.

Isocyanate-based crosslinking agent (B) is a compound having at least two isocyanate groups (-NCO) in the molecule, and specifically, for example, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylene Diisocyanate, hydrogenated xylyl diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthyl diisocyanate, triphenylmethane triisocyanate, and the like. The isocyanate-based crosslinking agent (B) may be an adduct of a polyol compound of the isocyanate compound (for example, an adduct of glycerol or trimethylolpropane), an isocyanurate compound, or a polycondensate. Biuret type compounds, and amine ester prepolymers with addition reactions such as polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, polyisoprene polyols, etc. Derivatives such as isocyanate compounds. Among the above, in particular, xylylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, or polyol compound adducts of these isocyanate compounds are preferable. From the optical film 1 and the From the viewpoint of the durability of the laminated body, a xylylene diisocyanate or an adduct of a polyol compound thereof is more preferable.

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

The adhesive composition may be used together with the isocyanate-based crosslinking agent (B), and other crosslinking agents such as epoxy compounds, aziridine compounds, metal clamp compounds, peroxides, etc. From the standpoint of the metal corrosion resistance and durability of the optical film 1 and the optical laminate with the adhesive layer, the adhesive composition contains only an isocyanate-based crosslinking agent (B), and particularly does not substantially contain a peroxide. More ideal. The term "substantially not included" means that the content of the (meth) acrylic resin (A) is 0.01 parts by weight or less.

    [2-3] Silane compound (C)    

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

Examples of the silane compound (C) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, and 3-glycidoxypropyltrimethoxy Silane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane , 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacrylium Oxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

The silane compound (C) may include a polysiloxane oligomer type. When the polysiloxane oligomer is expressed as a combination of monomers, it is as shown below.

3-mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane Mercaptopropyl-containing oligomers such as methoxysilane oligomers, 3-mercaptopropyltriethoxysilane-tetraethoxysilane oligomers; mercaptomethyltrimethoxysilane-tetramethoxy Silane oligomer, mercaptomethyltrimethoxysilane-tetraethoxysilane oligomer, mercaptomethyltriethoxysilane-tetramethoxysilane oligomer, mercaptomethyltriethoxysilane-tetraol Mercaptomethyl-containing oligomers such as ethoxysilane oligomers; 3-glycidoxypropyltrimethoxysilane-tetramethoxysilane oligomers, 3-glycidoxypropyl Trimethoxysilane-tetraethoxysilane oligomer, 3-glycidoxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-glycidoxypropyltriethoxy Silane-tetraethoxysilane oligomer, 3-glycidoxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-glycidoxypropylmethyldi Methoxysilane-tetraethoxysilane Oligomer, 3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-glycidoxypropylmethyldiethoxysilane-tetraethoxy 3-glycidyloxypropyl-containing oligomers such as silane oligomers; 3-methacryloxypropyltrimethoxysilane-tetramethoxysilane oligomers, 3-methyl Acrylic methoxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-methacrylic acid propyltriethoxysilane-tetramethoxysilane oligomer, 3-methylpropene Methoxypropyltriethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-methyl Propylene alkoxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer Oligomers including methacryloxypropyl, 3, 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane oligomers; Trimethoxysilane-tetramethoxysilane oligomer, 3-propenefluorene Propyltrimethoxysilane-tetraethoxysilane oligomer, 3-propenyloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropyltriethyl Oxysilane-tetraethoxysilane oligomer, 3-propenyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropylmethyldimethyl Oxysilane-tetraethoxysilane oligomer, 3-propenyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropylmethyldiethyl Propylene methoxypropyl group-containing oligomers such as oxysilane-tetraethoxysilane oligomer; vinyltrimethoxysilane-tetramethoxysilane oligomer, vinyltrimethoxysilane-tetrayl Ethoxysilane oligomer, vinyltriethoxysilane-tetramethoxysilane oligomer, vinyltriethoxysilane-tetraethoxysilane oligomer, vinylmethyldimethoxy Silane-tetramethoxysilane oligomer, vinylmethyldimethoxysilane-tetraethoxysilane oligomer, vinylmethyldiethoxysilane-tetramethoxysilane oligomer, Vinyl armor Vinyl-containing oligomers such as didiethoxysilane-tetraethoxysilane oligomer; 3-aminopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-aminopropyl Trimethoxysilane-tetraethoxysilane oligomer, 3-aminopropyltriethoxysilane-tetramethoxysilane oligomer, 3-aminopropyltriethoxysilane-tetraethyl Oxysilane oligomer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane oligomer Polymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-aminopropylmethyldiethoxysilane-tetraethoxysilane oligomer, etc. Amine-containing oligomers and the like.

