JP2016194694A - Optical film with adhesive layer and liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical film with an adhesive layer that can suppress corrosion of a metal layer, such as a metal wiring layer and has excellent durability, and a liquid crystal display including the same.SOLUTION: There is provided an optical film with an adhesive layer comprising: an optical film; and an adhesive layer that is laminated thereon, and formed of an adhesive composition including 100 parts by weight of a (meth)acrylic resin (A), 0.08 to 2.5 parts by weight of an isocyanate crosslinking agent (B), a silane compound (C), and a predetermined ionic compound (D) represented by the formula (I), wherein the (meth)acrylic resin (A) contains a constitutional unit derived from alkyl acrylate (a1) where Tg of a homopolymer is less than 0°C and a constitutional unit derived from alkyl acrylate (a2) where Tg of a homopolymer is 0°C or more, and the optical film has a single peak within a range of a weight average molecular weight of 1000 to 2500000 on an exhaust curve in GPC. Also provided is a liquid crystal display including the optical film.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an optical film with an adhesive layer and a liquid crystal display device including the same.

  An optical film typified by a polarizing plate obtained by laminating and laminating a transparent resin film on one or both sides of a polarizer is widely used as an optical member constituting an image display device such as a liquid crystal display device. An optical film such as a polarizing plate is often used by being bonded to another member (for example, a liquid crystal cell or the like in a liquid crystal display device) via an adhesive layer [for example, Japanese Patent Application Laid-Open No. 2010-229321 (patent). Reference 1)]. For this reason, the optical film with an adhesive layer by which the adhesive layer was previously provided in the one surface as an optical film is known. Moreover, what added the ionic compound to the adhesive layer in order to provide antistatic property is also known.

JP 2010-229321 A

  2. Description of the Related Art In recent years, liquid crystal display devices have been developed for mobile device applications having a touch panel function typified by smartphones, tablet terminals, and in-vehicle car navigation systems. In such a touch input type liquid crystal display device, the optical film with the pressure-sensitive adhesive layer is disposed so that the pressure-sensitive adhesive layer is in direct contact with, for example, a resin layer or a metal layer made of metal wiring. Sometimes. However, in a configuration in which a metal layer made of a metal material and an adhesive layer containing an ionic compound are combined, the metal layer may corrode in a high temperature and high humidity environment. Among corrosion, pitting corrosion is a particular problem because the metal layer penetrates when the thickness of the metal layer is thin, or when the line width is narrow when the metal layer is a metal wiring.

  In general, durability is required for an optical film with an adhesive layer constituting a liquid crystal display device or the like. That is, the pressure-sensitive adhesive layer incorporated in a liquid crystal display device or the like may be placed in a high temperature or high temperature and high humidity environment, or may be placed in an environment where high and low temperatures are repeated. The optical film is required to be able to suppress problems such as floating and peeling at the interface between the pressure-sensitive adhesive layer and the optical member to which the optical film is bonded, foaming of the pressure-sensitive adhesive layer, and the like even under these circumstances. It is also required that the optical characteristics do not deteriorate.

  An object of this invention is to provide the optical film with an adhesive layer which can suppress corrosion of a metal layer like a metal wiring layer, and is excellent in durability, and a liquid crystal display device including the same.

  This invention provides the optical film with an adhesive layer shown below, a liquid crystal display device containing the same, and an adhesive composition.

[1] An optical film, and an adhesive layer laminated on at least one surface thereof,
The pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive composition containing a (meth) acrylic resin (A), an isocyanate-based crosslinking agent (B), a silane compound (C), and an ionic compound (D),
The (meth) acrylic resin (A) includes a structural unit derived from an alkyl acrylate (a1) having a glass transition temperature of a homopolymer of less than 0 ° C., and an alkyl acrylate having a glass transition temperature of the homopolymer of 0 ° C. or more ( a (meth) acrylic resin containing a structural unit derived from a2) and having a single peak in the weight average molecular weight range of 1000 to 2.5 million on the discharge curve in gel permeation chromatography;
Content of the said isocyanate type crosslinking agent (B) is 0.08-2.5 weight part with respect to 100 weight part of said (meth) acrylic-type resins (A),
The ionic compound (D) has the following formula (I):

(In the formula, R ^{1 to} R ⁸ may each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. A good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, wherein R ^{1 to} R ⁴ form a ring with adjacent substituents; R ^{5 to} R ⁸ may form a ring with adjacent substituents.
An optical film with an adhesive layer, which is an ionic compound represented by:

  [2] The anion of the ionic compound (D) is represented by the following formula (II):

(In the formula, R ^{9 to} R ¹³ may each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. It represents a good alkynyl group, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or a halogen atom, and adjacent substituents may form a ring. )
The optical film with an adhesive layer according to [1], which is a borate anion represented by:

  [3] The optical film with an adhesive layer according to [1] or [2], wherein the anion of the ionic compound (D) is a tetrakis (pentafluorophenyl) borate anion.

  [4] Any of [1] to [3], wherein the anion of the ionic compound (D) is a tetrakis (pentafluorophenyl) borate anion, and the cation has a nitrogen atom-containing heterocyclic structure containing an unsaturated bond An optical film with a pressure-sensitive adhesive layer according to claim 1.

  [5] The anion of the ionic compound (D) is a tetrakis (pentafluorophenyl) borate anion, and the cation is represented by the following formula (III):

(In the formula, R ^{14 to} R ¹⁹ may each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Represents a good alkynyl group, optionally substituted aryl group, optionally substituted heterocyclic group, hydroxyl group, ether group, carboxyl group, carbonyl group, or halogen atom, adjacent substitution A group may form a ring.)
The optical film with an adhesive layer in any one of [1]-[4] which is a pyridinium cation represented by these.

