CN106010382B

CN106010382B - Optical laminate and liquid crystal display device

Info

Publication number: CN106010382B
Application number: CN201610184870.8A
Authority: CN
Inventors: 浅津悠司; 韩银九; 柳智熙
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2015-03-31
Filing date: 2016-03-29
Publication date: 2020-03-27
Anticipated expiration: 2036-03-29
Also published as: JP2016193605A; KR20160117281A; JP6668147B2; TWI721972B; TW201700289A; CN106010382A; KR20240046454A

Abstract

The invention provides an optical laminate comprising an optical film, an adhesive layer and a metal layer in this order, wherein the adhesive layer is composed of an adhesive composition containing a (meth) acrylic resin (A), a silane compound (B) and an ionic compound (C), and the silane compound (B) is a silane compound represented by formula (I), and a liquid crystal display device comprising the optical laminate.

Description

Optical laminate and liquid crystal display device

Technical Field

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

Background

Optical films, represented by polarizing plates obtained by laminating a transparent resin film on one or both surfaces of a polarizing plate, are widely used as optical members constituting image display devices such as liquid crystal display devices. Optical films such as polarizing plates are often used by being bonded to other members (e.g., liquid crystal cells in liquid crystal display devices) with an adhesive layer interposed therebetween (see, for example, japanese patent application laid-open No. 2010-229321). Therefore, as an optical film, an optical film with an adhesive layer is known, in which an adhesive layer is provided on one surface thereof in advance. In addition, an optical film containing an ionic compound in a pressure-sensitive adhesive layer in order to impart antistatic properties is also known.

Disclosure of Invention

In recent years, liquid crystal display devices have been expanded to mobile devices having a touch panel function, such as smart phones, tablet terminals, and car navigation systems. In such a touch input type liquid crystal display device, the optical film with an adhesive layer may be disposed on a metal layer made of, for example, metal wiring, with the adhesive layer interposed therebetween or in direct contact therewith. However, in a configuration in which a metal layer containing a metal material and a binder layer containing an ionic compound are combined, the metal layer may be corroded in a high-temperature and high-humidity environment. In the case of pitting corrosion, the pitting corrosion penetrates the metal layer when the thickness of the metal layer is small or when the line width of the metal layer is narrow when the metal layer is a metal wiring, and this is particularly problematic.

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

The invention provides an optical laminate, a liquid crystal display device comprising the optical laminate, and an adhesive composition.

[1] An optical laminate comprising an optical film, an adhesive layer, and a metal layer in this order,

the adhesive layer is composed of an adhesive composition containing a (meth) acrylic resin (A), a silane compound (B), and an ionic compound (C),

the silane compound (B) is a silane compound represented by the following formula (I):

[ solution 1]

Wherein A represents an alkylene group having 1 to 20 carbon atoms or an alicyclic hydrocarbon group having a valence of 2 and having 3 to 20 carbon atoms, -CH constituting the alkylene group and the alicyclic hydrocarbon group₂-may also be substituted by-O-or-C (═ O) -, R¹Represents an alkyl group having 1 to 5 carbon atoms, R²、R³、R⁴、R⁵And R⁶Each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

[2] The optical laminate according to [1], wherein the metal layer contains 1 or more selected from the group consisting of aluminum, copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and an alloy containing 2 or more metals selected from these metals.

[3] The optical laminate according to [1] or [2], wherein the metal layer contains an aluminum element.

[4] The optical laminate according to any one of [1] to [3], wherein the metal layer is a layer formed by sputtering.

[5] The optical laminate according to any one of [1] to [4], wherein the metal layer has a thickness of 3 μm or less.

[6] The optical laminate according to any one of [1] to [5], wherein the silane compound (B) represented by the formula (I) is a silane compound represented by the following formula (II):

[ solution 2]

In the formula, R¹、R³、R⁴、R⁵And R⁶Each represents the same meaning as described above, R⁷Represents an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 1 to 20.

[7] The optical laminate according to [6], wherein m in the formula (II) is an integer of 4 to 20.

[8] The optical laminate according to [6], wherein m in the formula (II) is an integer of 6 to 8.

[9] The optical laminate according to [6], wherein m in the formula (II) is 6.

[10] The optical laminate according to any one of [1] to [9], wherein the silane compound (B) is 1, 6-bis (trimethoxysilyl) hexane.

[11] The optical laminate according to any one of [1] to [10], wherein the silane compound (B) is contained in the adhesive composition in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the (meth) acrylic resin (A).

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

[13] The optical laminate according to any one of [1] to [12], wherein the (meth) acrylic resin (A) contains a constituent unit derived from an alkyl acrylate (a1) having a homopolymer glass transition temperature of less than 0 ℃ and a constituent unit derived from an alkyl acrylate (a2) having a homopolymer glass transition temperature of 0 ℃ or higher.

[14] The optical laminate according to any one of [1] to [13], wherein the (meth) acrylic resin (A) has a weight-average molecular weight of 50 to 250 ten thousand.

[15] The optical laminate according to any one of [1] to [14], wherein the pressure-sensitive adhesive composition further contains an isocyanate-based crosslinking agent (D).

[16] The optical laminate according to any one of [1] to [15], wherein the pressure-sensitive adhesive composition contains substantially no triazole-based compound.

[17] A liquid crystal display device comprising the optical laminate according to any one of [1] to [16 ].

[18] An adhesive composition comprising a (meth) acrylic resin (A), a silane compound (B), and an ionic compound (C),

[ solution 3]

The adhesive composition is used to form an adhesive layer laminated on a metal layer.

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

Drawings

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

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

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

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

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

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

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

Detailed Description

< optical layered body >

Fig. 1 is a schematic cross-sectional view showing an example of an optical laminate of the present invention. As shown in fig. 1, the optical laminate of the present invention includes an optical film 10, an adhesive layer 20, and a metal layer 30 in this order, and may further include a substrate 40. The optical laminate may be an optical laminate in which an optical film 1 with a pressure-sensitive adhesive layer, which includes an optical film 10 and a pressure-sensitive adhesive layer 20 laminated on at least one surface thereof, is laminated on a metal layer 30 formed on a substrate 40 with the pressure-sensitive adhesive layer 20 interposed therebetween.

The adhesive layer 20 is generally directly laminated to the surface of the optical film 10. In addition, the optical film 1 with an adhesive layer is generally laminated on the metal layer 30 such that the adhesive layer 20 is in direct contact with the metal layer 30. According to the present invention, in the optical layered body, corrosion of the metal layer 30 can be effectively suppressed. Hereinafter, the property of suppressing corrosion of the metal layer 30 is also referred to as "metal corrosion resistance".

The optical film 10 may be a single-layer structure or a multilayer structure. The pressure-sensitive adhesive layer 20 is composed of a pressure-sensitive adhesive composition containing a (meth) acrylic resin (a), a silane compound (B), an ionic compound (C), and preferably further an isocyanate-based crosslinking agent (D). The adhesive composition may also contain other ingredients. In the present specification, "(meth) acrylic" means at least one selected from acrylic and methacrylic. The same applies to "(meth) acrylate" or "(meth) acryloyl group", and the like.

[1] optical film

The optical film 10 included in the optical laminate of the present invention is an optical member constituting the optical film 1 with a pressure-sensitive adhesive layer, and may be any of various optical films (films having optical properties) that can be incorporated into an image display device such as a liquid crystal display device. The optical film 10 may be a single-layer structure or a multilayer structure. Specific examples of the optical film having a single-layer structure include optical functional films such as a retardation film, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, and a light-condensing film, in addition to a polarizing plate. Specific examples of the optical film having a multilayer structure include a polarizing plate and a retardation plate. In the present specification, the polarizing plate refers to a member in which a resin film or a resin layer is laminated on at least one surface of a polarizer. The retardation plate is a member in which a resin film or a resin layer is laminated on at least one surface of a retardation film. The optical film 10 is preferably a polarizing plate, a phase difference plate, or a phase difference film, and more preferably a polarizing plate or a polarizing plate.

[ 1-1 ] polarizing plate

Fig. 2 and 3 are schematic cross-sectional views showing examples of the layer structure of the polarizing plate. The polarizing plate 10a shown in fig. 2 is a single-sided protective polarizing plate in which the first resin film 3 is laminated and bonded to one surface of the polarizer 2, and the polarizing plate 10b shown in fig. 3 is a double-sided protective polarizing plate in which the second resin film 4 is further laminated and bonded to the other surface of the polarizer 2. The first and

second resin films

3 and 4 may be bonded to the polarizing plate 2 with an adhesive layer or a pressure-sensitive adhesive layer not shown interposed therebetween. The

polarizing plates

10a and 10b may include other films or layers than the first and

second resin films

3 and 4.

Fig. 4 and 5 show examples of the layer structure of the optical laminate when the

polarizing plates

10a and 10b shown in fig. 2 and 3 are used as the optical film 10. The optical laminate 5 shown in fig. 4 is an example in which the polarizing plate 10a shown in fig. 2 is used as the optical film 10, and the optical laminate 6 shown in fig. 5 is an example in which the polarizing plate 10b shown in fig. 3 is used as the optical film 10.

The polarizing plate 2 is a film having properties of absorbing linearly polarized light having a vibration plane parallel to the absorption axis thereof and transmitting linearly polarized light having a vibration plane orthogonal to the absorption axis (parallel to the transmission axis), and for example, a film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol resin film can be used. Iodine or a dichroic organic dye may be used as the dichroic dye.

The polyvinyl alcohol resin can be obtained by saponifying a polyvinyl acetate resin. Examples of the polyvinyl acetate resin include polyvinyl acetate which is a homopolymer of vinyl acetate, and a copolymer 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, and (meth) acrylamides having an ammonium group.

The saponification degree of the polyvinyl alcohol resin is usually 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, and for example, polyvinyl formal, polyvinyl acetal, or the like modified with aldehydes may be used. The polyvinyl alcohol resin has an average polymerization degree of usually 1000 to 10000, preferably 1500 to 5000. The average polymerization degree of the polyvinyl alcohol resin can be determined in accordance with JIS K6726.

A film obtained by forming a polyvinyl alcohol resin film is generally used as a raw material film of the polarizing plate 2. The polyvinyl alcohol resin can be formed into a film by a known method. The thickness of the raw material film is usually 1 to 150 μm, and preferably 10 μm or more in consideration of ease of stretching and the like.

The polarizing plate 2 can be produced, for example, by subjecting a raw material film to uniaxial stretching, dyeing the film with a dichroic dye to adsorb the dichroic dye, treating the film with an aqueous boric acid solution, washing the film with water, and finally drying the film. The thickness of the polarizing plate 2 is usually 1 to 30 μm, and from the viewpoint of making the optical film 1 with an adhesive layer thinner, it is preferably 20 μm or less, more preferably 15 μm or less, and still more preferably 10 μm or less.

The polarizing plate 2 in which the dichroic dye is adsorbed and oriented on the polyvinyl alcohol resin film can be obtained by the method 1 in which a single film of the polyvinyl alcohol resin film is used as a raw material film, and the film is subjected to uniaxial stretching treatment and dyeing treatment of the dichroic dye, and in addition to the method 2 in which a coating liquid (aqueous solution or the like) containing a polyvinyl alcohol resin is applied to a base material film, dried to obtain a base material film having a polyvinyl alcohol resin layer, then the base material film is uniaxially stretched together with the base material film, the stretched polyvinyl alcohol resin layer is subjected to dyeing treatment of the dichroic dye, and then the base material film is peeled off and removed. As the base film, a film containing the same thermoplastic resin as that which can constitute the first and

second resin films

3 and 4 described later can be used, and a film containing a polyester resin such as polyethylene terephthalate, a polycarbonate resin, a cellulose resin such as triacetyl cellulose, a cyclic polyolefin resin such as a norbornene resin, a polystyrene resin, or the like is preferable. According to the above method 2, the polarizing plate 2 of a film can be easily produced, and the polarizing plate 2 having a thickness of 7 μm or less, for example, can be easily produced.

The first and

second resin films

3 and 4 are each independently a polyolefin-based resin including a light-transmitting, preferably optically transparent thermoplastic resin, for example, a chain polyolefin-based resin (e.g., a polyethylene-based resin and a polypropylene-based resin) or a cyclic polyolefin-based resin (e.g., a norbornene-based resin); cellulose resins (cellulose ester resins and the like); polyester resins (polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and the like); a polycarbonate-based resin; (meth) acrylic resins; a polystyrene-based resin; a polyether ether ketone resin; polysulfone-based resins, or mixtures and copolymers thereof. Among them, the first and

second resin films

3 and 4 are preferably made of a resin selected from among cyclic polyolefin resins, polycarbonate resins, cellulose resins, polyester resins, and (meth) acrylic resins, and more preferably made of a resin selected from among cellulose resins and cyclic polyolefin resins.

Examples of the chain polyolefin resin include homopolymers of chain olefins such as polyethylene resins and polypropylene resins, and copolymers containing 2 or more kinds of chain olefins.

The cyclic polyolefin resin is a generic name of resins containing, as a polymerization unit, a cyclic olefin typified by norbornene, tetracyclododecene (also known as dimethyloctahydronaphthalene) or a derivative thereof. Specific examples of the cyclic polyolefin resin include ring-opened (co) polymers of cyclic olefins and hydrogenated products thereof, addition polymers of cyclic olefins, copolymers of cyclic olefins with linear olefins such as ethylene and propylene or aromatic compounds having a vinyl group, and modified (co) polymers thereof modified with unsaturated carboxylic acids or derivatives thereof. Among them, norbornene-based resins using norbornene-based monomers such as norbornene-based monomers or condensed ring norbornene-based monomers as cyclic olefins are preferably used.