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

    [2-4] Ionic compound (D)    

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

In the formula (I), M ⁺ represents an inorganic cation. Specific examples of the inorganic cation include alkali metal ions such as lithium cation [Li ⁺ ], sodium cation [Na ⁺ ], potassium cation [K ⁺ ], cesium cation [Cs ⁺ ]; beryllium cation [Be ²⁺ ], and magnesium cation Alkaline earth metal ions such as [Mg ²⁺ ], calcium cation [Ca ²⁺ ], and the like. Among them, it is preferable to use lithium cation [Li ⁺ ], sodium cation [Na ⁺ ], and potassium cation [K ⁺ ] from the viewpoint of the metal corrosion resistance of the optical film 1 with the adhesive layer and the optical laminate. From the viewpoint of 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. The anion containing a fluorine atom tends to easily impart an ionic compound (D) having an excellent antistatic function. As the anion containing a fluorine atom, either an inorganic anion or an organic anion can be used. Specific examples of inorganic anions can form ionic compound (D), comprising tetrafluoroborate anion [BF ₄ ^-], hexafluorophosphate anions [PF ₆ ^-], hexafluoroarsenate anion [AsF ₆ ^-], six hexafluoroarsenate anion [SbF ₆ ^-], niobium hexafluorophosphate anion [NbF ₆ ^-], six tantalum fluoride anion [TaF ₆ ^-], bis (sulfo-fluoro-acyl) imide anion [(FSO _{2) 2} N ^- ], (poly) fluoride anion fluoride ^{_{[F (HF) n -]}} (n is about 1 to 3) and the like.

Specific examples may be configured ionic compound (D) is an organic anion, trifluoroacetate anion comprising [CF ₃ COO ^-], trifluoromethanesulfonate anion [CF ₃ SO ₃ ^-], bis (trifluoromethane sulfonic acyl ) imide anion _{[(CF 3 SO 2) 2} N -], tris (trifluoromethane sulfonic acyl) methyl (methanide) anion _{[(CF 3 SO 2) 3} C -], perfluoro butane sulfonate anion ^{_{[C 4 F 9 SO 3 -}} ], bis (pentafluoroethane sulfonic acyl) imide anion _{[(C 2 F 5 SO 2} ) 2 N -], perfluoro butyrate 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 anions (e.g. tetrakis (pentafluorophenyl) borate anion, etc.), dicyanimide anion [(CN) ₂ N ^-] and the following formula (III): Shown imine anions and the like.

The fluorine atom-containing anion is preferably from the viewpoint of the antistatic function, the metal corrosion resistance, and the durability of the optical film 1 with the adhesive layer and the optical laminate, and 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 An anion represented by). 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 tris (trifluoromethanesulfonyl) Methyl anion, bis (pentafluoroethanesulfonyl) imide anion, etc. Wherein, using bis (fluorosulfonyl acyl) imide anion [FSI ^-] or bis (trifluoromethane sulfonic acyl) imide anion [TFSI ^-] of the ionic compound (D), in particular, help to improve the adhesive attachment layer The optical film 1 and the optical laminated body have antistatic function, metal corrosion resistance and durability. Y is preferably a nitrogen atom, m is an integer of 0 to 4 is more desirable, an integer of 0 to 1 is more desirable, and 0 is particularly desirable.

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

Bis (fluorosulfonyl) imide lithium

Bis (trifluoromethanesulfonyl) imide lithium

Bis (pentafluoroethanesulfonyl) imide lithium

Tris (trifluoromethanesulfonyl) methyl lithium

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, and 0.3 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic resin (A). Part by weight is more preferable, and 0.5 to 3 parts by weight is particularly preferable. The content of the ionic compound (D) is 0.2 parts by weight or more, which is helpful to improve the antistatic function. When the content is 8 parts by weight or less, it is beneficial to the resistance to metal corrosion and durability of the optical film 1 and the optical laminate with the adhesive layer.

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 metal film 1 of the optical film 1 with an adhesive layer and the optical multilayer body, etc. From the viewpoint, it is preferable that the adhesive composition contains only the ionic compound (D) represented by the formula (I) as an antistatic agent.

    [2-5] other ingredients    

Adhesive composition, which may contain one or more solvents, cross-linking catalysts, ultraviolet absorbers, weather stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, light scattering properties Additives such as micro particles. In addition, an ultraviolet curable compound is blended in the adhesive composition to form an adhesive layer, and then is irradiated with ultraviolet rays to harden it. This is useful for making a harder adhesive layer. Examples of cross-linking catalysts include hexamethylene diamine, ethylene diamine, polyethylenimine, hexamethylene tetramine, diethylene triamine, triethylene tetramine, isophor Amine compounds such as ketodiamine, trimethylenediamine, polyamine resin, and melamine resin.

The adhesive composition may contain a rust preventive agent that can improve the metal corrosion resistance of the optical film 1 with the adhesive layer and the optical laminate. Examples of rust inhibitors include triazole compounds such as benzotriazole compounds and other triazole compounds; thiazoly compounds such as benzothiazole compounds and other thiazole compounds; benzimidazole compounds and other imidazoles Imidazole compounds; imidazoline compounds; quinoline compounds; pyridine compounds; pyrimidine compounds; indole compounds; amine compounds; urea compounds; sodium benzoate; benzyl mercaptan compounds; Di-second butyl sulfide; and diphenylsulfinium.