  [6] The optical film with an adhesive layer according to any one of [1] to [5], wherein the (meth) acrylic resin (A) contains a structural unit derived from a monomer having a hydroxyl group.

  [7] The optical film with an adhesive layer according to any one of [1] to [6], wherein the (meth) acrylic resin (A) has a weight average molecular weight of 500,000 to 2,500,000.

  [8] The optical film with an adhesive layer according to any one of [1] to [7], wherein the adhesive composition does not substantially contain a peroxide.

  [9] The optical film with the pressure-sensitive adhesive layer according to any one of [1] to [8], wherein the pressure-sensitive adhesive composition does not substantially contain a triazole compound.

  [10] The optical film with an adhesive layer according to any one of [1] to [9], wherein the (meth) acrylic resin (A) does not substantially contain a structural unit derived from a methacrylate monomer. .

[11] The optical film includes a polarizer made of a polyvinyl alcohol resin dyed with iodine,
The said adhesive layer is an optical film with an adhesive layer in any one of [1]-[10] laminated | stacked directly on the said polarizer.

  [12] A liquid crystal display device comprising the optical film with the pressure-sensitive adhesive layer according to any one of [1] to [11].

[13] A (meth) acrylic resin (A), an isocyanate crosslinking agent (B), a silane compound (C), and an ionic compound (D),
The (meth) acrylic resin (A) includes a structural unit derived from an alkyl acrylate (a1) having a glass transition temperature of a homopolymer of less than 0 ° C., and an alkyl acrylate having a glass transition temperature of the homopolymer of 0 ° C. or more ( a (meth) acrylic resin containing a structural unit derived from a2) and having a single peak in the weight average molecular weight range of 1000 to 2.5 million on the discharge curve in gel permeation chromatography;
Content of the said isocyanate type crosslinking agent (B) is 0.08-2.5 weight part with respect to 100 weight part of said (meth) acrylic-type resins (A),
The ionic compound (D) has the following formula (I):

(In the formula, R ^{1 to} R ⁸ may each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. A good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, wherein R ^{1 to} R ⁴ form a ring with adjacent substituents; R ^{5 to} R ⁸ may form a ring with adjacent substituents.
An ionic compound represented by
The adhesive composition used for formation of the adhesive layer laminated | stacked on a metal layer.

  ADVANTAGE OF THE INVENTION According to this invention, the optical film with an adhesive layer which can suppress the corrosion of the metal layer arrange | positioned in contact with an adhesive layer, and is excellent also in durability, and a liquid crystal display device including the same are provided. it can.

It is a schematic sectional drawing which shows an example of the optical film with an adhesive layer which concerns on this invention. It is a schematic sectional drawing which shows an example of the laminated constitution of a polarizing plate. It is a schematic sectional drawing which shows another example of the laminated constitution of a polarizing plate. It is a schematic sectional drawing which shows an example of the layer structure of an optical laminated body. It is a schematic sectional drawing which shows another example of the layer structure of an optical laminated body. It is a schematic sectional drawing which shows another example of the layer structure of an optical laminated body. It is a schematic sectional drawing which shows another example of the layer structure of an optical laminated body. It is a schematic sectional drawing which shows another example of the layer structure of an optical laminated body.

<Optical film with adhesive layer>
FIG. 1 is a schematic cross-sectional view showing an example of an optical film with an adhesive layer according to the present invention. As FIG. 1 shows, the optical film 1 with an adhesive layer which concerns on this invention contains the optical film 10 and the adhesive layer 20 laminated | stacked on the at least one surface. The pressure-sensitive adhesive layer 20 is usually laminated directly on the surface of the optical film 10.

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

[1] Optical Film The optical film 10 provided in the optical film 1 with an adhesive layer can be various optical films (films having optical characteristics) that can be incorporated into an image display device such as a liquid crystal display device. The optical film 10 may be an optical film having a single layer structure or an optical film having a multilayer structure. Specific examples of the optical film having a single layer structure include, in addition to a polarizer, optical functional films such as a retardation film, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, and a light collecting film. Specific examples of the multilayered optical film include a polarizing plate and a retardation plate. In the present specification, the polarizing plate refers to a film in which a resin film or a resin layer is laminated on at least one surface of a polarizer. A phase difference plate means that a resin film or a resin layer is laminated on at least one surface of a phase difference film. The optical film 10 is preferably a polarizing plate, a polarizer, a retardation plate or a retardation film, and more preferably a polarizing plate or a polarizer.

[1-1] Polarizing Plate FIGS. 2 and 3 are schematic cross-sectional views illustrating examples of the layer configuration 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. It is a double-sided protective polarizing plate in which the second resin film 4 is further laminated and bonded to the other surface. The first and second resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer and an adhesive layer (not shown). The polarizing plates 10a and 10b may include other films and layers other than the first and second resin films 3 and 4.

  The polarizer 2 is a film having a property of absorbing linearly polarized light having a vibration surface parallel to the absorption axis and transmitting linearly polarized light having a vibration surface orthogonal to the absorption axis (parallel to the transmission axis). A film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin film can be used. As the dichroic dye, iodine or a dichroic organic dye is used.

  The polyvinyl alcohol-based resin can be obtained by saponifying a polyvinyl acetate-based 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 acid, olefin, vinyl ether, unsaturated sulfonic acid, (meth) acrylamide having an ammonium group, and the like.

  The saponification degree of the polyvinyl alcohol resin is usually 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. The average degree of polymerization of the polyvinyl alcohol-based resin is usually 1000 to 10000, preferably 1500 to 5000. The average degree of polymerization of the polyvinyl alcohol resin can be determined according to JIS K 6726.