The cellulose-based resin is preferably a cellulose ester-based resin, that is, a partially or completely esterified product of cellulose, and examples thereof include an acetate, a propionate, a butyrate, and a mixed ester thereof. Among them, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and the like are preferably used.

The polyester resin is a resin other than the cellulose ester resin having an ester bond, and generally includes a polycondensate of a polycarboxylic acid or a derivative thereof and a polyol. Specific examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polypropylene terephthalate, polypropylene naphthalate, polycyclohexanedimethanol terephthalate, and polycyclohexanedimethanol naphthalate.

The polycarbonate-series resin is a polyester formed from carbonic acid and a diol or bisphenol. Among them, from the viewpoint of heat resistance, weather resistance and acid resistance, an aromatic polycarbonate having diphenylalkane in the molecular chain is preferably used. Examples of the polycarbonate include polycarbonates derived from bisphenols such as 2, 2-bis (4-hydroxyphenyl) propane (also referred to as bisphenol a), 2-bis (4-hydroxyphenyl) butane, 1-bis (4-hydroxyphenyl) cyclohexane, 1-bis (4-hydroxyphenyl) isobutane, and 1, 1-bis (4-hydroxyphenyl) ethane.

(meth) acryl film capable of constituting the first and second resin films 3 and 4The acid-based resin may be a polymer mainly composed of a constituent unit derived from a methacrylate ester (for example, containing 50 wt% or more of the constituent unit), and is preferably a copolymer having another copolymerization component copolymerized therein. The (meth) acrylic resin may contain 2 or more types of constituent units derived from a methacrylic acid ester. Examples of the methacrylic acid ester include C of methacrylic acid such as methyl methacrylate, ethyl methacrylate and butyl methacrylate₁～C₄An alkyl ester.

The copolymerizable component copolymerizable with the methacrylic acid ester is an acrylic acid ester. The acrylic ester is preferably C of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc₁～C₈Specific examples of the other copolymerizable component include unsaturated acids such as (meth) acrylic acid, aromatic vinyl compounds such as styrene, halogenated styrene, α -methylstyrene and vinyltoluene, vinyl cyanide compounds such as (meth) acrylonitrile, unsaturated acid anhydrides such as maleic anhydride and citraconic anhydride, and unsaturated imides such as phenylmaleimide and cyclohexylmaleimide, which have 1 polymerizable carbon-carbon double bond in the molecule, and compounds other than acrylates, and compounds having 2 or more polymerizable carbon-carbon double bonds in the molecule may be used as the copolymerizable component, and only 1 kind of copolymerizable component may be used, or 2 or more kinds of copolymerizable components may be used in combination.

The (meth) acrylic resin may have a ring structure in the main chain of the polymer 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 imide structure, or a lactone ring structure. Specific examples of the cyclic acid anhydride structure include a glutaric anhydride structure and a succinic anhydride structure, specific examples of the cyclic imide structure include a glutarimide structure and a succinimide structure, and specific examples of the lactone ring structure include a butyrolactone ring structure and a valerolactone ring structure.

The (meth) acrylic resin may contain acrylic rubber particles from the viewpoint of film-forming properties of the film, impact resistance of the film, and the like.The acrylic rubber particles are particles containing an elastic polymer as an essential component, and the elastic polymer mainly contains an acrylic ester, and examples thereof include particles having a single-layer structure substantially containing only the elastic polymer and particles having a multi-layer structure containing 1 layer of the elastic polymer. Examples of the elastic polymer include a crosslinked elastic copolymer containing an alkyl acrylate as a main component and copolymerized with another vinyl monomer copolymerizable therewith and a crosslinkable monomer. Examples of the alkyl acrylate which is the main component of the elastic polymer include C of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate₁～C₈An alkyl ester. The number of carbon atoms of the alkyl group is preferably 4 or more.

Examples of the other vinyl monomer copolymerizable with the alkyl acrylate include compounds having 1 polymerizable carbon-carbon double bond in the molecule, and more specifically, methacrylic acid esters such as methyl methacrylate, aromatic vinyl compounds such as styrene, and vinyl cyanide compounds such as (meth) acrylonitrile. Examples of the crosslinkable monomer include crosslinkable compounds having at least 2 polymerizable carbon-carbon double bonds in the molecule, and more specifically, include (meth) acrylic acid esters of polyhydric alcohols such as ethylene glycol di (meth) acrylate and butanediol di (meth) acrylate, alkenyl esters of (meth) acrylic acid such as allyl (meth) acrylate, and divinylbenzene.

The content of the acrylic rubber particles is preferably 5 parts by weight or more, and more preferably 10 parts by weight or more, based on 100 parts by weight of the (meth) acrylic resin. If the content of the acrylic rubber particles is too large, the surface hardness of the film may decrease, and in the case of surface-treating the film, the solvent resistance to the organic solvent in the surface-treating agent may decrease. Therefore, the content of the acrylic rubber particles is usually 80 parts by weight or less, 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 additives that are generally used in the technical field of the present invention. Specific examples of the additives include ultraviolet absorbers, infrared absorbers, organic dyes, pigments, inorganic pigments, antioxidants, antistatic agents, surfactants, lubricants, dispersants, and heat stabilizers.

Examples of the ultraviolet absorber include salicylate compounds, benzophenone compounds, benzotriazole compounds, triazine compounds, (meth) acrylic cyano ester compounds, and nickel complexes.

The first and

second resin films

3 and 4 may be either unstretched films or uniaxially or biaxially stretched films. The biaxial stretching may be simultaneous biaxial stretching in which stretching is performed simultaneously in 2 stretching directions, or sequential biaxial stretching in which stretching is performed in a predetermined direction and then in another direction. The first resin film 3 and/or the second resin film 4 may be a protective film that plays a role of protecting the polarizing plate 2, or may be a protective film that has an optical function, such as a retardation film described later. The retardation film is an optical film exhibiting optical anisotropy. For example, a retardation film to which an arbitrary retardation value is given can be produced by stretching a film containing the above thermoplastic resin (uniaxial stretching, biaxial stretching, or the like), or forming a liquid crystal layer or the like on the thermoplastic resin film.

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 or different in thickness, presence or absence of an additive, type thereof, retardation characteristics, and the like.

The first resin film 3 and/or the second resin film 4 may be provided with a surface treatment layer (coat layer) such as a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, an antistatic layer, an antifouling layer, and a conductive layer on the outer surface (surface on the opposite side of the polarizing plate 2).

The thickness of each of the first resin film 3 and the second resin film 4 is usually 1 to 150 μm, preferably 5 to 100 μm, and more preferably 5 to 60 μm. The thickness may be 50 μm or less, or even 30 μm or less. Reducing the thickness of the first and

second resin films

3 and 4 is advantageous in making the optical film 1 with an adhesive layer and the optical laminate thinner, and further in making the optical film 1 with an adhesive layer or a liquid crystal display device including the optical laminate thinner.

In particular, for small and medium-sized polarizing plates for smartphones and flat-panel terminals, a thin resin film having a thickness of 30 μm or less is often used as the first resin film 3 and/or the second resin film 4 in view of the demand for thin films, but such a polarizing plate is weak in the force of suppressing the shrinkage force of the polarizer 2 and is liable to have insufficient durability. According to the present invention, even when such a polarizing plate is used as the optical film 10, the optical film 1 with an adhesive layer and the optical laminate having good durability can be provided. The durability of the optical film 1 with an adhesive layer and the optical laminate means that, for example, in a high-temperature environment, a high-temperature and high-humidity environment, or an environment in which high temperatures and low temperatures are repeated, defects such as lifting or falling off at the interface between the adhesive layer 20 and an optical member adjacent thereto, foaming of the adhesive layer 20, and the like can be suppressed.

In addition, from the viewpoint of making the polarizing plate thinner, a configuration in which a resin film is disposed only on one surface of the polarizer 2, like the polarizing plate 10a shown in fig. 2, is advantageous. In this case, the pressure-sensitive adhesive layer 20 is usually directly bonded to the other surface of the polarizing plate 2 to form the pressure-sensitive adhesive layer-equipped optical film 1 (see fig. 4). In the case of the polarizing plate having such a structure, the problem of deterioration of the optical performance of the polarizing plate in a high-temperature and high-humidity environment due to the ionic compound contained in the pressure-sensitive adhesive layer 20 becomes particularly remarkable. According to the present invention, even when such a polarizing plate is used as the optical film 10, the optical film 1 with an adhesive layer and the optical laminate having good optical durability (property capable of suppressing deterioration of optical characteristics) can be provided.

The first and

second resin films

3 and 4 may be bonded to the polarizing plate 2 with an adhesive layer or a pressure-sensitive adhesive layer interposed therebetween. As the adhesive for forming the adhesive layer, an aqueous adhesive or an active energy ray-curable adhesive can be used.

Examples of the water-based adhesive include an adhesive containing a polyvinyl alcohol resin aqueous solution, a water-based two-pack type urethane emulsion adhesive, and the like. Among them, an aqueous adhesive containing an aqueous solution of a polyvinyl alcohol resin is suitably used. As the polyvinyl alcohol resin, not only a vinyl alcohol homopolymer obtained by saponifying polyvinyl acetate as a homopolymer of vinyl acetate, but also a polyvinyl alcohol copolymer obtained by saponifying a copolymer of vinyl acetate and another monomer copolymerizable therewith, a modified polyvinyl alcohol polymer obtained by partially modifying hydroxyl groups thereof, and the like can be used. The aqueous adhesive may contain a crosslinking agent such as an aldehyde compound, an epoxy compound, a melamine compound, a methylol compound, an isocyanate compound, an amine compound, or a polyvalent metal salt.

In the case of using the water-based adhesive, after the polarizing plate 2 is bonded to the first and

second resin films

3 and 4, a step of drying the polarizing plate is preferably performed in order to remove water contained in the water-based adhesive. After the drying step, a curing step of curing at a temperature of, for example, about 20 to 45 ℃ may be provided.

The active energy ray-curable adhesive is an adhesive that is cured by irradiation with an active energy ray such as ultraviolet ray or electron beam, and examples thereof include a curable composition containing a polymerizable compound and a photopolymerization initiator, a curable composition containing a photoreactive resin, and a curable composition containing a binder resin and a photoreactive crosslinking agent. Preferably an ultraviolet-curable adhesive. Examples of the polymerizable compound include photopolymerizable monomers such as a photocurable epoxy-based monomer, a photocurable (meth) acrylic monomer, and a photocurable urethane-based monomer, and oligomers derived from the photopolymerizable monomers. Examples of the photopolymerization initiator include those containing active species that generate neutral radicals, anionic radicals, cationic radicals, and the like by irradiation with active energy rays. As the active energy ray-curable adhesive containing a polymerizable compound and a photopolymerization initiator, a curable composition containing a photocurable epoxy-based monomer and a photocationic polymerization initiator, a curable composition containing a photocurable (meth) acrylic monomer and a photoradical polymerization initiator, or a mixture of these curable compositions can be preferably used.

In the case of using an active energy ray-curable adhesive, after the polarizing plate 2 is bonded to the first and

second resin films

3 and 4, a drying step is performed as necessary, and then a curing step of curing the active energy ray-curable adhesive by irradiation with an active energy ray is performed. The light source of the active energy ray is not particularly limited, but ultraviolet rays having a light emission distribution at a wavelength of 400nm or less are preferable, and specifically, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, a metal halide lamp, or the like can be used.

When the polarizing plate 2 is bonded to the first and

second resin films

3 and 4, at least one of the bonding surfaces may be subjected to a surface activation treatment such as saponification treatment, corona treatment, or plasma treatment. When resin films are bonded to both surfaces of the polarizing plate 2, the adhesives used for bonding the resin films may be the same type of adhesive or different types of adhesives.

The

polarizing plates

10a, 10b may further include other films or layers. Specific examples thereof include a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, a light-condensing film, an adhesive layer other than the adhesive layer 20, a coating layer, and a protective film, in addition to 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 damage or contamination, and is conventionally removed by peeling after the optical film 1 with an adhesive layer is bonded to, for example, the metal layer 30.

The protective film is generally composed of a base film and an adhesive layer laminated thereon. The base film may be made of a thermoplastic resin, for example, a polyolefin resin such as a polyethylene resin or a polypropylene resin; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; a polycarbonate-based resin; (meth) acrylic resins, and the like.

[ 1-2 ] phase difference plate

As described above, the retardation film included in the retardation plate is an optical film exhibiting optical anisotropy, and as the retardation film that can be used in the first and

second resin films

3 and 4, in addition to the stretched film obtained by stretching the resin film including the thermoplastic resin exemplified above, for example, a stretched film obtained by stretching a resin film including a polyvinyl alcohol-based resin, a polyarylate-based resin, a polyimide-based resin, a polyether sulfone-based resin, a polyvinylidene fluoride/polymethyl methacrylate-based resin, a liquid crystal polyester-based resin, a saponified ethylene-vinyl acetate copolymer, a polyvinyl chloride-based resin, or the like by about 1.01 to 6 times can be used. Among them, preferred is a stretched film obtained by uniaxially or biaxially stretching a polycarbonate-based resin film or a cycloolefin-based resin film, a (meth) acrylic-based resin film, or a cellulose-based resin film. In the present specification, a zero retardation film is also included in the retardation film (but may be used as a protective film). In addition, films such as uniaxial retardation film, wide-angle retardation film, and low photoelastic-modulus retardation film may be used as the retardation film.