However, according to the present invention, sufficient corrosion resistance can be obtained even if no rust inhibitor is contained. Therefore, the content of the rust inhibitor is preferably as small as possible. In particular, the adhesive composition is substantially not contained as an antirust agent. A triazole-based compound of a rusting agent is preferable, and a rust preventive agent not substantially selected from the above-mentioned compound group is more preferable. The term "substantially not included" means that the content of the (meth) acrylic resin (A) is 0.01 parts by weight or less.

    [3] Metal layers and substrates    

The metal layer 30 may be, for example, a group consisting of an alloy selected from the group consisting of aluminum, copper, silver, gold, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and two or more metals selected from these. One or more layers are more 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 an aluminum element from the viewpoint of conductivity and cost. More preferably, it is a layer containing an aluminum element as a main component. Including 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 the total metal component.

The metal layer 30 may be, for example, a metal oxide layer such as ITO. As for the optical film with an adhesive layer of the present invention, the metal layer 30 contains the above-mentioned metal element because of its excellent corrosion resistance to metal monomers and alloys. The constituent metal monomer and / or two or more alloys containing the above-mentioned metal element are preferred. However, the optical laminate may include a transparent electrode layer made of a metal oxide such as ITO together with such a metal layer 30.

The form (for example, thickness, etc.) and the method of preparing the metal layer 30 are not particularly limited. In addition to being a metal foil, a vacuum evaporation method, a sputtering method, an ion plating method, an inkjet printing method, or a gravure printing method may be used. 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. The metal layer and the metal foil formed by sputtering tend to have poor corrosion resistance. However, according to the optical multilayer body of the present invention, the metal layer formed by sputtering has good metal corrosion resistance. The thickness of the metal layer 30 is usually 3 μm or less, more preferably 1 μm or less, and even more preferably 0.8 μm or less. The thickness of the metal layer 30 is usually 0.01 μm or more. When the metal layer 30 is a metal wiring layer, the line width of the metal wiring included in the metal wiring layer is usually 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The line width of the metal wiring is usually 0.01 μm or more, more preferably 0.1 μm or more, and even more preferably 0.5 μm or more. The optical layered body of the present invention exhibits good resistance to metal corrosion even with such a thin-film metal layer 30 and a thin-wire metal wiring. In particular, when the metal wiring has 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 is formed by sputtering, corrosion, especially pitting, can 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 a touch input liquid crystal display device. In this case, the metal layer 30 is usually patterned into a predetermined shape. When the adhesive layer 20 is laminated 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 including the above-mentioned metal or alloy.

In addition, the metal layer 30 may have a single-layer structure or a multi-layer structure of two or more layers. Examples of the metal layer having a multilayer structure include a metal-containing layer (metal mesh, etc.) having a three-layer structure shown by molybdenum / aluminum / molybdenum.

As shown in FIG. 1, a metal layer 30 such as a metal wiring layer is usually formed on a substrate 40. In this case, the optical laminate of the present invention includes the substrate 40. The metal layer 30 on the substrate 40 can be formed 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. Examples of the material of the glass substrate include soda-lime glass, low-alkali glass, and alkali-free glass. 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, and when the metal layer 30 is formed on a part of the surface of the substrate 40, a part of the adhesive layer 20, for example, comes into direct contact with the substrate 40 made of glass. The adhesive layer 20 of the optical laminated body of the invention has good adhesion to glass, and the optical laminated body and the liquid crystal display device provided with the optical laminated body are also excellent in durability in this case.

    [4] Structure and manufacturing method of optical laminated body    

In an embodiment, as shown in FIG. 4 and FIG. 5, the optical laminated body of the present invention includes an optical film 1 with an adhesive layer 1 and a metal layer 30 laminated on the adhesive layer 20. In the optical laminates 5 and 6 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 if the optical laminated body having such a configuration that the adhesive layer 20 directly contacts the metal layer 30 can effectively suppress the corrosion of the metal layer 30.

Fig. 6 is a schematic cross-sectional view showing another example of the layer constitution of the optical laminated body of the present invention. In other embodiments, as for the optical laminate of the present invention, as shown in FIG. 6, the adhesive layer 20 of the optical film 1 with the adhesive layer is laminated on the metal layer 30 via the resin layer 50. . The adhesive layer 20 is in direct contact with the resin layer 50. Even in such an optical multilayer body 7, the 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 product layer of a curable resin. As the curable resin capable of forming the resin layer 50, a known person can be used, for example, the one described in Japanese Patent Application Laid-Open No. 2009-217037.

As described above, the metal layer 30 may be a metal wiring layer. An example of a case where the metal layer 30 is a metal wiring layer is shown in FIG. 7. In the optical laminated body shown in FIG. 7, the resin layer 50 may be omitted.

The optical laminated body is, for example, an optical film 1 with an adhesive layer including an optical film 10 and an adhesive layer 20 laminated on at least one side of the metal layer 30 formed on the substrate 40 with the optical film 1 interposed therebetween. The adhesive layer 20 is bonded and manufactured.

As described above, the optical film 1 with an adhesive layer includes an optical film 10 and an adhesive layer 20 (FIG. 1) laminated on at least one side of the optical film 10. An adhesive layer 20 may be layered on two areas of the optical film 10. Generally, 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 is ideal, and corona treatment is more ideal.