  Usually, what formed the polyvinyl alcohol-type resin into a film is used as a raw film of the polarizer 2. A polyvinyl alcohol-type resin can be formed into a film by a well-known method. The thickness of the raw film is usually 1 to 150 μm, and preferably 10 μm or more in consideration of easiness of stretching.

  The polarizer 2 is, for example, a step of uniaxially stretching the original film, a step of dyeing the film with a dichroic dye and adsorbing the dichroic dye, a step of treating the film with an aqueous boric acid solution, and The film is washed with water and finally dried. The thickness of the polarizer 2 is usually 1 to 30 μm, and preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less, from the viewpoint of thinning the optical film 1 with an adhesive layer.

  A polarizer 2 formed by adsorbing and orienting a dichroic dye on a polyvinyl alcohol-based resin film is as follows: 1) A single film of a polyvinyl alcohol-based resin film is used as a raw film, and this film is uniaxially stretched and dichroic. In addition to the method of dyeing dyes, 2) A base film having a polyvinyl alcohol resin layer was obtained by applying a coating liquid (such as an aqueous solution) containing a polyvinyl alcohol resin to the base film and drying it. Thereafter, this can also be obtained by uniaxially stretching the whole base film, subjecting the stretched polyvinyl alcohol resin layer to a dichroic dye dyeing process, and then peeling and removing the base film. As the base film, a film made of a thermoplastic resin similar to the thermoplastic resin that can constitute the first and second resin films 3 and 4 described later can be used, and preferably a polyester-based resin such as polyethylene terephthalate. , Polycarbonate resins, cellulose resins such as triacetyl cellulose, cyclic polyolefin resins such as norbornene resins, polystyrene resins, and the like. According to the method 2), the production of the thin film polarizer 2 is facilitated. For example, the production of the polarizer 2 having a thickness of 7 μm or less is also facilitated.

  The first and second resin films 3 and 4 are each independently a light-transmitting, preferably optically transparent thermoplastic resin such as a chain polyolefin resin (polyethylene resin, polypropylene resin, etc.). Polyolefin resins such as cyclic polyolefin resins (norbornene resins, etc.); cellulose resins (cellulose ester resins, etc.); polyester resins (polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, etc.); polycarbonate resins; It can be a film made of (meth) acrylic resin; polystyrene resin; polyether ether ketone resin; polysulfone resin, or a mixture or copolymer thereof. Among these, the first and second resin films 3 and 4 are each composed of a resin selected from the group consisting of a cyclic polyolefin resin, a polycarbonate resin, a cellulose resin, a polyester resin, and a (meth) acrylic resin. It is preferable that the resin is selected from the group consisting of a cellulose resin and a cyclic polyolefin resin.

  Examples of the chain polyolefin-based resin include homopolymers of chain olefins such as polyethylene resins and polypropylene resins, and copolymers composed of two or more chain olefins.

  Cyclic polyolefin-based resin is a general term for resins containing, as polymerized units, cyclic olefins typically represented by norbornene, tetracyclododecene (also known as dimethanooctahydronaphthalene) or their derivatives. Specific examples of cyclic polyolefin resins include cyclic olefin ring-opening (co) polymers and hydrogenated products thereof, cyclic olefin addition polymers, cyclic olefins and chain olefins such as ethylene and propylene, or vinyl groups. A copolymer with an aromatic compound, a modified (co) polymer obtained by modifying these with an unsaturated carboxylic acid or a derivative thereof, and the like. Among these, norbornene resins using norbornene monomers such as norbornene and polycyclic norbornene monomers as cyclic olefins are preferably used.

  The cellulose-based resin is preferably a cellulose ester-based resin, that is, a cellulose partial or completely esterified product, and examples thereof include cellulose acetate, propionate, butyrate, and mixed esters thereof. Of these, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and the like are preferably used.

  The polyester-based resin is a resin other than the cellulose ester-based resin having an ester bond, and is generally made of a polycondensate of a polyvalent carboxylic acid or a derivative thereof and a polyhydric alcohol. Specific examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethyl terephthalate, and polycyclohexanedimethyl naphthalate.

  The polycarbonate-based resin is a polyester formed from carbonic acid and glycol or bisphenol. Among these, an aromatic polycarbonate having a diphenylalkane in the molecular chain is preferably used from the viewpoints of heat resistance, weather resistance and acid resistance. As polycarbonate, 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1 Illustrative are polycarbonates derived from bisphenols such as -bis (4-hydroxyphenyl) isobutane, 1,1-bis (4-hydroxyphenyl) ethane.

The (meth) acrylic resin that can constitute the first and second resin films 3 and 4 can be a polymer mainly composed of a structural unit derived from a methacrylic ester (for example, containing 50% by weight or more). The copolymer is preferably a copolymer in which another copolymer component is copolymerized. The (meth) acrylic resin may contain two or more structural units derived from methacrylic acid esters. Examples of the methacrylic acid ester include C _{1 to} C ₄ alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate.

Examples of the copolymer component that can be copolymerized with the methacrylic acid ester include acrylic acid esters. Acrylic acid ester is preferably methyl acrylate, ethyl acrylate, butyl acrylate, C ₁ -C ₈ alkyl esters of acrylic acid such as 2-ethylhexyl acrylate. Specific examples of other copolymer components include unsaturated acids such as (meth) acrylic acid; aromatic vinyl compounds such as styrene, halogenated styrene, α-methylstyrene and vinyltoluene; vinylcyan compounds such as (meth) acrylonitrile ; Unsaturated acid anhydrides such as maleic anhydride and citraconic anhydride; unsaturated imides such as phenylmaleimide and cyclohexylmaleimide, etc. other than acrylic acid esters having one polymerizable carbon-carbon double bond in the molecule A compound can be mentioned. A compound having two or more polymerizable carbon-carbon double bonds in the molecule may be used as a copolymerization component. Only 1 type may be used for a copolymerization component and it may use 2 or more types together.