The zero retardation film means an in-plane retardation value R_eAnd a phase difference value R in the thickness direction_thAll are-15 to 15nm films. The retardation film can be suitably used for an IPS mode liquid crystal display device. In-plane phase difference value R_eAnd a phase difference value R in the thickness direction_thPreferably, the particle sizes are all-10 to 10nm, and more preferably-5 to 5 nm. In-plane retardation value R as used herein_eAnd a phase difference value R in the thickness direction_thIs the value at a wavelength of 590 nm.

In-plane phase difference value R_eAnd a phase difference value R in the thickness direction_thAre respectively defined by the following formula:

R_e＝(n_x-n_y)×d

R_th＝〔(n_x+n_y)/2-n_z〕×d

in the formula, n_xIs a refractive index in a slow axis direction (x axis direction) in a film plane, n_yIs a refractive index in a fast axis direction (a y axis direction orthogonal to an x axis in a plane) in a film plane, n_zIs the film thickness direction (perpendicular to the film)Z-axis direction of the face) and d is the thickness of the film.

As the zero-retardation film, for example, a resin film containing a polyolefin resin such as a cellulose resin, a chain polyolefin resin, or a cyclic polyolefin resin, a polyethylene terephthalate resin, or a (meth) acrylic resin can be used. In particular, since the phase difference value can be easily controlled and obtained, a cellulose-based resin, a polyolefin-based resin, or a (meth) acrylic resin is preferably used.

In addition, a film in which optical anisotropy is exhibited by coating and aligning a liquid crystalline compound and a film in which optical anisotropy is exhibited by coating an inorganic layered compound can also be used as a retardation film. As such a retardation film, there are a retardation film called a temperature compensation type retardation film, and further, there are a film obtained by obliquely aligning rod-like liquid crystals sold under the trade name "NH film" by JX japanese stone energy (ltd), a film obtained by obliquely aligning disk-like liquid crystals sold under the trade name "WV film" by fuji film (ltd), a completely biaxially oriented type film sold under the trade name "VAC film" by sumitomo chemical (ltd), and a biaxially oriented type film sold under the trade name "new film" by sumitomo chemical (ltd) as well.

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

[2] adhesive layer

The pressure-sensitive adhesive layer 20 disposed between the optical film 10 and the metal layer 30 is composed of a pressure-sensitive adhesive composition containing a (meth) acrylic resin (a), a silane compound (B), and an ionic compound (C), and preferably further contains an isocyanate-based crosslinking agent (D). The silane compound (B) in the adhesive composition is a silane compound represented by the following formula (I):

[ solution 4]

Wherein A represents an alkylene group having 1 to 20 carbon atoms or a 2-valent alicyclic hydrocarbon group having 3 to 20 carbon atomsThe alkylene group and-CH of the alicyclic hydrocarbon group₂-may also be substituted by-O-or-C (═ O) -, R¹Represents an alkyl group having 1 to 5 carbon atoms, R²、R³、R⁴、R⁵And R⁶Each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

According to the pressure-sensitive adhesive layer 20 composed of the pressure-sensitive adhesive composition, in the optical laminate including the pressure-sensitive adhesive layer 20 and the metal layer 30, corrosion of the metal layer 30 can be suppressed, and the durability of the pressure-sensitive adhesive layer-attached optical film 1 and the optical laminate can be improved. Further, according to the pressure-sensitive adhesive layer 20 composed of the pressure-sensitive adhesive composition, the optical film 1 with a pressure-sensitive adhesive layer and the optical laminate can exhibit excellent optical durability even when the pressure-sensitive adhesive layer 20 is directly bonded to the polarizing plate 2.

The thickness of the pressure-sensitive adhesive layer 20 is usually 2 to 40 μm, and is preferably 5 to 30 μm, more preferably 10 to 25 μm from the viewpoints of the durability of the pressure-sensitive adhesive layer-attached optical film 1 and optical laminate, the reworkability of the pressure-sensitive adhesive layer-attached optical film 1, and the like. Further, if the thickness of the pressure-sensitive adhesive layer 20 is 10 μm or more, the pressure-sensitive adhesive layer 20 has good followability to dimensional changes of the optical film 10, and if it is 25 μm or less, the reworkability becomes good.

The adhesive layer 20 is preferably a layer exhibiting a storage elastic modulus of 0.1 to 5MPa in a temperature range of 23 to 80 ℃. This can more effectively improve the durability of the optical film 1 with an adhesive layer and the optical laminate. The phrase "exhibits a storage elastic modulus of 0.1 to 5MPa in a temperature range of 23 to 80 ℃ means that the storage elastic modulus is a value within the above range at any temperature in the above range. Since the storage elastic modulus generally decreases gradually with increasing temperature, if the storage elastic modulus at 23 ℃ and that at 80 ℃ both fall within the above range, it can be considered that the storage elastic modulus in the above range is exhibited at a temperature in the range. The storage elastic modulus of the pressure-sensitive adhesive layer 20 can be measured using a commercially available viscoelasticity measuring apparatus, for example, a viscoelasticity measuring apparatus "DYNAMIC ANALYZER RDA II" manufactured by REMOMETRIC.

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

The (meth) acrylic resin (a) is a polymer or copolymer mainly composed of a constituent unit derived from a (meth) acrylic monomer (preferably containing 50 wt% or more). The (meth) acrylic monomer contains, for example, a monomer having a (meth) acryloyl group, and preferably contains an alkyl (meth) acrylate. The alkyl group of the alkyl (meth) acrylate has preferably 1 to 14 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 8 carbon atoms, and may be linear, branched, or cyclic. As the alkyl (meth) acrylate, a substituted alkyl (meth) acrylate such as a substituted alkyl acrylate in which a substituent is introduced into an alkyl group, which will be described later, may be used. The alkyl (meth) acrylate may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-and isopropyl (meth) acrylate, n-, iso-and tert-butyl (meth) acrylate, n-and iso-amyl acrylate, n-and iso-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-and iso-heptyl (meth) acrylate, n-and iso-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-and iso-nonyl (meth) acrylate, n-and iso-decyl (meth) acrylate, isobornyl (meth) acrylate, n-and iso-dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like.

The (meth) acrylic resin (A) preferably contains a constituent unit derived from an alkyl acrylate (a1) having a homopolymer glass transition temperature Tg of less than 0 ℃ and a constituent unit derived from an alkyl acrylate (a2) having a homopolymer Tg of 0 ℃ or higher. This arrangement is advantageous in improving the metal corrosion resistance and durability of the optical film 1 with an adhesive layer and the optical laminate. The Tg of the homopolymer of the alkyl acrylate may be obtained, for example, from literature values such as POLYMER HANDBOOK (Wiley-Interscience).

Specific examples of the alkyl acrylate (a1) include alkyl acrylates having an alkyl group of about 2 to 12 carbon atoms such as ethyl acrylate, n-and iso-propyl acrylate, n-and iso-butyl acrylate, n-pentyl acrylate, n-and iso-hexyl acrylate, n-heptyl acrylate, n-and iso-octyl acrylate, 2-ethylhexyl acrylate, n-and iso-nonyl acrylate, n-and iso-decyl acrylate, and n-dodecyl acrylate. Other specific examples of the alkyl acrylate (a1) include substituted alkyl acrylates in which a substituent is introduced into the alkyl group of an alkyl acrylate having an alkyl group with about 2 to 12 carbon atoms. The substituent of the alkyl acrylate having a substituent is a group which substitutes 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 having 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, but is preferably a linear or branched alkyl group.

The alkyl acrylate (a1) may be used in a single amount of 1 kind, or may be used in combination of 2 or more kinds. Among them, the alkyl acrylate (a1) preferably contains 1 or 2 or more selected from ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. The alkyl acrylate (a1) preferably contains n-butyl acrylate from the viewpoint of the ability of the pressure-sensitive adhesive layer 20 of the pressure-sensitive adhesive layer-attached optical film 1 to follow the optical film 10 and the reworkability.

The alkyl acrylate (a2) is an alkyl acrylate other than the alkyl acrylate (a 1). Specific examples of the alkyl acrylate (a2) include methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, stearyl acrylate, t-butyl acrylate and the like.

The alkyl acrylate (a2) may be used in a single amount of 1 kind, or may be used in combination of 2 or more kinds. Among them, the alkyl acrylate (a2) preferably contains methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, etc., and more preferably contains methyl acrylate, from the viewpoint of metal corrosion resistance and durability.

The content of the constituent unit derived from the alkyl acrylate (a2) in the (meth) acrylic resin (a) is preferably 10 parts by weight or more, more preferably 15 parts by weight or more, further preferably 20 parts by weight or more, and particularly preferably 25 parts by weight or more, of all the constituent units constituting the (meth) acrylic resin (a), from the viewpoint of metal corrosion resistance and durability of the optical film 1 with an adhesive layer and the optical laminate. From the viewpoint of the follow-up property and reworkability of the pressure-sensitive adhesive layer 20 to the optical film 10, the content of the constituent unit derived from the alkyl acrylate (a2) is preferably 70 parts by weight or less, more preferably 60 parts by weight or less, and still more preferably 50 parts by weight or less.

The (meth) acrylic resin (a) may contain a constituent unit derived from a monomer other than the alkyl acrylates (a1) and (a 2). The (meth) acrylic resin (a) may contain 1 kind of the constituent unit derived from another monomer, or may contain 2 or more kinds. Specific examples of the other monomers are shown below.

1) A monomer having a polar functional group.

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 amino group, or a heterocyclic group such as an epoxy group. Specific examples thereof include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- (2-hydroxyethoxy) ethyl (meth) acrylate, 2-chloro-2-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, and the like; monomers having a heterocyclic group such as acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, 2, 5-dihydrofuran, etc.; monomers having a substituted or unsubstituted amino group such as aminoethyl (meth) acrylate, N-dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and the like; carboxyl group-containing monomers such as (meth) acrylic acid and carboxyethyl (meth) acrylate. Among these, a monomer having a hydroxyl group is preferable, and a (meth) acrylate having a hydroxyl group is more preferable in view of reactivity of the (meth) acrylic resin (a) with the crosslinking agent.

The other polar functional group-containing monomer may be blended with the hydroxyl group-containing (meth) acrylate, and it is preferable that the monomer substantially not containing an amino group is contained from the viewpoint of preventing an excessive increase in the peeling force of the separator that can be laminated on the outer surface of the pressure-sensitive adhesive layer 20. In addition, from the viewpoint of improving corrosion resistance against ITO, it is preferable that a monomer having a carboxyl group is not substantially contained. The term "substantially not contained" as used herein means 0.1 parts by weight or less based on 100 parts by weight of all the constituent units constituting the (meth) acrylic resin (A).

2) Acrylamide monomer

Examples thereof include N-methylolacrylamide, N- (2-hydroxyethyl) acrylamide, N- (3-hydroxypropyl) acrylamide, N- (4-hydroxybutyl) acrylamide, N- (5-hydroxypentyl) acrylamide, N- (6-hydroxyhexyl) acrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-isopropylacrylamide, N- (3-dimethylaminopropyl) acrylamide, N- (1, 1-dimethyl-3-oxobutyl) acrylamide, N- [ 2- (2-oxo-1-imidazolidinyl) ethyl ] acrylamide, 2-acryloylamino-2-methyl-1-propanesulfonic acid, N- (3-hydroxybutyl) acrylamide, N- (5-hydroxypentyl) acrylamide, N- (6-hydroxyhexyl) acrylamide, N-dimethylacrylamide, N-diethylacrylamide, N-isopropylacrylamide, N- (3-dimethylaminopropyl) acrylamide, N- (1, 1-dimethyl-3-, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (1-methylethoxymethyl) acrylamide, N- (1-methylpropoxymethyl) acrylamide, N- (2-methylpropoxymethyl) acrylamide [ alternative names: n- (isobutoxymethyl) acrylamide ], N- (butoxymethyl) acrylamide, N- (1, 1-dimethylethoxymethyl) acrylamide, N- (2-methoxyethyl) acrylamide, N- (2-ethoxyethyl) acrylamide, N- (2-propoxyethyl) acrylamide, N- [ 2- (1-methylethoxy) ethyl ] acrylamide, N- [ 2- (1-methylpropoxy) ethyl ] acrylamide, N- [ 2- (2-methylpropoxy) ethyl ] acrylamide [ also known as N- (isobutoxymethyl) acrylamide ]: n- (2-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 preferably used.

3) Methacrylate (i.e. methacrylate)

Examples of the alkyl ester include linear alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, and lauryl methacrylate; branched alkyl esters of methacrylic acid such as isobutyl methacrylate, 2-ethylhexyl methacrylate and isooctyl methacrylate; alicyclic alkyl esters of methacrylic acid such as isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, cyclododecyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, t-butylcyclohexyl methacrylate, cyclohexylphenyl methacrylate, and the like; alkoxyalkyl esters of methacrylic acid such as 2-methoxyethyl methacrylate and ethoxymethyl methacrylate; aralkyl methacrylates such as benzyl methacrylate; alkyl esters of methacrylic acid having a hydroxyl group such as 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2- (2-hydroxyethoxy) ethyl methacrylate, 2-chloro-2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monomethacrylate, etc.; alkyl esters of methacrylic acid having a substituted or unsubstituted amino group such as aminoethyl methacrylate, N-dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, and the like; and esters of methacrylic acid having a phenoxyethyl group such as 2-phenoxyethyl methacrylate, 2- (2-phenoxyethoxy) ethyl methacrylate, ethylene oxide-modified nonylphenol ester of (meth) acrylic acid, and 2- (o-phenylphenoxy) ethyl methacrylate.