In the case where the optical film 10 is a single-sided protected polarizing plate as shown in FIG. 2, the adhesive layer 20 is usually ideally laminated directly on the surface of the polarizer, that is, the surface opposite to the first resin film 3 of the polarizer 2 . In the case where the optical film 10 is a polarizing plate protected on both sides as shown in FIG. 3, the adhesive layer 20 may be laminated on either of the first and second resin films 3 and 4 or may be laminated on both of them. outside.

An antistatic layer can also be provided between the optical film 10 and the adhesive layer 20. The adhesive layer 20 of the present invention can provide good antistatic properties because of the separate adhesive layer. In terms of simplification, it is preferable that there is no antistatic layer between the optical film 10 and the adhesive layer 20.

The optical film 1 with the adhesive layer may also include a release film (release film) laminated on the outside of the adhesive layer 20. This release film is usually peeled and removed when the adhesive layer 20 is used (for example, when it is laminated on the metal layer 30). The release film can be, for example, a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate, and the like. Polysilicon can be formed on the surface forming the adhesive layer 20. Release processors such as oxygen treatment.

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

By bonding the optical film 1 with an adhesive layer to the metal layer 30 (or the above-mentioned resin layer) via the adhesive layer 20, an optical laminate can be obtained. The optical film 1 with the adhesive layer is adhered to the metal layer 30. After making the optical laminate, if there is any defect, the optical film 1 with the adhesive layer is peeled off from the metal layer 30, and other adhesives are re-attached. The layer of the optical film 1 is adhered to the metal layer 30, and so-called heavy work is necessary. With regard to the optical multilayer body of the present invention, the surface of the metal layer 30 after peeling off the optical film 1 with the adhesive layer from the metal layer 30 is less prone to turbidity, adhesive residue, and the like, and has excellent reworkability. According to the optical multilayer body of the present invention, when the surface of the adhesive layer 20 is bonded to the glass substrate or the ITO layer instead of the metal layer 30, good reworkability can be exhibited.

    <Liquid crystal display device>    

The liquid crystal display device of the present invention includes the optical laminate of the present invention. The liquid crystal display device of the present invention can suppress corrosion of the metal layer 30 and exhibit good durability.

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

    [Example]    

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

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

In a reaction vessel provided with a cooling tube, a nitrogen 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 parts by weight) with 81.8 parts of ethyl acetate was placed. After replacing the air in the reaction vessel with nitrogen, the internal temperature was raised to 60 ° C. Then, a solution in which 0.12 parts of azobisisobutyronitrile was 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 into the reaction container at an addition rate of 17.3 parts / hour, so that the concentration of the polymer became approximately 35%. After maintaining the temperature at 54 to 56 ° C. for 12 hours from the start of the addition of ethyl acetate, 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. In the range of Mw 1000 to 2.5 million, there were no other peaks.

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

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

In the above manufacturing examples, the weight average molecular weight Mw and the number average molecular weight Mn are based on GPC equipment and are sold as 4 "TSKgel XL" made by Tosoh Co., Ltd. and "Shokotsu Corporation" made by Showa Denko Corporation. A total of 5 Shodex GPC KF-802 "s were arranged in series as a column, and tetrahydrofuran was used as the eluent. The sample concentration was 5 mg / mL, and the sample introduction amount was 100 μL. The temperature was 40 ° C and the flow rate was 1 mL / min. Under the conditions, it is measured by converting standard polystyrene. The conditions under which the GPC discharge curve is obtained are also the same.

The glass transition temperature Tg is measured using a differential scanning calorimeter (DSC) "EXSTAR DSC600" manufactured by SII Nano Technology Co., Ltd., under a nitrogen environment, the measurement temperature range is -80 to 50 ° C, and the temperature rise temperature is 10 ° C / min. .

The composition of the monomers in each manufacturing example (the numerical values in Table 1 are parts by weight) and the number of peaks in the range of Mw1000 to 2.5 million (expressed as "GPC peak number" in Table 1) on the GPC discharge curve are summarized in Table 1.

The abbreviations in the column of "monomer composition" in Table 1 refer to 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 and Comparative Example 1>         (1) Preparation of adhesive composition    

In the ethyl acetate solution (resin concentration: 20%) of the (meth) acrylic resin obtained in the above-mentioned production example, 100 parts of the solid content of the solution was mixed as shown in Table 2 (parts by weight). The isocyanate-based cross-linking agent (B), the silane compound (C), and the ionic compound (D) were added to ethyl acetate to make the solid content concentration 14% to obtain an adhesive composition. The blending amount of each blending ingredient shown in Table 2 is the weight part of the active ingredient contained in the case where the product used includes a solvent or the like.

The details of each of the compounding components shown by abbreviations in Table 2 are as follows.