  The (meth) acrylic resin may have a ring structure in the polymer main chain in that the durability of the film can be improved. 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. Specific examples of the lactone ring structure include a butyrolactone ring. Structure and valerolactone ring structure.

The (meth) acrylic resin may contain acrylic rubber particles from the viewpoints of film-formability on the film and impact resistance of the film. Acrylic rubber particles are particles having an elastic polymer mainly composed of an acrylate ester as an essential component. The acrylic rubber particles have a single-layer structure consisting essentially of this elastic polymer, or an elastic polymer in one layer. And a multilayer structure having Examples of the elastic polymer include a cross-linked elastic copolymer obtained by copolymerizing an alkyl acrylate as a main component with another vinyl monomer and a cross-linkable monomer copolymerizable therewith. Examples of the alkyl acrylate as the main component of the elastic polymer include C ₁ -C ₈ alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. The number of carbon atoms of the alkyl group is preferably 4 or more.

  Examples of other vinyl monomers copolymerizable with alkyl acrylate include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methacrylic acid such as methyl methacrylate. Examples thereof include aromatic vinyl compounds such as esters and styrene, vinylcyan compounds such as (meth) acrylonitrile, and the like. Examples of the crosslinkable monomer include a crosslinkable compound having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, ethylene glycol di (meth) acrylate, butanediol di ( Examples include (meth) acrylates of polyhydric alcohols such as (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, more preferably 10 parts by weight or more with respect to 100 parts by weight of the (meth) acrylic resin. When the content of the acrylic rubber particles is too large, the surface hardness of the film is lowered, and when the film is subjected to surface treatment, the solvent resistance against the organic solvent in the surface treatment agent can be lowered. Accordingly, the content of the acrylic rubber particles is usually 80 parts by weight or less, preferably 60 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic resin.

  The 1st, 2nd resin films 3 and 4 can contain the usual additive in the technical field of the present invention. Specific examples of additives include, for example, ultraviolet absorbers, infrared absorbers, organic dyes, pigments, inorganic dyes, antioxidants, antistatic agents, surfactants, lubricants, dispersants, heat stabilizers, and the like. .

  Examples of the ultraviolet absorber include salicylic acid ester compounds, benzophenone compounds, benzotriazole compounds, triazine compounds, cyano (meth) acrylate compounds, nickel complex salts, and the like.

  Each of the first and second resin films 3 and 4 may be an unstretched film or a uniaxially or biaxially stretched film. Biaxial stretching may be simultaneous biaxial stretching in which stretching is performed simultaneously in two stretching directions, or sequential biaxial stretching in which stretching is performed in a predetermined direction and then stretching 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 polarizer 2 or a protective film having an optical function such as a retardation film described later. You can also. The retardation film is an optical film that exhibits optical anisotropy. For example, an arbitrary retardation value is given by stretching a film made of the thermoplastic resin (uniaxial stretching or biaxial stretching) or by forming a liquid crystal layer or the like on the thermoplastic resin film. It can be set as a retardation film.

  The first resin film 3 and the second resin film 4 may be films made of the same thermoplastic resin, or may be 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 / absence of additives, types thereof, retardation characteristics, and the like.

  The first resin film 3 and / or the second resin film 4 has a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, an antistatic layer, an antistatic layer on the outer surface (the surface opposite to the polarizer 2). You may provide surface treatment layers (coating layer), such as a dirty layer and a conductive layer.

  The thickness of the 1st resin film 3 and the 2nd resin film 4 is 1-150 micrometers normally, respectively, Preferably it is 5-100 micrometers, More preferably, it is 5-60 micrometers. The thickness may be 50 μm or less, and further 30 μm or less. Reducing the thickness of the first and second resin films 3 and 4 includes reducing the thickness of the optical film 1 with an adhesive layer and an optical laminate including the same, and consequently including the optical film 1 with an adhesive layer or the optical laminate. This is advantageous for thinning the liquid crystal display device.

  In particular, a polarizing plate for small and medium-sized devices such as smartphones and tablet terminals is often used as a thin film having a thickness of 30 μm or less as the first resin film 3 and / or the second resin film 4 because of the demand for thinning. Such a polarizing plate has a weak force to suppress the contraction force of the polarizer 2 and tends to have insufficient durability. According to this invention, even if it is a case where such a polarizing plate is used as the optical film 10, the optical film 1 with an adhesive layer which has favorable durability, and an optical laminated body containing this can be provided. The durability of the optical film 1 with an adhesive layer and the optical laminate is, for example, an adhesive layer 20 and an optical layer adjacent to the adhesive layer 20 in a high temperature environment, a high temperature and high humidity environment, an environment where high and low temperatures are repeated, The property which can suppress malfunctions, such as a float and peeling in the interface with a member, and foaming of the adhesive layer 20, is said.

  Further, from the viewpoint of reducing the thickness of the polarizing plate, a configuration in which the resin film is disposed only on one side of the polarizer 2 is advantageous as in the polarizing plate 10a shown in FIG. In this case, the pressure-sensitive adhesive layer 20 is usually directly bonded to the other surface of the polarizer 2 to obtain the pressure-sensitive adhesive layer-attached optical film 1 (see FIG. 4). In the case of the polarizing plate having such a configuration, the problem of reducing 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 significant. 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 having good optical durability (property capable of suppressing deterioration of optical characteristics), and An optical layered body can be provided.