4) Methacrylamide monomer

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

5) Styrene monomer

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

6) Vinyl monomer

Examples of the vinyl ester include vinyl esters of fatty acids such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl laurate; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride; nitrogen-containing aromatic vinyl monomers such as vinylpyridine, vinylpyrrolidone and vinylcarbazole; conjugated diene monomers such as butadiene, isoprene and chloroprene; unsaturated nitriles such as acrylonitrile and methacrylonitrile.

7) Monomer having multiple (meth) acryloyl groups in molecule

Examples of the monomer include monomers having 2 (meth) acryloyl groups in the molecule, such as 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, and tripropylene glycol di (meth) acrylate; and a monomer having 3 (meth) acryloyl groups in the molecule, such as trimethylolpropane tri (meth) acrylate.

As described above, the (meth) acrylic resin (a) preferably contains a constituent unit derived from a monomer having a polar functional group in addition to a constituent unit derived from an alkyl (meth) acrylate, from the viewpoint of durability and metal corrosion resistance of the optical film 1 with an adhesive layer and the optical laminate. The monomer having a polar functional group is 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 0.1 to 10 parts by weight, more preferably 0.25 to 5 parts by weight, and still more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total constituent units constituting the (meth) acrylic resin (a).

From the viewpoint of the reworkability of the optical film 1 with an adhesive layer, the smaller the content of the constituent unit derived from a methacrylic monomer such as a methacrylate or a methacrylamide monomer in the (meth) acrylic resin (a), the better, specifically, the content of the constituent unit is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and further preferably substantially not contained (0.1 parts by weight or less) in 100 parts by weight of all the constituent units constituting the (meth) acrylic resin (a).

The (meth) acrylic resin (A) preferably has a single peak in a range of weight average molecular weight Mw of 1000 to 250 ten thousand on an outflow curve of Gel Permeation Chromatography (GPC), more preferably has a single peak in a range of Mw of 1000 to 250 ten thousand, and contains a constituent unit derived from alkyl acrylates (a1) and (a 2). The pressure-sensitive adhesive layer 20 containing the (meth) acrylic resin (a) as a base polymer is advantageous in improving the durability of the pressure-sensitive adhesive layer-attached optical film 1 and the optical laminate. When the number of peaks in the Mw range is 2 or more, sufficient durability tends not to be obtained.

When the number of peaks of a GPC outflow curve in the Mw range of 1000 to 250 ten thousand is calculated, the outflow curve is obtained under the GPC measurement conditions described in the first example. The expression "having a single peak" in the above-mentioned range of the obtained elution curve means that the Mw ranges from 1000 to 250 ten thousand with only 1 maximum value. In the present specification, a curve having an S/N ratio of 30 or more in a GPC outflow curve is defined as a peak.

The Mw of the (meth) acrylic resin (a) in terms of polystyrene standard GPC is preferably in the range of 50 to 250 ten thousand, and more preferably in the range of 60 to 200 ten thousand. When Mw is 50 ten thousand or more, the metal corrosion resistance and durability of the optical film 1 with an adhesive layer and the optical laminate are improved, and the reworkability of the optical film 1 with an adhesive layer tends to be improved. Further, if Mw is 250 ten thousand or less, the pressure-sensitive adhesive layer 20 has good followability to dimensional changes of the optical film 10. The molecular weight distribution expressed by the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn is usually 2 to 10. The Mw and Mn of the (meth) acrylic resin (a) were determined according to the GPC measurement conditions described in the first example.

When the (meth) acrylic resin (A) is dissolved in ethyl acetate to give a 20 wt% concentration solution, the viscosity at 25 ℃ is preferably 20 pas or less, more preferably 0.1 to 7 pas. The viscosity in this range is advantageous for improving the durability of the optical film 1 with an adhesive layer and the optical laminate, and for improving the reworkability of the optical film 1 with an adhesive layer. The viscosity can be measured using a Brookfield viscometer.

The glass transition temperature Tg of the (meth) acrylic resin (A) as measured by a Differential Scanning Calorimeter (DSC) is preferably from-60 to-10 ℃, more preferably from-55 to-15 ℃. The Tg in this range is advantageous for improving the metal corrosion resistance and durability of the optical film 1 with an adhesive layer and the optical laminate.

The adhesive composition may contain 2 or more (meth) acrylic resins belonging to the (meth) acrylic resin (a). The adhesive composition may contain another (meth) acrylic resin different from the (meth) acrylic resin (a). Among these, from the viewpoint of metal corrosion resistance and durability of the optical film 1 with an adhesive layer and the optical laminate, the content of the (meth) acrylic resin (a) is preferably 70% by weight or more, more preferably 80% by weight or more, and further preferably 90% by weight or more of the total (meth) acrylic resin, and the adhesive composition particularly preferably contains only the (meth) acrylic resin (a) as a base polymer.

The (meth) acrylic resin (a) and, if necessary, other (meth) acrylic resins that can be used in combination can be produced by a known method such as solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization. In the production of (meth) acrylic resins, a polymerization initiator is generally used. About 0.001 to 5 parts by weight of a polymerization initiator is used based on 100 parts by weight of the total of all monomers used for producing the (meth) acrylic resin. The (meth) acrylic resin can also be produced by a method of polymerizing with an active energy ray such as ultraviolet ray.

As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, or the like is used. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone and the like. Examples of the thermal polymerization initiator include azo compounds such as 2, 2 ' -azobisisobutyronitrile, 2 ' -azobis (2-methylbutyronitrile), 1 ' -azobis (cyclohexane-1-carbonitrile), 2 ' -azobis (2, 4-dimethylvaleronitrile), 2 ' -azobis (2, 4-dimethyl-4-methoxyvaleronitrile), dimethyl-2, 2 ' -azobis (2-methylpropionate), and 2, 2 ' -azobis (2-hydroxymethylpropionitrile); organic peroxides such as lauroyl peroxide, t-butyl hydroperoxide, benzoyl peroxide, t-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, and (3, 5, 5-trimethylhexanoyl) peroxide; inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide. Further, a redox initiator or the like using a peroxide and a reducing agent in combination may be used as the polymerization initiator.

Among the above-mentioned methods, the solution polymerization method is preferable as a method for producing a (meth) acrylic resin. An example of the solution polymerization method is a method in which the monomer and the organic solvent to be used are mixed, and a thermal polymerization initiator is added under a nitrogen atmosphere, and the mixture is stirred at about 40 to 90 ℃ and preferably about 50 to 80 ℃ for about 3 to 15 hours. In order to control the reaction, the monomer or the thermal polymerization initiator may be continuously or intermittently added during the polymerization, or may be added in a state of being dissolved in an organic solvent. As the organic solvent, for example, aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

[ 2-2 ] silane Compound (B)

The adhesive composition contains a silane compound (B). The silane compound (B) is a silane compound represented by the following formula (I):

[ solution 5]

According to the pressure-sensitive adhesive layer 20 containing the silane compound (B) represented by the above formula (I), the metal corrosion resistance and durability of the pressure-sensitive adhesive layer-attached optical film 1 and the optical laminate can be improved as compared with the case of using another silane compound, and the adhesion between the pressure-sensitive adhesive layer 20 and the metal layer 30, the glass substrate, and the like can be improved. It is also possible to use 2 or more silane compounds (B).

Specific examples of the alkylene group having 1 to 20 carbon atoms which may constitute A in the formula (I) include methylene, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 1, 6-hexylene, 1, 7-heptylene, 1, 8-octylene, 1, 9-nonylene, 1, 10-decylene, 1, 12-dodecylene, 1, 14-tetradecylene, 1, 16-hexadecylene, 1, 18-octadecylene and 1, 20-eicosylene. Specific examples of the alicyclic hydrocarbon group having 2 valence of 3 to 20 carbon atoms include 1, 3-cyclopentylene group and 1, 4-cyclohexylene group. -CH constituting the alkylene group and the alicyclic hydrocarbon group₂Specific examples of the group substituted with-O-or-C (═ O) -include-CH₂CH₂-O-CH₂CH₂-、-CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂-、-CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂-、-CH₂CH₂-C(＝O)-O-CH₂CH₂-、-CH₂CH₂-O-CH₂CH₂-C(＝O)-O-CH₂CH₂-、-CH₂CH₂CH₂CH₂-O-CH₂CH₂-、-CH₂CH₂CH₂CH₂-O-CH₂CH₂CH₂CH₂-。

As R capable of constituting the above formula (I)¹、R²、R³、R⁴、R⁵And R⁶Examples of the alkyl group having 1 to 5 carbon atoms include various pentyl groups such as methyl, ethyl, n-and I-propyl, n-, I-and t-butyl, and n-, I-and t-pentyl groups, and R in the formula (I) can be represented by²、R³、R⁴、R⁵And R⁶Examples of the alkoxy group having 1 to 5 carbon atoms include various pentyloxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-, iso-and tert-pentyloxy. The alkyl group and the alkoxy group each have a carbon number independently of each other, preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 or 2.

Specific examples of the silane compound represented by the above formula (I) are shown below.

Bis (trimethoxysilyl) methane,

Bis (triethoxysilyl) methane,

Bis (tripropoxysilyl) methane,

Bis (tributoxysilyl) methane,

Bis (tripentoxysilyl) methane,

Bis (dimethoxymethylsilyl) methane,

Bis (dimethoxyethylsilyl) methane,

Bis (dimethoxypropylsilyl) methane,

Bis (dimethoxyethylsilyl) methane,

Bis (dimethoxypropylsilyl) methane,

Bis (diethoxymethylsilyl) methane,

Bis (dipropoxymethylsilyl) methane,

Bis (methoxydimethylsilyl) methane,

1- (trimethylsilyl) -1- (methoxydimethylsilyl) methane,

1- (trimethylsilyl) -1- (dimethoxymethylsilyl) methane,

1- (trimethoxysilyl) -1- (triethoxysilyl) methane,

Bis (dimethoxyethoxysilyl) methane,

1, 2-bis (trimethoxysilyl) ethane,

1, 2-bis (triethoxysilyl) ethane,

1, 2-bis (tripropoxysilyl) ethane,

1, 2-bis (tributoxysilyl) ethane,

1, 2-bis (tripentyloxysilyl) ethane,

1, 2-bis (dimethoxymethylsilyl) ethane,

1, 2-bis (dimethoxyethylsilyl) ethane,

1, 2-bis (dimethoxypropylsilyl) ethane,

1, 2-bis (diethoxymethylsilyl) ethane,

1, 2-bis (dipropoxymethylsilyl) ethane,

1, 2-bis (methoxydimethylsilyl) ethane,

1- (trimethylsilyl) -2- (methoxydimethylsilyl) ethane,

1- (trimethylsilyl) -2- (dimethoxymethylsilyl) ethane,

1- (trimethoxysilyl) -2- (triethoxysilyl) ethane,

1, 2-bis (dimethoxyethoxysilyl) ethane,

1, 3-bis (trimethoxysilyl) propane,

1, 3-bis (triethoxysilyl) propane,

1, 3-bis (tripropoxysilyl) propane,

1, 4-bis (trimethoxysilyl) butane,

1, 4-bis (triethoxysilyl) butane,

1, 4-bis (tripropoxysilyl) butane,

1, 4-bis (tributoxysilyl) butane,

1, 4-bis (tripentyloxysilyl) butane,

1, 4-bis (dimethoxymethylsilyl) butane,

1, 4-bis (dimethoxyethylsilyl) butane,

1, 4-bis (dimethoxypropylsilyl) butane,

1, 4-bis (diethoxymethylsilyl) butane,

1, 4-bis (dipropoxymethylsilyl) butane,

1, 4-bis (methoxydimethylsilyl) butane,

1- (trimethylsilyl) -4- (methoxydimethylsilyl) butane,

1- (trimethylsilyl) -4- (dimethoxymethylsilyl) butane,

1- (trimethoxysilyl) -4- (triethoxysilyl) butane,

1, 4-bis (dimethoxyethoxysilyl) butane,

1, 5-bis (trimethoxysilyl) pentane,

1, 5-bis (triethoxysilyl) pentane,

1, 5-bis (tripropoxysilyl) pentane,

1, 6-bis (trimethoxysilyl) hexane,

1, 6-bis (triethoxysilyl) hexane,

1, 6-bis (tripropoxysilyl) hexane,

1, 6-bis (tributoxysilyl) hexane,

1, 6-bis (tripentyloxysilyl) hexane,

1, 6-bis (dimethoxymethylsilyl) hexane,

1, 6-bis (dimethoxyethylsilyl) hexane,

1, 6-bis (dimethoxypropylsilyl) hexane,

1, 6-bis (dimethoxyethylsilyl) hexane,

1, 6-bis (dimethoxypropylsilyl) hexane,

1, 6-bis (diethoxymethylsilyl) hexane,

1, 6-bis (dipropoxymethylsilyl) hexane,

1, 6-bis (methoxydimethylsilyl) hexane,

1- (trimethylsilyl) -6- (methoxydimethylsilyl) hexane,

1- (trimethylsilyl) -6- (dimethoxymethylsilyl) hexane,

1- (trimethoxysilyl) -6- (triethoxysilyl) hexane,

1, 6-bis (dimethoxyethoxysilyl) hexane,

1, 8-bis (trimethoxysilyl) octane,

1, 8-bis (triethoxysilyl) octane,

1, 8-bis (tripropoxysilyl) octane,

1, 8-bis (tributoxysilyl) octane,

1, 8-bis (tripentoxysilyl) octane,

1, 8-bis (dimethoxymethylsilyl) octane,

1, 8-bis (dimethoxyethylsilyl) octane,

1, 8-bis (dimethoxypropylsilyl) octane,

1, 8-bis (dimethoxyethylsilyl) octane,

1, 8-bis (dimethoxypropylsilyl) octane,

1, 8-bis (diethoxymethylsilyl) octane,

1, 8-bis (dipropoxymethylsilyl) octane,

1, 8-bis (methoxydimethylsilyl) octane,

1- (trimethylsilyl) -8- (methoxydimethylsilyl) octane,

1- (trimethylsilyl) -8- (dimethoxymethylsilyl) octane,

1- (trimethoxysilyl) -8- (triethoxysilyl) octane,

1, 8-bis (dimethoxyethoxysilyl) octane,

1, 10-bis (trimethoxysilyl) decane,

1, 12-bis (trimethoxysilyl) dodecane,

1, 14-bis (trimethoxysilyl) tetradecane,

1, 16-bis (trimethoxysilyl) hexadecane,

1, 18-bis (trimethoxysilyl) octadecane,

1, 20-bis (trimethoxysilyl) eicosane, and the like.