    (Isocyanate-based crosslinking agent)    

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

    (Silane compound)    

C-1: 3-glycidoxypropyltrimethoxysilane, trade name "KBM403" obtained from Shin-Etsu Chemical Industry 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 adhesive composition prepared in the above (1) was applied to a release film made of polyethylene terephthalate subjected to a release treatment using an applicator [available from LINTEC Corporation] "PLR-382051"], releasing the treated surface to a thickness of 20 μm after drying, and drying 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 with an average degree of polymerization of about 2400, a degree of saponification 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. , And 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 (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100) at 56.5 ° C. The film was washed with pure water at 10 ° C, and then dried at 85 ° C to obtain a polarizer having a thickness of about 23 μm that is iodine-adsorbed and aligned with polyvinyl alcohol. Stretching is mainly performed in the steps of iodine staining and boric acid treatment, and the total stretching ratio is 5.3 times.

On one side of the obtained polarizer, a transparent protective film composed of a triethylfluorene-based cellulose film having a thickness of 25 μm was bonded through an adhesive made of an aqueous solution of a polyvinyl alcohol resin [Konica Minolta Optics ( "KC2UA"). Then, on the surface opposite to the triacetamyl cellulose film of the above-mentioned polarizer, an adhesive made of an aqueous solution of a polyvinyl alcohol-based resin was laminated to a zero-thickness of a cyclic polyolefin resin having a thickness of 23 μm. A retardation film [trade name "ZEONOR" manufactured by ZEON (Japan)] was used to produce a polarizing plate. Then, a corona discharge treatment is performed on the surface of the zero-phase retardation film opposite to the surface in contact with the polarizer to improve adhesion, and then the lamination machine is used to bond the release layer of the adhesive layer prepared in (2) above. After the surface (adhesive layer) on the opposite side of the mold film was aged at a temperature of 23 ° C. and a relative humidity of 65% for 7 days, an optical film (P-1) with an adhesive layer was obtained.

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

A polyvinyl alcohol film with an average degree of polymerization of about 2400, a degree of saponification of 99.9 mol%, and a thickness of 30 μm [Kuraray Vinylon VF-PE # 3000 manufactured by Kuraray Co., Ltd.] was immersed in pure water at 37 ° C. , And 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 (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100) at 56.5 ° C. The film was washed with pure water at 10 ° C, and then dried at 85 ° C to obtain a polarizer having a thickness of about 12 μm that is iodine-adsorbed and aligned with polyvinyl alcohol. Stretching is mainly performed in the steps of iodine staining and boric acid treatment, and the total stretching ratio is 5.3 times.

On one side of the obtained polarizer, a transparent protective film composed of a triethylfluorene-based cellulose film having a thickness of 25 μm was bonded through an adhesive made of an aqueous solution of a polyvinyl alcohol resin [Konica Minolta Optics ( Under the trade name "KC2UA"] to make a polarizing plate. Then, the opposite surface (adhesive layer) of the release film of the adhesive layer prepared in the above (2) was bonded to the surface opposite to the bonding surface of the protective film of the polarizer by a laminator, and the temperature was 23 at a temperature of 23 The film was aged for 7 days at a temperature of 65 ° C and a relative humidity of 65% to obtain an optical film (P-2) with an adhesive layer.

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

The optical film (P-1) with an adhesive layer prepared in the above (3) was cut into a test piece having a size of 20 mm × 50 mm, and the metal layer was attached to the metal layer side of the glass substrate with a metal layer through the adhesive layer. . The glass substrate with a metal layer is a glass substrate (manufactured by GEOMATEC) used on the surface of an alkali-free glass by sputtering a metal aluminum layer having a thickness of about 500 nm. After the obtained optical laminated body was stored in an oven at a temperature of 60 ° C and a relative humidity of 90% for 500 hours, the state of the metal layer of the portion to which the optical film with the adhesive layer was attached was directed from the back of the glass substrate to the light, The surface of the polarizing plate was observed with a magnifying glass, and the pitting corrosion (the occurrence of holes having a diameter of 0.1 mm or more that can penetrate 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, and 2: the number of pitting corrosion occurring on the surface of the metal layer is 6 More than one, 1: The entire surface of the metal layer surface has a large number of pitting corrosions and white turbidity.

    (6) Evaluation of Durability of Optical Film with Adhesive Layer    

The optical film (P-1) with an adhesive layer prepared in the above (3) was cut to a length of 200 mm × 150 mm so that the extension axis direction of the polarizing plate became a long side, and the release film was peeled off to expose the exposed adhesive layer. Laminated on a glass substrate. The obtained test piece (the optical film with an adhesive layer attached to the glass substrate) to which the obtained 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. As the glass substrate, alkali-free glass manufactured by Corning Corporation and trade name "Eagle XG" was used. The obtained optical laminated body was subjected to the following three types of durability tests.

    [Durability test]    

‧Heat resistance test for 750 hours under dry conditions at a temperature of 85 ℃; ‧Heat resistance test for 750 hours under an environment with a temperature of 60 ℃ and a relative humidity of 90%; It was maintained at 40 ° C. for 30 minutes as one cycle, and the heat shock (HS) test was repeated for 400 cycles.