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

  Examples of the water-based adhesive include an adhesive made of a polyvinyl alcohol-based resin aqueous solution, an aqueous two-component urethane emulsion adhesive, and the like. Among these, a water-based adhesive composed of a polyvinyl alcohol-based resin aqueous solution is preferably used. Polyvinyl alcohol resins include vinyl alcohol homopolymers obtained by saponifying polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith. A polyvinyl alcohol copolymer obtained by saponifying a polymer, a modified polyvinyl alcohol polymer obtained by partially modifying the hydroxyl group thereof, or the like can be used. The water-based adhesive can 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.

  When using an aqueous adhesive, after bonding the polarizer 2 and the first and second resin films 3 and 4, carry out a drying process to remove water contained in the aqueous adhesive. Is preferred. After the drying process, for example, a curing process for curing at a temperature of about 20 to 45 ° C. may be provided.

  The active energy ray-curable adhesive refers to an adhesive that cures when irradiated with active energy rays such as ultraviolet rays and electron beams. For example, a curable composition containing a polymerizable compound and a photopolymerization initiator, light Examples thereof include a curable composition containing a reactive resin, a curable composition containing a binder resin and a photoreactive crosslinking agent. An ultraviolet curable adhesive is preferable. Examples of the polymerizable compound include photopolymerizable monomers such as photocurable epoxy monomers, photocurable (meth) acrylic monomers, and photocurable urethane monomers, and oligomers derived from the photopolymerizable monomers. . Examples of the photopolymerization initiator include those containing substances that generate active species such as neutral radicals, anion radicals, and cation radicals upon irradiation with active energy rays. As an active energy ray-curable adhesive containing a polymerizable compound and a photopolymerization initiator, a curable composition containing a photocurable epoxy monomer and a cationic photopolymerization initiator, a photocurable (meth) acrylic monomer, and light A curable composition containing a radical polymerization initiator or a mixture of these curable compositions can be preferably used.

  When an active energy ray-curable adhesive is used, after the polarizer 2 and the first and second resin films 3 and 4 are bonded, a drying process is performed as necessary, and then an active energy ray is irradiated. A curing step of curing the active energy ray-curable adhesive is performed. Although the light source of the active energy ray is not particularly limited, ultraviolet light having a light emission distribution at a wavelength of 400 nm or less is preferable. A wave excitation mercury lamp, a metal halide lamp, etc. can be used.

  In bonding the polarizer 2 and the first and second resin films 3 and 4, at least one of these bonding surfaces is subjected to a surface activation process such as a saponification process, a corona process, or a plasma process. be able to. When resin films are bonded to both sides of the polarizer 2, the adhesive for bonding these resin films may be the same type of adhesive or different types of adhesives.

  The polarizing plates 10a and 10b can further include other films or layers. Specific examples thereof include a retardation film, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, a condensing film, an adhesive layer other than the adhesive layer 20, a coating layer, a protective film, and the like. . 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 scratches and dirt, and is peeled and removed after the optical film 1 with an adhesive layer is bonded onto, for example, the metal layer 30. It is customary.

  The protective film is usually composed of a base film and a pressure-sensitive adhesive layer laminated thereon. The base film is composed of a thermoplastic resin, for example, a polyolefin resin such as polyethylene resin or polypropylene resin; a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; a polycarbonate resin; a (meth) acrylic resin, or the like. be able to.

[1-2] Phase difference plate The phase difference film included in the phase difference plate is an optical film showing optical anisotropy as described above, and can be used for the first and second resin films 3 and 4. In addition to the thermoplastic resins exemplified above, for example, polyvinyl alcohol resins, polyarylate resins, polyimide resins, polyether sulfone resins, polyvinylidene fluoride / polymethyl methacrylate resins, liquid crystal polyester resins, It can be a stretched film obtained by stretching a resin film made of an ethylene-vinyl acetate copolymer saponified product, a polyvinyl chloride resin, etc. by about 1.01 to 6 times. Among them, a stretched film obtained by uniaxially stretching or biaxially stretching a polycarbonate resin film, a cyclic olefin resin film, a (meth) acrylic resin film, or a cellulose resin film is preferable. In the present specification, a zero retardation film is also included in the retardation film (however, it can also be used as a protective film). In addition, a film called a uniaxial retardation film, a wide viewing angle retardation film, a low photoelastic modulus retardation film, or the like is also applicable as the retardation film.

The zero Letters retardation film in-plane retardation value R _e and the thickness direction retardation R _th means a film are both -15～15Nm. This retardation film is suitably used for an IPS mode liquid crystal display device. Plane retardation value R _e and the thickness direction retardation R _th are preferably both -10～10Nm, more preferably both -5～5Nm. Here plane retardation value refers R _e and the thickness direction retardation R _th is a value at a wavelength of 590 nm.

The in-plane retardation value _Re and the thickness direction retardation value R _th are respectively expressed by the following formulas:
_{R e = (n x -n y} ) × d
R _th = [(n _x + _ny ) / 2−n _z ] × d
Defined by Wherein, n _x is a refractive index in a slow axis direction (x-axis direction) in the film plane, n _y is the fast axis direction in the film plane of the (y-axis direction orthogonal to the x-axis in a plane) It is a refractive index, _nz is the refractive index in the film thickness direction (z-axis direction perpendicular to the film surface), and d is the thickness of the film.

  As the zero retardation film, for example, a resin film made of a polyolefin resin such as a cellulose resin, a chain polyolefin resin, and a cyclic polyolefin resin, a polyethylene terephthalate resin, or a (meth) acrylic resin can be used. In particular, a cellulose resin, a polyolefin resin, or a (meth) acrylic resin is preferably used because the retardation value is easily controlled and easily available.