Among them, the silane compound (B) is preferably a silane compound represented by the following formula (II) from the viewpoints of metal corrosion resistance of the optical film 1 with an adhesive layer and the optical laminate, and adhesion of the adhesive layer 20 to the metal layer 30, the glass substrate, and the like:

[ solution 6]

In the formula, R¹、R³、R⁴、R⁵And R⁶Each represents the same meaning as described above, R⁷Represents an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 1 to 20. Can form R⁷Specific examples of the alkyl group having 1 to 5 carbon atoms in the above are the same as those described above. From the same viewpoint as above, the silane compound (B) is more preferably a silane compound represented by the above formula (II) wherein m is an integer of 4 to 20, still more preferably a silane compound represented by the above formula (II) wherein m is an integer of 6 to 8, and particularly preferablyM selected from 1, 6-bis (trimethoxysilyl) hexane, 1, 6-bis (triethoxysilyl) hexane, 1, 8-bis (trimethoxysilyl) octane, 1, 8-bis (triethoxysilyl) octane and the like is an integer of 6 to 8, OR¹、R²、R³、R⁴、R⁵、R⁶And OR⁷Each independently a silane compound represented by the formula (II) having 1 to 3 carbon atoms (for example, 1 or 2 carbon atoms). Examples of suitable m are 6 or 8.

The adhesive composition may further contain 1 or 2 or more silane compounds other than the silane compound (B) along with the silane compound (B) represented by the above formula (I). Examples of the other silane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.

Other silane compounds may include compounds of the silicone oligomer type. Specific examples of the silicone oligomer are shown below if they are expressed as combinations between monomers.

3-mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer,

3-mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer,

3-mercaptopropyltriethoxysilane-tetramethoxysilane oligomer,

Oligomers containing a mercaptopropyl group such as 3-mercaptopropyltriethoxysilane-tetraethoxysilane oligomers;

mercaptomethyltrimethoxysilane-tetramethoxysilane oligomer,

Mercaptomethyltrimethoxysilane-tetraethoxysilane oligomer,

Mercaptomethyltriethoxysilane-tetramethoxysilane oligomer,

Mercapto methyl group-containing oligomers such as mercaptomethyltriethoxysilane-tetraethoxysilane oligomers;

3-glycidoxypropyltrimethoxysilane-tetramethoxysilane copolymer,

3-glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer,

3-glycidoxypropyltriethoxysilane-tetramethoxysilane copolymer,

3-glycidoxypropyltriethoxysilane-tetraethoxysilane copolymer,

3-glycidoxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,

3-glycidoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,

3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,

3-glycidoxypropyl group-containing copolymers such as 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymers;

3-methacryloxypropyltrimethoxysilane-tetramethoxysilane oligomer,

3-methacryloxypropyltrimethoxysilane-tetraethoxysilane oligomer,

3-methacryloxypropyltriethoxysilane-tetramethoxysilane oligomer,

3-methacryloxypropyltriethoxysilane-tetraethoxysilane oligomer,

3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer,

3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer,

3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer,

Methacryloxypropyl-containing oligomers such as 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane oligomers;

3-acryloxypropyltrimethoxysilane-tetramethoxysilane oligomer,

3-acryloxypropyltrimethoxysilane-tetraethoxysilane oligomer,

3-acryloxypropyltriethoxysilane-tetramethoxysilane oligomer,

3-acryloxypropyltriethoxysilane-tetraethoxysilane oligomer,

3-acryloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer,

3-acryloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer,

3-acryloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer,

Acryloxypropyl-containing oligomers such as 3-acryloxypropylmethyldiethoxysilane-tetraethoxysilane oligomers;

vinyltrimethoxysilane-tetramethoxysilane oligomer,

Vinyltrimethoxysilane-tetraethoxysilane oligomer,

A vinyl triethoxysilane-tetramethoxysilane oligomer,

A vinyl triethoxysilane-tetraethoxysilane oligomer,

Vinylmethyldimethoxysilane-tetramethoxysilane oligomer,

Vinylmethyldimethoxysilane-tetraethoxysilane oligomer,

Vinyl methyl diethoxy silane-tetramethoxy silane oligomer,

Vinyl group-containing oligomers such as vinylmethyldiethoxysilane-tetraethoxysilane oligomers;

3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer,

3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer,

3-aminopropyltriethoxysilane-tetramethoxysilane copolymer,

3-aminopropyltriethoxysilane-tetraethoxysilane copolymer,

3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer,

3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer,

3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer,

And amino group-containing copolymers such as 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymers.

Among them, from the viewpoint of metal corrosion resistance of the optical film 1 and the optical laminate with an adhesive layer and adhesion between the adhesive layer 20 and the metal layer 30 or the glass substrate, the content of the silane compound (B) represented by the above formula (I) is preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, in the total amount of all silane compounds, and particularly preferably the adhesive composition contains only the silane compound (B) as the silane compound.

The content of the silane compound (B) in the adhesive composition is usually 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, and still more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the (meth) acrylic resin (A). If the content of the silane compound (B) is 0.01 parts by weight or more, the effect of improving the metal corrosion resistance of the optical film 1 with an adhesive layer and the optical laminate, and the effect of improving the adhesion between the adhesive layer 20 and the metal layer 30 or the glass substrate, etc. can be easily obtained. Further, if the content is 10 parts by weight or less, bleeding of the silane compound (B) from the adhesive layer 20 can be suppressed.

[ 2-3 ] Ionic Compound (C)

The adhesive composition contains an ionic compound (C). By containing the ionic compound (C), antistatic ability can be imparted to the pressure-sensitive adhesive layer 20. Conventionally, if the pressure-sensitive adhesive layer 20 containing an ionic compound is laminated on the metal layer 30, the metal layer 30 may be corroded in a high-temperature and high-humidity environment, but according to the present invention, the optical film 1 with a pressure-sensitive adhesive layer and the optical laminate can be provided, which can suppress the corrosion. The ionic compound (C) is a compound composed of a cation and an anion. The cation may be any of an organic cation and an inorganic cation, and the anion may be any of an organic anion and an inorganic anion. The adhesive composition may contain 1 or 2 or more kinds of ionic compounds (C).

Specific examples of the organic cation include pyridinium cation, imidazolium cation, piperidinium cation, pyrrolidinium cation, tetrahydropyridinium cation, dihydropyridinium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, pyrazolium cation, pyrazolinium cation, ammonium cation, sulfonium cation, phosphonium cation and the like. The organic cation may have a substituent. Specific examples of the inorganic cation include lithium cation [ Li ]⁺Sodium cation [ Na ]⁺Potassium cation [ K ]⁺C, cesium cation [ Cs ]⁺Alkali metal ions such as aluminum ions; beryllium cation [ Be ]²⁺Magnesium cation [ Mg ]²⁺Calcium cation [ Ca ]²⁺Alkaline earth metal ions, etc.

Among them, the cation is preferably an organic cation from the viewpoint of compatibility with the (meth) acrylic resin (a), and from the viewpoint of antistatic performance, an organic cation containing a nitrogen atom (which may have a substituent) such as a pyridinium cation, an imidazolium cation, a piperidinium cation, a pyrrolidinium cation, a tetrahydropyridinium cation, a dihydropyridinium cation, a tetrahydropyrimidinium cation, a dihydropyrimidinium cation, a pyrazolium cation, a pyrazolinium cation, or an ammonium cation is more preferable, and a cation having a heterocyclic structure containing a nitrogen atom including an unsaturated bond is more preferable.

A suitable example of 1 kind of pyridinium cation which may have a substituent and belongs to the cations having a nitrogen atom-containing heterocyclic structure containing an unsaturated bond is a pyridinium cation represented by the following formula (III):

[ solution 7]

In the above formula (III), R⁸～R¹³Each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a hydroxyl group, an ether group, a carboxyl group, a carbonyl group, or a halogen atom, and a ring may be formed between adjacent substituents.

As the alkyl group which may have a substituent, preferred is an alkyl group having 1 to 30 carbon atoms, and specific examples thereof include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylthiophenacyl group, 4-phenylthiophenacyl group, 4-dimethylaminobenzoylmethyl group, 4-cyanobenzoylmethyl group, 4-methylbenzoylmethyl group, 2-methylbenzoylmethyl group, 3-fluorobenzoylmethyl group, 3-trifluoromethylbenzoylmethyl group and 3-nitrobenzoylmethyl group.

The alkenyl group which may have a substituent(s) is preferably an alkenyl group having 2 to 10 carbon atoms, and specific examples thereof include a vinyl group, an allyl group and a styryl group. The alkynyl group which may have a substituent(s) is preferably an alkynyl group having 2 to 10 carbon atoms, and specific examples thereof include an ethynyl group, a propynyl group and a propargyl group.

As the aryl group which may have a substituent(s), preferred is an aryl group having 6 to 30 carbon atoms, and specific examples thereof include, for example, phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 9-phenanthryl, 1-pyrenyl, 5-tetracenyl, 1-indenyl, 2-azulenyl, 9-fluorenyl, terphenyl, quaterphenyl, o-, m-, and p-tolyl, xylyl, o-, m-, and p-cumenyl,

A radical, a pentalene radical,Binaphthyl, terphenyl, tetrabinaphthyl, heptenylene, biphenylene, indacenyl, fluoranthenyl, acenaphthenyl, benzoacenaphthenyl, periphthyl, fluorenyl, anthracenyl, dianthranyl, terpanthryl, tetradianthranyl, anthraquinonyl, phenanthrenyl, benzophenanthrenyl, pyrenyl, indacenaphthenyl, acenaphthenyl, phenanthrenyl,

a phenyl group, a tetracenyl group, a pleiadienyl group, a picene group, a perylene group, a pentaphenyl group, a benzene pentaphenyl group, a tetraphenylene group, a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a binaphthyl group (trinaphenylenyl group), a heptaphenyl group, a heptaphthyl group, a pyranthryl group, and an ovophenyl group (ovalenyl group).

As the heterocyclic group which may have a substituent(s), an aromatic or aliphatic heterocyclic group containing a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom is preferable, and specific examples thereof include, for example, thienyl, benzo [ b ] thienyl, naphtho [2, 3-b ] thienyl, thianthrenyl, furyl, pyranyl, isobenzofuryl, chromenyl, xanthenyl, phenoxazinyl, 2H-pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, 3H-indolyl, 1H-indazolyl, purinyl, 4H-quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalyl, quinazolinyl, cinnolinyl, pteridinyl, 4 aH-carbazolyl, β -carbolinyl, phenanthridinyl, pyrimidyl (ペリミジン), phenanthrolinyl, phenazinyl (phenazinyl), phenazinyl, pyrazinyl, isothiazolinyl, indolinyl, pyrazolinyl, indolinyl, pyrazolinyl, indolinyl, pyrazolinyl, indolinyl, quinolinyl, pyrazolinyl, indolinyl, pyrazolinyl, indolinyl, and cinnolinyl (チオキサントリル) may be mentioned.

Specific examples of the substituent which may be substituted for the hydrogen atom of the alkyl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, the aryl group which may have a substituent, and the heterocyclic group which may have a substituent include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; an alkoxycarbonyl group such as an aryloxy group such as a phenoxy group or a p-tolyloxy group, a methoxycarbonyl group, a butoxycarbonyl group, a phenoxycarbonyl group, a vinyloxycarbonyl group, or an aryloxycarbonyl group; acyloxy groups such as acetoxy, propionyloxy, benzoyloxy and the like; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, methoxyoxalyl and the like; alkylthio groups such as methylthio and tert-butylthio; arylthio groups such as phenylthio and p-tolylthio; alkylamino groups such as methylamino and cyclohexylamino; dialkylamino groups such as dimethylamino, diethylamino, morpholinyl, and piperidyl; arylamino groups such as phenylamino groups and p-tolylamino groups; alkyl groups such as methyl, ethyl, tert-butyl and dodecyl; aryl groups such as phenyl, p-tolyl, xylyl, cumyl, naphthyl, anthryl, and phenanthryl; hydroxyl, carboxyl, sulfonamide, formyl, mercapto, sulfo, methanesulfonyl, p-toluenesulfonyl, amino, nitro, nitroso, cyano, trifluoromethyl, trichloromethyl, trimethylsilyl, phospho-imino, phosphonic acid, alkylsulfonyl, arylsulfonyl, trialkylammonium, dimethylsulfonium, triphenylphenacylphosphonium (ホスホニウミル).