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

4: It is impossible to recognize appearance changes such as floating, peeling, and foaming

3: It is almost impossible to recognize appearance changes such as floating, peeling, and foaming

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

1: Significantly confirm appearance changes such as floating, peeling, and foaming

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

The optical film (P-1) with an adhesive layer prepared in the above (3) was cut into a test piece of 25 mm × 150 mm. After releasing the release film from the test piece, the adhesive layer was attached to a glass substrate. The obtained glass substrate-attached test piece (the optical film with an adhesive layer attached to the glass substrate) was pressed 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 keeping it in an oven at a temperature of 50 ° C. for 48 hours, the optical film was bonded to the adhesive layer at a speed of 300 mm / min from the test piece at 180 ° C. in an environment of a temperature of 23 ° C. and a relative humidity of 50%. Direction peeling. The state of the surface of the glass substrate after peeling was observed, and it evaluated using the following evaluation criteria. The results are shown in Table 3.

4: Cloudiness cannot be confirmed on the surface of the glass substrate at all, 3: Cloudiness can not be confirmed on the surface of the glass substrate at all, 2: Cloudiness can be confirmed on the surface of the glass substrate, 1: Residue of the adhesive layer can be confirmed on the surface of the glass substrate

    (8) Evaluation of discoloration of optical film with adhesive layer    

The optical film (P-2) with an adhesive layer prepared in the above (4) was cut into a size of 30 mm × 30 mm, the release film was peeled off, and the exposed adhesive layer was bonded to a glass substrate. As the glass substrate, alkali-free glass manufactured by Corning Corporation and trade name "Eagle XG" was used. For the obtained optical multilayer body, using a spectrophotometer with a integrating sphere [product name "V7100" manufactured by JASCO Corporation), the MD transmittance and TD transmittance in the range of 380 to 780 nm were measured, and each was calculated. The single-wavelength transmittance and polarization degree of the wavelength, and then the visual sensitivity of the 2-degree field of view (C light source) according to JIS Z8701: 1999 "Color display method-XYZ color system and X ₁₀ Y ₁₀ Z ₁₀ color system" Correction: Obtain the visual sensitivity correction unit transmittance (Ty) and visual sensitivity correction polarization (Py) before the endurance test. In addition, the optical laminated body is a spectrophotometer with an integrating sphere, with the triethyl cellulose film side of the polarizing plate as the detector side, and the light entering from the glass substrate side.

The cell transmittance and polarization are defined by the following formulas: cell transmittance (λ) = 0.5 × (Tp (λ) + Tc (λ))

Polarization (λ) = 100 × ((Tp (λ) -Tc (λ)) / (Tp (λ) + Tc (λ))). Tp (λ) is the transmittance (%) of the optical multilayer as measured by the relationship between the linearly polarized light at the incident wavelength λ (nm) and Parallel Nicol, and Tc (λ) is the incident wavelength λ (nm) The transmittance (%) of the optical laminate as measured by the relationship between linear polarized light and Cross Nicol.

Then, the optical laminated body was left for 24 hours in a hot and humid environment at a temperature of 80 ° C and a relative humidity of 90%, and then left for 24 hours in an environment of a temperature of 23 ° C and a relative humidity of 60% by the same method as before the endurance test. , Find the Ty and Py after the endurance test. Then, subtract the Py and Ty before the test from the Py and Ty after the test to calculate the change before and after the endurance test, and obtain the change in polarization (△ Py) and the change in monomer transmittance (△ Ty). . ΔPy is shown in Table 3.

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

In a reaction vessel including a cooling tube, a nitrogen 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 parts by weight) with 81.8 parts of ethyl acetate was placed. After replacing the air in the reaction vessel with nitrogen, the internal temperature was raised to 60 ° C. Then, a solution in which 0.12 parts of azobisisobutyronitrile was 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 into the reaction vessel at an addition rate of 17.3 parts / hour, so that the polymer concentration became approximately 35%. After maintaining the temperature at 54 to 56 ° C. for 12 hours from the start of the addition of ethyl acetate, 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 discharge curve of gel permeation chromatography (GPC), the composition of Mw 1.39 million showed a single peak. In the range of Mw 1000 to 2.5 million, no other peak was seen.

In the above manufacturing example, the weight average molecular weight Mw and the number average molecular weight Mn were sold in a GPC device with 4 "TSKgel XL" manufactured by Tosoh Corporation, and "Shodex" sold by Showa Denki Co., Ltd. A total of 5 GPC KF-802 "s were arranged in series as a column, using tetrahydrofuran as an eluent, a sample concentration of 5 mg / mL, a sample introduction amount of 100 μL, and a temperature of 40 ° C and a flow rate of 1 mL / min. In the following, it is measured by converting standard polystyrene. The conditions under which the GPC discharge curve is obtained are also the same.

The glass transition temperature Tg is measured using a differential scanning calorimeter (DSC) "EXSTAR DSC600" manufactured by SII Nano Technology Co., Ltd., under a nitrogen environment, the measurement temperature range is -80 to 50 ° C, and the temperature rise temperature is 10 ° C / min. .