  Moreover, the film which expressed optical anisotropy by application | coating and orientation of a liquid crystalline compound, and the film which expressed optical anisotropy by application | coating of an inorganic layered compound can also be used as retardation film. In such a retardation film, a so-called temperature compensation type retardation film, and a rod-like liquid crystal sold under the trade name “NH film” from JX Nippon Mining & Energy Co., Ltd. are tilted. Film, a film with a disc-shaped liquid crystal sold under the trade name “WV film” from FUJIFILM Corporation, and a complete biaxial film sold under the trade name “VAC film” from Sumitomo Chemical Co., Ltd. Examples of the orientation type film include a biaxial orientation type film sold by Sumitomo Chemical Co., Ltd. under the trade name “new VAC film”.

  The resin film laminated | stacked on the at least one surface of retardation film can be the above-mentioned protective film, for example.

[2] Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer 20 laminated on at least one surface of the optical film 10 includes a (meth) acrylic resin (A), an isocyanate-based crosslinking agent (B), a silane compound (C), and ions. It is comprised from the adhesive composition containing an adhesive compound (D). In this pressure-sensitive adhesive composition, the (meth) acrylic resin (A) is a structural unit derived from an alkyl acrylate (a1) whose homopolymer has a glass transition temperature of less than 0 ° C., and the homopolymer has a glass transition temperature of 0 ° C. or higher. (Meth) having a structural unit derived from alkyl acrylate (a2) and having a single peak in the weight average molecular weight range of 1000 to 2.5 million on the emission curve in gel permeation chromatography (GPC) Acrylic resin. Content of isocyanate type crosslinking agent (B) is 0.08-2.5 weight part with respect to 100 weight part of (meth) acrylic-type resin (A).

  The ionic compound (D) has the following formula (I):

(In the formula, R ^{1 to} R ⁸ may each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Represents a good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and R ^{5 to} R ⁸ form a ring with adjacent substituents. May be.)
It is an ionic compound represented by.

  According to the pressure-sensitive adhesive layer 20 composed of the above-mentioned pressure-sensitive adhesive composition, even when the pressure-sensitive adhesive layer 20 is disposed on a substrate including a metal layer, the corrosion of the metal layer can be suppressed. Moreover, durability of the optical film 1 with an adhesive layer and an optical laminated body containing this can be improved. Furthermore, according to the adhesive layer 20 comprised by said adhesive composition, the adhesive layer 20 is directly bonded by the polarizer 2 with the optical film 1 with an adhesive layer, and the optical laminated body containing this. Even with this configuration, good optical durability can be exhibited. Hereinafter, the property capable of suppressing the corrosion of the metal layer is also referred to as “metal corrosion resistance”.

  The thickness of the pressure-sensitive adhesive layer 20 is usually 2 to 40 μm, and is preferable from the viewpoint of the durability of the optical film 1 with the pressure-sensitive adhesive layer and the optical laminate including the same, the reworkability of the optical film 1 with the pressure-sensitive adhesive layer, and the like. Is 5-30 μm, more preferably 10-25 μm. Moreover, the followability of the adhesive layer 20 with respect to the dimensional change of the optical film 10 becomes favorable as the thickness of the adhesive layer 20 is 10 micrometers or more, and rework property becomes favorable as it is 25 micrometers or less.

  The pressure-sensitive adhesive layer 20 preferably exhibits a storage elastic modulus of 0.1 to 5 MPa in a temperature range of 23 to 80 ° C. Thereby, durability of the optical film 1 with an adhesive layer and an optical laminated body containing this can be improved more effectively. “Shows a storage elastic modulus of 0.1 to 5 MPa in a temperature range of 23 to 80 ° C.” means that the storage elastic modulus is a value within the above range at any temperature within this range. Since the storage elastic modulus usually decreases gradually as the temperature rises, if both the storage elastic modulus at 23 ° C. and 80 ° C. are within the above range, the storage elastic modulus within the above range is exhibited at the temperature in this range. Can be seen. The storage elastic modulus of the pressure-sensitive adhesive layer 20 can be measured using a commercially available viscoelasticity measuring device, for example, a viscoelasticity measuring device “DYNAMIC ANALYZER RDA II” manufactured by REOMETRIC.

[2-1] (Meth) acrylic resin (A)
It is a polymer or copolymer having a structural unit derived from a (meth) acrylic monomer as a main component (preferably containing 50% by weight or more). A specific example of the (meth) acrylic monomer is a monomer having a (meth) acryloyl group such as an alkyl (meth) acrylate, and the (meth) acrylic resin (A) is a glass transition of a homopolymer. It is a resin containing a structural unit derived from an alkyl acrylate (a1) having a temperature Tg of less than 0 ° C. and a structural unit derived from an alkyl acrylate (a2) having a Tg of a homopolymer of 0 ° C. or higher. Thereby, the metal corrosion resistance and durability of the optical film 1 with an adhesive layer and an optical laminate including the same can be enhanced. Literature values such as POLYMER HANDBOOK (Wiley-Interscience) can be adopted as the Tg of the alkyl acrylate homopolymer.

  Specific examples of the alkyl acrylate (a1) include ethyl acrylate, n- and i-propyl acrylate, n- and i-butyl acrylate, n-pentyl acrylate, n- and i-hexyl acrylate, n-heptyl acrylate, n- And alkyl acrylates having about 2 to 12 carbon atoms in the alkyl group, such as i-octyl acrylate, 2-ethylhexyl acrylate, n- and i-nonyl acrylate, n- and i-decyl acrylate, and n-dodecyl acrylate . As another specific example of the alkyl acrylate (a1), a substituent-containing alkyl acrylate in which a substituent is introduced into the alkyl group in the alkyl acrylate having an alkyl group having about 2 to 12 carbon atoms can be exemplified. The substituent of the substituent-containing alkyl acrylate is a group that substitutes a hydrogen atom of the alkyl group, and specific examples thereof include a phenyl group, an alkoxy group, and a phenoxy group. Specific examples of the substituent-containing alkyl acrylate 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.