The pyridinium cation represented by the above formula (III) is preferably an N-substituted pyridinium cation. In this case, R¹The alkyl group may preferably have a substituent, and more preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. The number of carbon atoms is preferably 1 to 16. R²～R⁶Independently of each other, a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a hydroxyl group, or a halogen atom is preferable, and a hydrogen atom or a linear alkyl group having 1 to 20 carbon atoms is more preferable.

Specific examples of the inorganic anion capable of constituting the ionic compound (C) include chloride anion [ Cl^-Bromide anion [ Br ]^-Iodide anion [ I ]^-Tetrachloroaluminate anion [ AlCl ]₄ ^-Heptachlorodialuminate anion [ Al ]₂Cl₇ ^-Tetrafluoroborate anion [ BF ]₄ ^-Hexafluorophosphate anion [ PF ]₆ ^-Perchlorate anion [ ClO ]₄ ^-Nitrate anion [ NO ]₃ ^-Hexafluoroarsenate anion [ AsF ]₆ ^-Hexafluoroantimonate anion [ SbF ]₆ ^-Hexafluoroniobate anion [ NbF ]₆ ^-Hexafluorotantalate anion [ TaF ]₆ ^-Bis (fluorosulfonyl) imide anion [ (FSO)₂)₂N^-Fluorine ((poly) hydrogen fluoride) anion [ F (HF)_n ^-And (n is about 1 to 3), and the like.

Specific examples of the organic anion capable of constituting the ionic compound (C) include acetate anion [ CH ]₃COO^-Trifluoroacetate anion [ CF ]₃COO^-Methanesulfonate anion [ CH ]₃SO₃ ^-Triflate anion [ CF ]₃SO₃ ^-P-toluenesulfonate anion [ p-CH ]₃C₆H₄SO₃ ^-Bis (trifluoromethanesulfonyl) imide anion [ (CF)₃SO₂)₂N^-Tri (trifluoromethanesulfonyl) methanide anion [ (CF)₃SO₂)₃C^-Dimethyl phosphinic acid anion [ (CH ]₃)₂POO^-Thiocyanate anion [ SCN ]^-Perfluoro butane sulfonate anion [ C ]₄F₉SO₃ ^-Bis (pentafluoroethanesulfo) imide anion [ (C)₂F₅SO₂)₂N^-Perfluorobutyrate anion [ C ]₃F₇COO^-(trifluoromethanesulfonyl) imide anion [ (CF)₃SO₂)(CF₃CO)N^-Perfluoro propane-1, 3-disulfonate anion [ ]^-O₃S(CF₂)₃SO₃ ^-Carbonate anion [ CO ]₃ ^2-Tetraarylborate anions (e.g., tetrakis (pentafluorophenyl) borate anion, etc.), dicyanamide anions [ (CN)₂N^-And imide anions represented by the following formula (IV):

[ solution 8]

Among these, the anion containing a fluorine atom is preferable because it tends to easily provide the ionic compound (C) excellent in antistatic performance. In particular, if the ionic compound (C) having an anion of bis (trifluoromethanesulfonyl) imide anion, bis (fluorosulfonyl) imide anion, imide anion represented by the above formula (IV), or tetrakis (pentafluorophenyl) borate anion is used, it is advantageous to improve the antistatic property, metal corrosion resistance, and optical durability of the optical film 1 and the optical laminate with an adhesive layer.

From the viewpoint of antistatic performance, metal corrosion resistance and optical durability, suitable examples of the ionic compound (C) are as follows.

1) An ionic compound in which the cation is a pyridinium cation represented by the following formula (III):

[ solution 9]

In the formula, R is preferred⁸Is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, R⁹～R¹³Each independently represents a hydrogen atom or a linear alkyl group having 1 to 20 carbon atoms, and the anion is any one anion selected from the above groups.

2) An ionic compound in which the cation is a lithium cation [ Li⁺Sodium cation [ Na ]⁺Potassium cation [ K ]⁺Inorganic cation, anion is any one anion selected from the above group.

The content of the ionic compound (C) in the adhesive composition is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 8 parts by weight, further preferably 0.3 to 5 parts by weight, and particularly preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the (meth) acrylic resin (a). If the content of the ionic compound (C) is 0.1 parts by weight or more, the antistatic property is improved, and if the content is 10 parts by weight or less, the metal corrosion resistance and durability of the optical film 1 with a pressure-sensitive adhesive layer and the optical laminate are improved.

[ 2-4 ] isocyanate-based crosslinking agent (D)

The adhesive composition preferably contains an isocyanate-based crosslinking agent (D). By using the isocyanate-based crosslinking agent (D) as the crosslinking agent, the metal corrosion resistance and durability of the optical film 1 with an adhesive layer and the optical laminate can be improved. The isocyanate crosslinking agent (D) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The isocyanate-based crosslinking agent (D) is a compound having at least 2 isocyanate groups (-NCO) in the molecule, and specific examples thereof include toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and the like. The isocyanate crosslinking agent (D) may be a polyol compound adduct of these isocyanate compounds (for example, an adduct of glycerin or trimethylolpropane), an isocyanurate compound, a biuret compound, or a urethane prepolymer type isocyanate compound obtained by addition reaction with a polyether polyol, a polyester polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol, or the like. Among the above, toluene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, or a polyol compound adduct of these isocyanate compounds are particularly preferable, and xylene diisocyanate or a polyol compound adduct thereof is more preferable from the viewpoint of durability of the optical film 1 with an adhesive layer and the optical laminate.

The content of the isocyanate crosslinking agent (D) is preferably 0.08 to 2.5 parts by weight, and more preferably 0.1 to 2 parts by weight (for example, 1 part by weight or less) based on 100 parts by weight of the (meth) acrylic resin (a). When the content of the isocyanate crosslinking agent (D) is in this range, it is advantageous in terms of metal corrosion resistance and durability of the optical film 1 with a pressure-sensitive adhesive layer and the optical laminate.

The adhesive composition may be used together with the isocyanate crosslinking agent (D) and other crosslinking agents such as an epoxy compound, an aziridine compound, a metal chelate compound, a peroxide, etc., but from the viewpoint of metal corrosion resistance and durability of the optical film 1 and the optical laminate with an adhesive layer, the adhesive composition preferably contains only the isocyanate crosslinking agent (D) as the crosslinking agent, and particularly preferably contains substantially no peroxide. The term "substantially not contained" as used herein means that the content is 0.01 parts by weight or less based on 100 parts by weight of the (meth) acrylic resin (A).

[ 2-5 ] other ingredients

The adhesive composition may contain 1 or 2 or more kinds of additives such as a solvent, a crosslinking catalyst, an ultraviolet absorber, a weather resistant stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, and light scattering fine particles. In addition, it is also useful to form a harder pressure-sensitive adhesive layer by mixing an ultraviolet-curable compound into the pressure-sensitive adhesive composition and then irradiating ultraviolet light to cure the mixture after forming the pressure-sensitive adhesive layer. Examples of the crosslinking catalyst include amine compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resins, and melamine resins.

The pressure-sensitive adhesive composition may contain a rust inhibitor capable of improving the metal corrosion resistance of the optical film 1 with a pressure-sensitive adhesive layer and the optical laminate. Examples of the rust inhibitor include triazole compounds such as benzotriazole compounds and other triazole compounds; thiazole compounds such as benzothiazole compounds and other thiazole compounds; imidazole compounds such as benzyl imidazole compounds and other imidazole compounds; an imidazoline-based compound; a quinoline-based compound; a pyridine-based compound; a pyrimidine-based compound; an indole-based compound; an amine-based compound; a urea-based compound; sodium benzoate; a benzylmercapto compound; di-sec-butyl sulfide; and diphenyl sulfoxide.

However, according to the present invention, sufficient metal corrosion resistance can be obtained even without containing a rust inhibitor, and therefore, the smaller the content of the rust inhibitor, the better. In particular, the pressure-sensitive adhesive composition preferably contains substantially no triazole-based compound as a rust inhibitor, and more preferably contains substantially no rust inhibitor selected from the above-described group of compounds. The term "substantially not contained" as used herein means that the content is 0.01 parts by weight or less based on 100 parts by weight of the (meth) acrylic resin (A).

[3] Metal layer and substrate

The metal layer 30 may be, for example, a layer containing 1 or more selected from the group consisting of aluminum, copper, silver, gold, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and an alloy containing 2 or more metals selected from these, preferably a layer containing a metal element selected from the group consisting of aluminum, copper, silver, and gold from the viewpoint of conductivity, more preferably a layer containing an aluminum element from the viewpoint of conductivity and cost, and still more preferably a layer containing an aluminum element as a main component. The main component contained means that the metal component constituting the metal layer 30 is 30% by weight or more, and further 50% by weight or more of the total metal component.

The metal layer 30 may be a metal oxide layer such as ITO, for example, but since the optical film 1 with an adhesive layer of the present invention has excellent corrosion resistance particularly against a simple metal or an alloy, the metal layer 30 preferably contains a simple metal containing the above-mentioned metal element and/or an alloy containing 2 or more kinds of the above-mentioned metal element. However, the optical laminate may further include a transparent electrode layer containing a metal oxide such as ITO together with the metal layer 30.

The form (e.g., thickness, etc.) and preparation method of the metal layer 30 are not particularly limited, and may be a metal foil, a metal layer formed by a vacuum deposition method, a sputtering method, an ion plating method, an inkjet printing method, or a gravure printing method, 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 sputtering. In the metal layer and the metal foil formed by sputtering, the former tends to have poor corrosion resistance, but the optical laminate according to the present invention also has good metal corrosion resistance with respect to the metal layer formed by sputtering. The thickness of the metal layer 30 is usually 3 μm or less, preferably 1 μm or less, and 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 is usually 10 μm or less, preferably 5 μm or less, and more preferably 3 μm or less. The line width of the metal wiring is usually 0.01 μm or more, preferably 0.1 μm or more, and more preferably 0.5 μm or more. The optical laminate of the present invention also exhibits excellent metal corrosion resistance to the metal layer 30 including the thin film and the metal layer 30 including the fine metal wiring. In particular, even when the metal wiring is formed by a sputtering method, for example, with a thickness of 3 μm or less and a line width of 10 μm or less, or with a thickness of 3 μm or less and a line width of 10 μm or less, corrosion thereof, particularly pitting corrosion, can be suppressed.

The metal layer 30 may be, for example, a metal wiring layer (i.e., an electrode layer) of a touch input element included in the touch input type liquid crystal display device. In this case, the metal layer 30 is usually patterned in a predetermined shape. In the case where the adhesive layer 20 is laminated on the patterned metal layer 30, the adhesive 20 may have a portion not in contact with the metal layer 30. The metal layer 30 may be a continuous film containing the above metal or alloy.

The metal layer 30 may have a single-layer structure, or may have a multilayer structure of 2 or 3 or more layers. Examples of the metal layer having a multilayer structure include a metal-containing layer (such as a metal mesh) having a 3-layer structure represented by molybdenum/aluminum/molybdenum.

As shown in fig. 1, the metal layer 30, for example, a metal wiring layer, is usually formed on the substrate 40, and 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 sputtering, for example. The substrate 40 may be a transparent substrate constituting a liquid crystal cell included in the 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. In the case where the patterned metal layer 30 is formed on the substrate 40, for example, when the metal layer 30 is formed on a part of the surface of the substrate 40, a part of the pressure-sensitive adhesive layer 20 is in direct contact with the substrate 40 made of glass, for example, but since the pressure-sensitive adhesive layer 20 of the optical laminate of the present invention is also excellent in adhesion to glass, the optical laminate and the liquid crystal display device including the optical laminate are also excellent in durability in this case.

[4] Structure of optical laminate and method for producing the same

As shown in fig. 4 and 5, the optical laminate of the present invention in 1 embodiment includes an optical film 1 with an adhesive layer and a metal layer 30 laminated on the adhesive layer 20 side thereof. In the optical

layered bodies

5 and 6 shown in fig. 4 and 5, the optical film 1 with an adhesive layer is layered on the metal layer 30 such that the adhesive layer 20 is in direct contact with the metal layer 30. According to the present invention, even in the optical laminate having the structure in which the pressure-sensitive adhesive layer 20 and the metal layer 30 are in direct contact with each other, corrosion of the metal layer 30 can be effectively suppressed.

Fig. 6 is a schematic cross-sectional view showing another example of the layer structure of the optical laminate of the present invention. In this another embodiment, the optical laminate of the present invention is, like the optical laminate 7 shown in fig. 6, such that the pressure-sensitive adhesive layer 20 of the pressure-sensitive adhesive layer-attached optical film 1 is laminated with the metal layer 30 via the resin layer 50. The adhesive layer 20 is in direct contact with the resin layer 50. In the optical layered body 7, corrosion of the metal layer 30 can be effectively suppressed. The resin layer 50 disposed between the adhesive layer 20 and the metal layer 30 may be a cured product layer of a curable resin, for example. As the curable resin capable of forming the resin layer 50, a known curable resin can be used, and examples thereof include the curable resins described in japanese patent application laid-open No. 2009-217037.