The composition of the monomers in each manufacturing example (the numerical values in Table 4 are parts by weight) and the number of peaks in the range of Mw1000 to 2.5 million (expressed as "GPC peak number" in Table 4) on the GPC discharge curve are summarized in Table 4.

The abbreviations in the column of "monomer composition" in Table 4 refer to 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) Preparation 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 in the amounts (parts by weight) shown in Table 5 respectively. Table 5 The isocyanate-based cross-linking agent (B), the silane compound (C), and the ionic compound (D) were added, and ethyl acetate was added to a solid content concentration of 14% to obtain an adhesive composition. The formulation amount of each formulation component shown in Table 5 is a weight part of the active ingredient contained in the case where the product used contains a solvent etc.

In Table 5, the details of each compounding component shown by the abbreviation are as follows.

    (Isocyanate-based crosslinking agent)    

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

    (Silane compound)    

C-1: 3-glycidoxypropyltrimethoxysilane, trade name "KBM403" obtained from Shin-Etsu Chemical Industry 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 made of polyethylene terephthalate subjected to a release treatment using an applicator [PLR-382051 obtained by LINTEC Corporation]. "] The release-treated surface was adjusted to a thickness of 20 µm after drying, 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 with an average degree of polymerization of about 2400, a degree of saponification 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. An aqueous solution (iodine / potassium iodide / water (weight ratio) = 0.04 / 1.5 / 100) containing iodine and potassium iodide was immersed at 30 ° C. Then, it was immersed in an aqueous solution containing potassium iodide and boric acid (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100) at 56.5 ° C. The film was washed with pure water at 10 ° C, and then dried at 85 ° C to obtain a polarizer having a thickness of about 23 μm that is iodine-adsorbed and aligned with polyvinyl alcohol. Stretching is mainly performed in the steps of iodine staining and boric acid treatment, and the total stretching ratio is 5.3 times.

On one side of the obtained polarizer, a transparent protective film composed of a triethylfluorene-based cellulose film having a thickness of 25 μm was bonded through an adhesive made of an aqueous solution of a polyvinyl alcohol resin [Konica Minolta Optics ( "KC2UA"). Then, on the surface opposite to the triacetamyl cellulose film of the above-mentioned polarizer, an adhesive made of an aqueous solution of a polyvinyl alcohol-based resin was laminated to a zero-thickness of a cyclic polyolefin resin having a thickness of 23 μm. A retardation film [trade name "ZEONOR" manufactured by ZEON (Japan)] was used to produce a polarizing plate. Then, a corona discharge treatment is performed on the surface of the zero-phase retardation film opposite to the surface in contact with the polarizer to improve adhesion, and then the lamination machine is used to bond the release layer of the adhesive layer prepared in (2) above. After the surface (adhesive layer) on the opposite side of the mold film was aged at a temperature of 23 ° C. and a relative humidity of 65% for 7 days, an optical film (P-1) with an adhesive layer was obtained.

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

The optical film (P-1) with an adhesive layer prepared in the above (3) was cut into a test piece having a size of 20 mm × 50 mm, and the metal layer was attached to the metal layer side of the glass substrate with a metal layer through the adhesive layer. . The glass substrate with a metal layer is a glass substrate (manufactured by GEOMATEC) used on the surface of an alkali-free glass by sputtering a metal aluminum layer having a thickness of about 500 nm. After the obtained optical laminated body was stored in an oven at a temperature of 60 ° C and a relative humidity of 90% for 500 hours, the state of the metal layer of the portion to which the optical film with the adhesive layer was attached was directed from the back of the glass substrate to the light, The surface of the polarizing plate was observed with a magnifying glass, and the pitting corrosion (the occurrence of holes having a diameter of 0.1 mm or more that can penetrate 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 an adhesive layer prepared in the above (3) was cut into a test piece having a size of 20 mm × 50 mm, and the metal layer was attached to the metal layer side of the glass substrate with the adhesive layer therebetween. . The glass substrate with a metal layer is a glass substrate using a silver alloy (containing silver as the main component, an alloy of palladium and copper, and APC) with a thickness of about 500 nm on the surface of an alkali-free glass by sputtering. After the obtained optical laminated body was stored in an oven at a temperature of 60 ° C and a relative humidity of 90% for 500 hours, the state of the metal layer of the portion to which the optical film with the adhesive layer was attached was directed from the back of the glass substrate to the light, The surface of the polarizing plate was observed with a magnifying glass, and the pitting corrosion (the occurrence of holes having a diameter of 0.1 mm or more that can penetrate 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, and the number of pitting corrosion occurring on the surface of the metal layer is 6 More than one, 1: The entire surface of the metal layer surface has a large number of pitting corrosions and white turbidity.