  Alkyl acrylate (a1) may use only 1 type and may use 2 or more types together. Among them, the alkyl acrylate (a1) preferably contains one or more selected from ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate. From the viewpoint of followability to the optical film 10 of the pressure-sensitive adhesive layer 20 included in the pressure-sensitive adhesive layer optical film 1 and reworkability, the alkyl acrylate (a1) preferably contains n-butyl acrylate.

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

  Alkyl acrylate (a2) may use only 1 type and may use 2 or more types together. Among these, from the viewpoint of metal corrosion resistance and durability, the alkyl acrylate (a2) preferably includes methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, and the like, and more preferably includes methyl acrylate.

  The content of the structural unit derived from the alkyl acrylate (a2) in the (meth) acrylic resin (A) is from the viewpoint of metal corrosion resistance and durability of the optical film 1 with an adhesive layer and an optical laminate including the same. , In 100 parts by weight of all the structural units constituting the (meth) acrylic resin (A), preferably 10 parts by weight or more, more preferably 15 parts by weight or more, further preferably 20 parts by weight or more, Particularly preferred is 25 parts by weight or more. Further, from the viewpoint of followability of the pressure-sensitive adhesive layer 20 to the optical film 10 and reworkability, the content of the structural unit derived from the alkyl acrylate (a2) is preferably 70 parts by weight or less, more preferably 60 parts by weight or less. More preferably, it is 50 parts by weight or less.

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

1) A monomer having a polar functional group.
Examples of the monomer having a polar functional group include (meth) acrylate having a substituent such as a hydroxy group, a carboxyl group, a substituted or unsubstituted amino group, and a heterocyclic group such as an epoxy group. Specifically, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- (2-hydroxyethoxy) ethyl (meth) acrylate, (Meth) acrylic acid 2-chloro-2-hydroxypropyl, (meth) acrylic acid 3-chloro-2-hydroxypropyl, monomers having a hydroxy group such as diethylene glycol mono (meth) acrylate; acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, 2,5-dihydride Monomers having a heterocyclic group such as furan; a monomer having a substituted or unsubstituted amino group such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, etc. Example: Monomers having a carboxyl group such as (meth) acrylic acid and carboxyethyl (meth) acrylate. Especially, the monomer which has a hydroxyl group is preferable, and the (meth) acrylate which has a hydroxyl group is more preferable at the reactive point of (meth) acrylic-type resin (A) and a crosslinking agent.

  In addition to the (meth) acrylate having a hydroxy group, the above-mentioned monomer having another polar functional group may be included, but the peel strength of the separate film that can be laminated on the outer surface of the pressure-sensitive adhesive layer 20 is increased. From the viewpoint of prevention, it is preferable that the monomer having an amino group is substantially not contained. Moreover, it is preferable that the monomer which has a carboxyl group is not included substantially from a viewpoint of improving the corrosion resistance with respect to ITO. Here, “substantially free” means that it is 0.1 parts by weight or less in 100 parts by weight of all the structural units constituting the (meth) acrylic resin (A).

2) Acrylamide monomer.
For example, N-methylolacrylamide, N- (2-hydroxyethyl) acrylamide, N- (3-hydroxypropyl) acrylamide, N- (4-hydroxybutyl) acrylamide, N- (5-hydroxypentyl) acrylamide, N- ( 6-hydroxyhexyl) acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-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- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylic Amide, N- (propoxymethyl) acrylamide, N- (1-methylethoxymethyl) acrylamide, N- (1-methylpropoxymethyl) acrylamide, N- (2-methylpropoxymethyl) acrylamide [alias: N- (isobutoxy Methyl) 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- (2-isobutoxy Chill) acrylamide], N- (2-butoxyethyl) acrylamide, N- [2- (1,1-dimethylethoxy) ethyl] acrylamide. Among these, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (butoxymethyl) acrylamide, and N- (2-methylpropoxymethyl) acrylamide are preferably used.

3) Methacrylate, ie methacrylic acid ester.
For example, linear alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate and lauryl methacrylate; methacrylic acid such as isobutyl methacrylate, 2-ethylhexyl methacrylate and i-octyl methacrylate Branched alkyl esters of methacrylic acid such as isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, cyclododecyl methacrylate, methyl cyclohexyl methacrylate, trimethyl cyclohexyl methacrylate, t-butyl cyclohexyl methacrylate, cyclohexyl phenyl methacrylate, etc. Alkyl ester; 2-methoxyethyl methacrylate And alkoxyalkyl esters of methacrylic acid such as ethoxymethyl methacrylate; aralkyl esters of methacrylic acid such as benzyl methacrylate; 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2- (2-hydroxyethoxy) ethyl Alkyl esters of methacrylic acid having hydroxyl groups such as methacrylate, 2-chloro-2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monomethacrylate; aminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate; Alkyl ester of methacrylic acid having a substituted or unsubstituted amino group such as dimethylaminopropyl methacrylate Ter; 2-phenoxyethyl methacrylate, 2- (2-phenoxyethoxy) ethyl methacrylate, ethylene oxide-modified nonylphenol ester of (meth) acrylic acid, methacrylic acid having a phenoxyethyl group such as 2- (o-phenylphenoxy) ethyl methacrylate Esters etc.

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

5) Styrene monomer.
For example, styrene; alkyl styrene such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene; fluorostyrene, chlorostyrene, bromostyrene, Halogenated styrene such as dibromostyrene and iodostyrene; nitrostyrene; acetylstyrene; methoxystyrene; divinylbenzene and the like.

6) Vinyl monomer.
For example, fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride; vinylpyridine Nitrogen-containing aromatic vinyl such as vinylpyrrolidone and vinylcarbazole; conjugated diene monomers such as butadiene, isoprene and chloroprene; unsaturated nitriles such as acrylonitrile and methacrylonitrile.