As described above, the metal layer 30 may be a metal wiring layer. Fig. 7 shows an example of the case where the metal layer 30 is a metal wiring layer. The resin layer 50 may also be omitted from the optical laminate shown in fig. 7.

The optical laminate can be produced, for example, by laminating an optical film 1 with a pressure-sensitive adhesive layer, which includes an optical film 10 and a pressure-sensitive adhesive layer 20 laminated on at least one surface thereof, on a metal layer 30 formed on a substrate 40 with the pressure-sensitive adhesive layer 20 interposed therebetween.

As described above, the optical film with an adhesive layer 1 includes the optical film 10 and the adhesive layer 20 laminated on at least one side thereof (fig. 1). The pressure-sensitive adhesive layer 20 may be laminated on both surfaces of the optical film 10. Typically, the adhesive layer 20 is directly laminated on the surface of the optical film 10. When the pressure-sensitive adhesive layer 20 is provided on the surface of the optical film 10, the bonding surface of the optical film 10 and/or the bonding surface of the pressure-sensitive adhesive layer 20 are preferably subjected to primer layer formation, surface activation treatment, such as plasma treatment or corona treatment, and more preferably subjected to corona treatment.

In the case where the optical film 10 is a one-sided protective polarizing plate as shown in fig. 2, the adhesive layer 20 is preferably laminated directly on the polarizer surface, that is, the surface of the polarizer 2 opposite to the first resin film 3. In the case where the optical film 10 is a double-sided protective polarizing plate as shown in fig. 3, the adhesive layer 20 may be laminated on the outer surface of either one of the first and

second resin films

3 and 4, or may be laminated on both outer surfaces.

Although an antistatic layer may be separately provided between the optical film 10 and the pressure-sensitive adhesive layer 20, the pressure-sensitive adhesive layer 20 of the present invention may be provided with excellent antistatic properties by a separate pressure-sensitive adhesive layer, and therefore, it is preferable that no antistatic layer be provided between the optical film 10 and the pressure-sensitive adhesive layer 20 in view of the reduction in thickness of the optical laminate and the simplification of the laminate production process.

The optical film 1 with an adhesive layer may include a separator (release film) laminated on the outer surface of the adhesive layer 20. The separator is usually peeled off and removed at the time of use of the adhesive layer 20 (for example, at the time of lamination onto the metal layer 30). The separator may be a film obtained by subjecting the surface of a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyarylate, on which the pressure-sensitive adhesive layer 20 is formed, to a release treatment such as a silicone treatment.

The optical film 1 with a pressure-sensitive adhesive layer can be obtained by dissolving or dispersing the components constituting the pressure-sensitive adhesive composition in a solvent to prepare a solvent-containing pressure-sensitive adhesive composition, applying the solvent-containing pressure-sensitive adhesive composition to the surface of the optical film 10, and drying the applied solvent-containing pressure-sensitive adhesive composition to form the pressure-sensitive adhesive layer 20. The pressure-sensitive adhesive layer-attached optical film 1 may be obtained by forming the pressure-sensitive adhesive layer 20 on the release-treated surface of the separator in the same manner as described above, and laminating (transferring) the pressure-sensitive adhesive layer 20 on the surface of the optical film 10.

The optical laminate can be obtained by laminating the optical film 1 with an adhesive layer on the metal layer 30 (or the resin layer) with the adhesive layer 20 interposed therebetween. In the case where there is a problem in the production of an optical laminate by bonding the optical film 1 with an adhesive layer to the metal layer 30, it is necessary to peel the optical film 1 with an adhesive layer from the metal layer 30 and bond another optical film 1 with an adhesive layer to the metal layer 30 again, that is, a so-called reworking operation is necessary. The optical laminate of the present invention is less likely to cause blurring, adhesive residue, and the like on the surface of the metal layer 30 after the optical film 1 with the pressure-sensitive adhesive layer is peeled off from the metal layer 30, and is excellent in reworkability. According to the optical laminate of the present invention, even when the surface to which the pressure-sensitive adhesive layer 20 is bonded is not the metal layer 30 but a glass substrate or an ITO layer, 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 exhibits excellent 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. The touch input type liquid crystal display device includes a touch input element including a liquid crystal cell, and a backlight. The touch panel may be configured In any conventionally known manner such as an Out-cell type, an On-cell type, an In-cell type, etc., and the touch panel may be operated In any conventionally known manner such as a resistive film type, a capacitive type (surface capacitive type, projection capacitive type), etc. The optical laminate of the present invention may be disposed on the viewing side of the touch input element (liquid crystal cell), may be disposed on the backlight side, or may be disposed on both sides. The liquid crystal cell may be driven by any conventionally known method such as a TN method, a VA method, an IPS method, a multi-domain method, or 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.

[ examples ]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. Hereinafter, the amounts used, the parts of contents and the% are based on the weight unless otherwise specified.

< production example 1: production of (meth) acrylic resin (A-1) for adhesive layer >

A reaction vessel equipped with a condenser, a nitrogen inlet, a thermometer, and a stirrer was charged with a solution obtained by mixing 81.8 parts of ethyl acetate with a monomer having a composition shown in table 1 (the numerical values in table 1 are parts by weight). The air in the reaction vessel was replaced with nitrogen, and the internal temperature was adjusted to 60 ℃. Thereafter, a solution prepared by dissolving 0.12 part of azobisisobutyronitrile in 10 parts of ethyl acetate was added. After the same temperature was maintained for 1 hour, ethyl acetate was continuously fed into the reaction vessel at an addition rate of 17.3 parts/Hr while maintaining the internal temperature at 54 to 56 ℃ so that the concentration of the polymer was approximately 35%. After the internal temperature was maintained at 54 to 56 ℃ for 12 hours from the start of the addition of ethyl acetate, ethyl acetate was added to adjust the polymer concentration to 20% to obtain an ethyl acetate solution of the (meth) acrylic resin (a-1). The weight average molecular weight Mw of the (meth) acrylic resin (A-1) was 139 ten thousand, and the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn was 5.32. The Gel Permeation Chromatography (GPC) showed a single peak for the Mw139 ten thousand component, and no other peak was observed in the Mw1000 to 250 ten thousand range.

< production example 2: production of (meth) acrylic resin (A-2) for adhesive layer >

An ethyl acetate solution of (meth) acrylic resin (a-2) (resin concentration: 20%) was obtained in the same manner as in production example 1, except that the monomer composition was as shown in table 1. The weight-average molecular weight Mw of the (meth) acrylic resin (A-2) was 141 ten thousand, and Mw/Mn was 4.71. In the GPC outflow curve, a single peak was observed for the Mw141 ten thousand component, and no other peak was observed in the Mw1000 to 250 ten thousand range.

In the above production examples, the weight average molecular weight Mw and the number average molecular weight Mn were measured by arranging 5 total of 4 "TSKgel XL" manufactured by Tosoh corporation and 1 "Shodex GPCKF-802" manufactured by Showa Denko K.K. onto a column in series in a GPC apparatus, using tetrahydrofuran as an eluent, and measuring the molecular weight Mw and the number average molecular weight Mn in terms of standard polystyrene under the conditions of a sample concentration of 5mg/mL, a sample introduction amount of 100. mu.L, a temperature of 40 ℃ and a flow rate of 1 mL/min. The conditions for obtaining the GPC flow-out curve were also the same.

The glass transition temperature Tg was measured using a Differential Scanning Calorimeter (DSC) "EXSTAR DSC 6000" manufactured by SII Nano Technology, under a nitrogen atmosphere, at a measurement temperature range of-80 to 50 ℃ and a temperature rise rate of 10 ℃/min.

The composition of the monomer in each production example (the numerical value in table 1 is part by weight) and the number of peaks in the Mw range of 1000 to 250 ten thousand on the GPC outflow curve (expressed as "GPC peak number" in table 1) are collectively shown in table 1.

[ Table 1]

Abbreviations in the column "monomer composition" of table 1 refer to the following monomers.

BA: butyl acrylate (glass transition temperature of homopolymer: -54 deg.C),

MA: methyl acrylate (glass transition temperature of homopolymer: 10 ℃), and,

HEA: 2-hydroxyethyl acrylate.

< examples 1 to 8 and comparative examples 1 to 7>

(1) Preparation of adhesive composition

The silane compound (B), the ionic compound (C), and the isocyanate-based crosslinking agent (D) shown in table 2 were mixed in amounts (parts by weight) shown in table 2 with respect to 100 parts of the solid content of the ethyl acetate solution of the (meth) acrylic resin (resin concentration: 20%) obtained in the above production example, and ethyl acetate was added so that the solid content concentration became 14% to obtain a pressure-sensitive adhesive composition. The blending amounts of the respective blending components shown in table 2 are parts by weight as effective components contained in a product containing a solvent or the like.

[ Table 2]

The details of each blending component shown in abbreviated form in table 2 are as follows.

(silane Compound)

B-1: a silane compound represented by the following formula:

[ solution 10]

B-2: a silane compound represented by the following formula:

[ solution 11]

B-3: 3-glycidoxypropyltrimethoxysilane, available under the trade name "KBM 403" from shin-Etsu chemical industries, Inc.

(Ionic Compound)

C-1: an ionic compound represented by the formula:

[ solution 12]

C-2: an ionic compound represented by the formula:

[ solution 13]

C-3: lithium bis (trifluoromethanesulfonyl) imide,

C-4: potassium bis (fluorosulfonyl) imide,

C-5: n-decylpyridinium bis (fluorosulfonyl) imide salts,

C-6: n-methylpyridinium tetrakis (pentafluorophenyl) borate,

C-7: n-decylpyridinium tetrakis (pentafluorophenyl) borate,

(isocyanate-based crosslinking agent)

D-1: an ethyl acetate solution of a trimethylolpropane adduct of xylylenediisocyanate (solid content concentration: 75%), which is available under the trade name "TAKENATE D-110N" from Mitsui chemical Co., Ltd.

(2) Production of adhesive layer

Each of the adhesive compositions prepared in (1) above was applied to a release-treated surface of a separator comprising a polyethylene terephthalate film subjected to release treatment [ trade name "PLR-382051" obtained from LINTEC (ltd) ] using a size applicator so that the thickness after drying was 20 μm, and dried at 100 ℃ for 1 minute to prepare an adhesive layer (adhesive sheet).

(3) Production of optical film (P-1) having adhesive layer

A polyvinyl alcohol film having an average polymerization degree of about 2400 and a saponification degree of 99.9 mol% and a thickness of 60 μm (trade name "Kuraray Vinylon VF-PE # 6000", manufactured by Kuraray Co., Ltd.) was immersed in pure water at 37 ℃ and then immersed in an aqueous solution containing iodine and potassium iodide (iodine/potassium iodide/water (weight ratio): 0.04/1.5/100) at 30 ℃. Thereafter, the resultant 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 ℃. The film was washed with pure water at 10 ℃ and then dried at 85 ℃ to obtain a polarizing plate having a thickness of about 23 μm, in which iodine was adsorbed and oriented on polyvinyl alcohol. The stretching was mainly performed in the steps of iodine dyeing and boric acid treatment, and the total stretching magnification was 5.3 times.

On one surface of the obtained polarizing plate, a transparent protective film containing a triacetyl cellulose film (trade name "KC 2 UA" manufactured by Konica Minolta Opt) having a thickness of 25 μm was bonded with an adhesive containing an aqueous solution of a polyvinyl alcohol resin interposed therebetween. Then, a zero retardation film containing a cyclic polyolefin resin (trade name "ZEONOR" manufactured by Zeon corporation, japan) having a thickness of 23 μm was laminated on the surface of the polarizer opposite to the triacetyl cellulose film with an adhesive containing an aqueous solution of a polyvinyl alcohol resin interposed therebetween to manufacture a polarizing plate. Then, the surface of the zero retardation film opposite to the surface in contact with the polarizing plate was subjected to corona discharge treatment for improving adhesion, and then the surface (adhesive layer surface) of the adhesive layer produced in (2) above opposite to the separator was laminated by a laminator, followed by curing at 23 ℃ and 65% relative humidity for 7 days to obtain an optical film (P-1) with an adhesive layer.

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

A polyvinyl alcohol film having an average polymerization degree of about 2400 and a saponification degree of 99.9 mol% and a thickness of 30 μm (trade name "Kuraray Vinylon VF-PE # 3000", manufactured by Kuraray Co., Ltd.) was immersed in pure water at 37 ℃ and then immersed in an aqueous solution containing iodine and potassium iodide (iodine/potassium iodide/water (weight ratio): 0.04/1.5/100) at 30 ℃. Thereafter, the resultant 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 ℃. The film was washed with pure water at 10 ℃ and then dried at 85 ℃ to obtain a polarizing plate having a thickness of about 12 μm, in which iodine was adsorbed and oriented on polyvinyl alcohol. The stretching was mainly performed in the steps of iodine dyeing and boric acid treatment, and the total stretching magnification was 5.3 times.

On one surface of the obtained polarizing plate, a transparent protective film containing a triacetyl cellulose film (trade name "KC 2 UA" manufactured by Konica Minolta Opt) having a thickness of 25 μm was bonded via an adhesive containing an aqueous solution of a polyvinyl alcohol resin, to produce a polarizing plate. Then, the surface of the pressure-sensitive adhesive layer produced in (2) above, which was opposite to the surface to which the protective film was bonded, was bonded to the surface of the polarizing plate, which was opposite to the surface to which the protective film was bonded (i.e., the surface of the pressure-sensitive adhesive layer), using a laminator, and then cured at 23 ℃ and 65% relative humidity for 7 days, to obtain an optical film with a pressure-sensitive adhesive layer (P-2).