Claims (20)

An optical laminated body includes: an optical film, an adhesive layer, and a metal layer in sequence; wherein the metal layer is a metal wiring layer; the adhesive layer is composed of a (meth) acrylic resin (A) and an isocyanate-based resin. crosslinking agent (B), the alkoxy silicon compound (C) and the following formula ^{(I): M + X -} (I) ( in the formula (I), M ⁺ represents an inorganic cation, X ^- represents an anion containing a fluorine atom) of FIG. It is composed of an adhesive composition of an ionic compound (D).     The optical multilayer body according to item 1 of the scope of patent application, wherein the aforementioned adhesive composition contains 0.01 to 2.5 parts by weight of the isocyanate-based cross-linking relative to 100 parts by weight of the (meth) acrylic resin (A). Agent (B), 0.01 to 10 parts by weight of the aforementioned silane compound (C), and 0.2 to 8 parts by weight of the aforementioned ionic compound (D).         The optical multilayer body according to item 1 or 2 of the scope of patent application, wherein the line width of the metal wiring layer is 10 μm or less.         The optical multilayer body according to item 1 or 2 of the scope of the patent application, wherein the inorganic cation is an alkali metal ion or an alkaline earth metal ion.         The optical laminated body according to item 4 of the scope of the patent application, wherein the alkali metal ion is a lithium cation, a potassium cation, or a sodium cation.         The optical laminated body according to item 4 of the scope of the patent application, wherein the alkali metal ion is a potassium cation.     The optical multilayer body according to item 1 or 2 of the scope of the patent application, wherein the foregoing fluorine atom-containing anion is the following formula (II): [Y (SO ₂ C _m F _{2m + 1} ) _n ] ^- (II) ( In formula (II), Y represents a carbon atom or a nitrogen atom, n represents 3 when Y represents a carbon atom, n represents 2 when Y represents a nitrogen atom, and m represents an integer from 0 to 10).     The optical layered body according to item 1 or 2 of the scope of the patent application, wherein the anion containing a fluorine atom is a bis (fluorosulfofluorenyl) fluorenimide anion or a bis (trifluoromethanesulfonyl) fluorenimide anion.         The optical layered body according to item 1 or 2 of the scope of the patent application, wherein the anion containing a fluorine atom is a bis (fluorosulfonyl) imide anion.         The optical multilayer body according to item 1 of the scope of the patent application, wherein the (meth) acrylic resin (A) contains a constituent unit derived from an alkyl acrylate (a1) having a glass transition temperature of less than 0 ° C of the homopolymer. And a structural unit derived from an alkyl acrylate (a2) having a glass transition temperature of 0 ° C or higher.         The optical laminate according to item 10 of the scope of application for a patent, wherein the content of the structural unit derived from the alkyl acrylate (a2) in the (meth) acrylic resin (A) is in the (meth) acrylic resin (A) It is 10 weight part or more among 100 weight part of all the structural units.         The optical laminate according to item 10 or 11 of the scope of application for a patent, wherein the aforementioned alkyl acrylate (a2) comprises methyl acrylate.         The optical multilayer body according to item 1 or 2 of the scope of patent application, wherein the (meth) acrylic resin (A) contains a structural unit derived from a monomer having a hydroxyl group.         The optical multilayer body according to item 1 or 2 of the scope of application for a patent, wherein the (meth) acrylic resin (A) does not substantially include a constituent unit derived from a monomer having a carboxyl group.         The optical multilayer body according to item 1 or 2 of the scope of the patent application, wherein the aforementioned adhesive composition does not substantially include a member selected from the group consisting of triazole-based compounds, thiazole-based compounds, imidazole-based compounds, imidazoline-based compounds, Quinoline-based compounds, pyridine-based compounds, pyrimidine-based compounds, indole-based compounds, amine-based compounds, urea-based compounds, sodium benzoate, benzylmercapto-based compounds, di-2nd butyl sulfide, and diphenyl A group of rust inhibitors from Kiyazumi.         The optical laminated body according to item 1 or 2 of the scope of the patent application, wherein the aforementioned metal layer is a layer formed by sputtering.         The optical multilayer body according to item 1 or 2 of the scope of patent application, wherein the thickness of the aforementioned metal layer is 3 μm or less.         A liquid crystal display device includes an optical laminate as described in item 1 or 2 of the scope of patent application.     An adhesive composition containing 0.01 to 2.5 parts by weight of an isocyanate-based crosslinking agent (B) and 0.01 to 10 parts by weight of silane based on 100 parts by weight of the (meth) acrylic resin (A) compound (C) 0.2 to 8 parts by weight and the following formula ^{(I): M + X -} (I) ( in the formula (I), M ⁺ represents an inorganic cation, X ^- represents an anion containing fluorine atoms) represented by An adhesive composition for forming an adhesive layer in which an ionic compound (D) is laminated on a metal layer; the metal layer is a metal wiring layer. An optical film with an adhesive layer includes an optical film and an adhesive layer laminated on at least one side of the optical film, and is adhered to the adhesive layer for a metal layer through the aforementioned adhesive layer. Optical film; wherein the aforementioned metal layer is a metal wiring layer; and the aforementioned adhesive layer is composed of 0.01 to 2.5 parts by weight of an isocyanate-based crosslinking agent based on 100 parts by weight of the (meth) acrylic resin (A). (B), 0.01 to 10 parts by weight of a silicon alkoxy 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, X ^- represents an anion containing fluorine atoms) formed by the ionic compound (D) represented by the adhesive composition.