(5) Evaluation of Metal Corrosion resistance of optical film with adhesive layer

The optical film with an adhesive layer (P-1) prepared in the above (3) was cut into a test piece of 20mm × 50mm in size, and was bonded to the metal layer side of the glass substrate with a metal layer therebetween. As the glass substrate with a metal layer, a glass substrate (manufactured by Geomatec) in which a metal aluminum layer having a thickness of about 500nm was laminated on the surface of an alkali-free glass by sputtering was used. The optical laminate thus obtained was kept in an oven at a temperature of 60 ℃ and a relative humidity of 90% for 500 hours, and then light was projected from the back surface of the glass substrate, and the state of the metal layer in the portion to which the optical film with the adhesive layer was bonded was observed from the surface of the polarizing plate through a magnifying glass (Lupe), and the evaluation was made on the following criteria with respect to pitting corrosion (occurrence of holes having a diameter of 0.1mm or more and capable of transmitting light). The results are shown in table 3.

5: no pitting corrosion and no white turbidity were observed on the surface of the metal layer,

4: the number of pitting corrosion occurring on the surface of the metal layer is 2 or less,

3: the number of pitting corrosion generated on the surface of the metal layer is 3-5,

2: the number of pitting corrosion occurring on the surface of the metal layer is 6 or more,

1: a plurality of spot corrosions are generated on the entire surface of the metal layer, and also white turbidity is generated.

(6) Evaluation of durability of optical film with adhesive layer

Subjecting the above-mentioned compound (3) toThe optical film (P-1) with the adhesive layer was cut into a size of 200mm × 150mm so that the stretching axis direction of the polarizing plate was the long side, and the separator was peeled off, and the exposed adhesive layer side was bonded to a glass substrate. The obtained test piece with the glass substrate attached (optical film with adhesive layer with glass substrate attached) was placed in an autoclave at a temperature of 50 ℃ and a pressure of 5kg/cm²(490.3kPa) for 20 minutes. As the glass substrate, alkali-free glass manufactured by Corning Corp under the trade name "Eagle XG" was used. The following 3 durability tests were performed on the optical laminate obtained.

[ durability test ]

Heat resistance test of keeping the temperature at 85 ℃ for 750 hours,

A wet heat resistance test in which the sample is maintained at 60 ℃ and 90% relative humidity for 750 hours,

The heat shock resistance (HS) test was repeated 400 cycles, with the operation set to 1 cycle, after 30 minutes of holding under the drying condition at 85 ℃ and 30 minutes of holding under the drying condition at-40 ℃.

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

4: no appearance change such as tilting, falling off and foaming,

3: almost no appearance change such as tilting, falling off and foaming,

2: slightly obvious appearance changes such as tilting, falling off, foaming and the like,

1: the appearance changes such as tilting, falling off, foaming and the like are obviously seen.

(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 having a size of 25mm × 150 mm. The separator was peeled from the test piece, and the adhesive surface thereof was bonded to a glass substrate. The obtained test piece (glass-bonded) with the glass substrate bonded thereto was usedOptical film with adhesive layer of glass substrate) in an autoclave at 50 ℃ and 5kg/cm pressure²(490.3kPa) for 20 minutes. Then, the optical film was kept in an oven at 50 ℃ for 48 hours, and then peeled from the test piece together with the adhesive layer at a speed of 300 mm/min in a 180 ℃ direction in an atmosphere at a temperature of 23 ℃ and a relative humidity of 50%. The state of the surface of the glass substrate after peeling was observed and evaluated by the following criteria. The results are shown in table 3.

4: no blur or the like was observed on the surface of the glass substrate,

3: hardly showing haze or the like on the surface of the glass substrate,

2: the surface of the glass substrate was observed to be blurred,

1: the adhesive layer was visible 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 (4) above was cut into a size of 30mm × 30mm, and the separator was peeled off, and the exposed adhesive layer surface was bonded to a glass substrate. As the glass substrate, alkali-free glass manufactured by Corning Corp under the trade name "Eagle XG" was used. The MD transmittance and TD transmittance at a wavelength of 380 to 780nm were measured with an integrating sphere spectrophotometer (product name "V7100" manufactured by japan spectrography corporation), the monomer transmittance and the degree of polarization at each wavelength were calculated, and the ratio of the monomer transmittance and the degree of polarization were measured according to JIS Z8701: 1999 "color expression method-XYZ color system and X₁₀Y₁₀Z₁₀The visual sensitivity was corrected in a 2-degree visual field (C light source) of the color system "to obtain the visual sensitivity correction single transmittance (Ty) and the visual sensitivity correction polarization degree (Py) before the endurance test. The optical laminate was set in a spectrophotometer with an integrating sphere so that the triacetyl cellulose film side of the polarizing plate was the detector side and light was incident from the glass substrate side.

The monomer transmittance and the degree of polarization are defined by the following formulas:

monomer transmittance (λ) ═ 0.5 × (Tp (λ) + Tc (λ))

Degree of polarization (λ) × 100 × (Tp (λ) -Tc (λ))/(Tp (λ) + Tc (λ))

Tp (λ) is the transmittance (%) of the optical laminate measured by the relationship between incident linearly polarized light of wavelength λ (nm) and parallel nicols, and Tc (λ) is the transmittance (%) of the optical laminate measured by the relationship between incident linearly polarized light of wavelength λ (nm) and orthogonal nicols.

Then, the optical laminate was left to stand in a moist heat environment at a temperature of 80 ℃ and a relative humidity of 90% for 24 hours, and then left to stand in an environment at a temperature of 23 ℃ and a relative humidity of 60% for 24 hours, and then Ty and Py after the durability test were determined by the same method as before the durability test. Then, the polarization degree change amount (Δ Py) and the cell transmittance change amount (Δ Ty) were obtained by subtracting Py and Ty before the test from Py and Ty after the test, respectively, to calculate the change amount before and after the endurance test. Δ Py is shown in table 3.

[ Table 3]

< production example 3: production of (meth) acrylic resin (A-1) for adhesive layer >

A reaction vessel equipped with a condenser, a nitrogen inlet, a thermometer, and a stirrer was charged with a solution obtained by mixing 81.8 parts of ethyl acetate with a monomer having a composition shown in table 4 (the numerical values in table 4 are parts by weight). The air in the reaction vessel was replaced with nitrogen, and the internal temperature was adjusted to 60 ℃. Thereafter, a solution prepared by dissolving 0.12 part of azobisisobutyronitrile in 10 parts of ethyl acetate was added. After the same temperature was maintained for 1 hour, ethyl acetate was continuously fed into the reaction vessel at an addition rate of 17.3 parts/Hr while maintaining the internal temperature at 54 to 56 ℃ so that the concentration of the polymer was approximately 35%. After the internal temperature was maintained at 54 to 56 ℃ for 12 hours from the start of the addition of ethyl acetate, ethyl acetate was added to adjust the polymer concentration to 20% to obtain an ethyl acetate solution of the (meth) acrylic resin (a-1). The weight average molecular weight Mw of the (meth) acrylic resin (A-1) was 139 ten thousand, and the ratio Mw/Mn of the weight average molecular weight Mw to the number average molecular weight Mn was 5.32. The Gel Permeation Chromatography (GPC) showed a single peak for the Mw139 ten thousand component, and no other peak was observed in the Mw1000 to 250 ten thousand range.

The composition of the monomer in production example 3 (the numerical value in table 4 is part by weight), and the number of peaks in the Mw range of 1000 to 250 ten thousand on the GPC outflow curve (expressed as "GPC peak number" in table 4) are collectively shown in table 4.

[ Table 4]

Abbreviations in the column "monomer composition" of table 4 refer to the following monomers.

BA: butyl acrylate (glass transition temperature of homopolymer: -54 deg.C),

MA: methyl acrylate (glass transition temperature of homopolymer: 10 ℃), and,

HEA: 2-hydroxyethyl acrylate.

< example 9 and comparative example 8>

(1) Preparation of adhesive composition

The silane compound (B), the ionic compound (C), and the isocyanate-based crosslinking agent (D) shown in table 5 were mixed in amounts (parts by weight) shown in table 5 with respect to 100 parts of the solid content of the ethyl acetate solution (resin concentration: 20%) of the (meth) acrylic resin obtained in the above production example, and ethyl acetate was added so that the solid content concentration became 14% to obtain a pressure-sensitive adhesive composition. The blending amounts of the respective blending components shown in table 5 are parts by weight as effective components contained in a product containing a solvent or the like.

[ Table 5]

The details of each blending component shown in abbreviated form in table 5 are as follows.

(silane Compound)

B-1: a silane compound represented by the following formula:

[ solution 14]

(Ionic Compound)

C-5: n-decylpyridinium bis (fluorosulfonyl) imide salt.

(isocyanate-based crosslinking agent)

(2) Production of adhesive layer

(3) Production of optical film (P-1) having adhesive layer

(4) Evaluation of Metal Corrosion resistance of optical film with adhesive layer

The optical film with an adhesive layer (P-1) prepared in the above (3) was cut into a test piece of 20mm × 50mm in size, and was bonded to the metal layer side of the glass substrate with a metal layer therebetween. As the glass substrate with a metal layer, a glass substrate (manufactured by geomantec) was used in which a silver alloy (an alloy containing silver as a main component and palladium and copper, APC) layer having a thickness of about 500nm was laminated on the surface of an alkali-free glass by sputtering. After the obtained optical laminate was kept in an oven at a temperature of 60 ℃ and a relative humidity of 90% for 500 hours, light was projected from the back surface of the glass substrate, and the state of the metal layer of the portion to which the optical film with the adhesive layer was bonded was observed from the surface of the polarizing plate through a magnifying glass, and pitting corrosion (generation of holes having a diameter of 0.1mm or more and capable of transmitting light) was evaluated by the following criteria. The results are shown in table 6.

[ Table 6]

Description of the symbols

1 an optical film with an adhesive layer, 2 a polarizer, 3 a first resin film, 4a second resin film, 5, 6, 7 an optical laminate, 10 an optical film, 10a, 10b a polarizer, 20 an adhesive layer, 30 a metal layer, 40 a substrate, 50 a resin layer.

Claims

1. An optical laminate comprising an optical film, an adhesive layer, and a metal layer in this order,

2. The optical stack of claim 1,

the metal layer contains 1 or more selected from the group consisting of aluminum, copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and an alloy containing 2 or more metals selected from these metals.

3. The optical stack of claim 1,

the metal layer contains aluminum element.

4. The optical stack of claim 1,

the metal layer is a layer formed by sputtering.

5. The optical stack of claim 1,

the thickness of the metal layer is less than 3 μm.

6. The optical stack of claim 1,

the metal layer is a metal wiring layer.

7. The optical stack of claim 6,

the metal wiring layer has a metal wiring line width of 10 [ mu ] m or less.

8. The optical stack of claim 1,

the silane compound (B) represented by the formula (I) is a silane compound represented by the following formula (II):

9. The optical stack of claim 8,

m in the formula (II) is an integer of 4-20.

10. The optical stack of claim 8,

m in the formula (II) is an integer of 6-8.

11. The optical stack of claim 8,

m in the formula (II) is 6.

12. The optical stack of claim 1,

the silane compound (B) is 1, 6-bis (trimethoxysilyl) hexane.

13. The optical stack of claim 1,

the content of the silane compound (B) in the adhesive composition is 0.01 to 10 parts by weight relative to 100 parts by weight of the (meth) acrylic resin (A).

14. The optical stack of claim 1,

the (meth) acrylic resin (A) contains a constituent unit derived from a monomer having a hydroxyl group.

15. The optical stack of claim 1,

the (meth) acrylic resin (A) contains a constituent unit derived from an alkyl acrylate a1 and a constituent unit derived from an alkyl acrylate a2, and has a glass transition temperature of a homopolymer of alkyl acrylate a1 of less than 0 ℃ and a glass transition temperature of a homopolymer of alkyl acrylate a2 of 0 ℃ or higher.

16. The optical stack of claim 1,

the weight average molecular weight of the (meth) acrylic resin (A) is 50 to 250 ten thousand.

17. The optical stack of claim 1,

the adhesive composition further contains an isocyanate-based crosslinking agent (D).

18. The optical stack of claim 1,

the adhesive composition is substantially free of triazole-based compounds.

19. A liquid crystal display device comprising the optical stack of any one of claims 1-18.

20. An adhesive composition comprising a (meth) acrylic resin (A), a silane compound (B), and an ionic compound (C),

wherein A represents an alkylene group having 1 to 20 carbon atoms or an alicyclic hydrocarbon group having a valence of 2 and having 3 to 20 carbon atoms, -CH constituting the alkylene group and the alicyclic hydrocarbon group₂-may also be substituted by-O-or-C (═ O) -, R¹Represents an alkyl group having 1 to 5 carbon atoms, R²、R³、R⁴、R⁵And R⁶Each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms;

21. An optical film with an adhesive layer, comprising an optical film and an adhesive layer laminated on at least one surface of the optical film, wherein the optical film with the adhesive layer is adhered to a metal layer via the adhesive layer in use,

the adhesive layer is formed of an adhesive composition comprising,

comprising a (meth) acrylic resin (A), a silane compound (B), and an ionic compound (C),