7) A monomer having a plurality of (meth) acryloyl groups in the molecule.
For example, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) ) Monomers having two (meth) acryloyl groups in the molecule such as acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate; molecules such as trimethylolpropane tri (meth) acrylate A monomer having three (meth) acryloyl groups in the inside.

  As described above, the (meth) acrylic resin (A) is 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 an optical laminate including the same. In addition to the structural unit to be formed, it is preferable to include a structural unit derived from a monomer having a polar functional group. The monomer having a polar functional group is preferably a (meth) acrylate monomer having a polar functional group, and more preferably a monomer having a hydroxyl group. Content of the structural unit derived from the monomer having a polar functional group is preferably 0.1 to 10 parts by weight in 100 parts by weight of all the structural units constituting the (meth) acrylic resin (A), More preferably, it is 0.25-5 weight part, More preferably, it is 0.5-5 weight part.

  Further, from the viewpoint of the reworkability of the optical film 1 with an adhesive layer, the (meth) acrylic resin (A) is derived from a methacrylic monomer such as a methacrylate (methacrylic acid ester) or a methacrylamide monomer. The content of the structural unit is preferably small, and specifically, the content of the structural unit is preferably 10 parts by weight in 100 parts by weight of all the structural units constituting the (meth) acrylic resin (A). It is below, More preferably, it is 5 parts weight or less, It is further more preferable that the said structural unit is not contained substantially (0.1 part weight or less).

  The (meth) acrylic resin (A) has a single peak in the range of the weight average molecular weight Mw of 1,000 to 2,500,000 on the discharge curve in gel permeation chromatography (GPC). The pressure-sensitive adhesive layer 20 having a base polymer of the (meth) acrylic resin (A) containing a structural unit derived from the alkyl acrylates (a1) and (a2) is 1 This is advantageous in enhancing the durability of the attached optical film 1 and the optical laminate including the same. When the number of peaks in the Mw range is 2 or more, sufficient durability cannot be obtained.

  In obtaining the number of peaks of the GPC discharge curve in the range of Mw 1000 to 2.5 million, the discharge curve is acquired according to the GPC measurement conditions described in the section of the examples. “Having a single peak” in the above range of the obtained emission curve means having only one maximum value in the range of Mw 1000 to 2.5 million. In the present specification, a peak having an S / N ratio of 30 or more in the GPC emission curve is defined.

  The (meth) acrylic resin (A) preferably has a standard polystyrene equivalent Mw by GPC in the range of 500,000 to 2,500,000, and more preferably in the range of 600,000 to 2,000,000. When Mw is 500,000 or more, it is advantageous for improving the metal corrosion resistance and durability of the optical film 1 with an adhesive layer and an optical laminate including the same, and the reworkability of the optical film 1 with an adhesive layer is also It tends to improve. Moreover, the followability of the adhesive layer 20 with respect to the dimensional change of the optical film 10 becomes favorable as Mw is 2.5 million or less. The molecular weight distribution represented by the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn is usually 2 to 10. Mw and Mn of the (meth) acrylic resin (A) are determined according to the GPC measurement conditions described in the Examples section.

  When the (meth) acrylic resin (A) is dissolved in ethyl acetate to give a solution having a concentration of 20% by weight, the viscosity at 25 ° C. is preferably 20 Pa · s or less, preferably 0.1 to 7 Pa · s. It is more preferable that The viscosity in such a range is advantageous for improving the durability of the optical film 1 with an adhesive layer and an optical laminate including the same, and for reworkability of the optical film 1 with an adhesive layer. The viscosity can be measured with a Brookfield viscometer.

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

  The pressure-sensitive adhesive composition may contain two or more (meth) acrylic resins belonging to the (meth) acrylic resin (A). The pressure-sensitive adhesive composition may contain another (meth) acrylic resin different from the (meth) acrylic resin (A). However, from the viewpoint of metal corrosion resistance and durability of the optical film 1 with an adhesive layer and an optical laminate including the same, the content of the (meth) acrylic resin (A) is all (meth) acrylic. The total amount of the resin is preferably 70% by weight or more, more preferably 80% by weight or more, and still more preferably 90% by weight or more. The pressure-sensitive adhesive composition is a (meth) acrylic resin (base polymer). It is particularly preferred to contain only A).

  The (meth) acrylic resin (A) and other (meth) acrylic resins that can be used together as necessary are, for example, by known methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization. Can be manufactured. In the production of the (meth) acrylic resin, a polymerization initiator is usually used. A polymerization initiator is used about 0.001-5 weight part with respect to a total of 100 weight part of all the monomers used for manufacture of (meth) acrylic-type resin. Moreover, you may manufacture a (meth) acrylic-type resin by the method of advancing superposition | polymerization by active energy rays, such as an ultraviolet-ray, for example.

  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. Examples of the thermal polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2′-azobis (2-methylpropio) Azo), 2,2′-azobis (2-hydroxymethylpropionitrile); lauryl peroxide, t-butyl hydroperoxide, benzoyl peroxide, t-butyl peroxybenzoate, cumene hydroper Oxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, t-butyl peroxy Organic peroxides such as neodecanoate, t-butylperoxypivalate, (3,5,5-trimethylhexanoyl) peroxide; inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide Can be mentioned. A redox initiator or the like using a peroxide and a reducing agent in combination can also be used as the polymerization initiator.

  As a method for producing the (meth) acrylic resin, the solution polymerization method is preferable among the methods shown above. As an example of the solution polymerization method, a monomer and an organic solvent to be used are mixed, a thermal polymerization initiator is added under a nitrogen atmosphere, and the temperature is about 40 to 90 ° C., preferably about 50 to 80 ° C. for 3 to 15 hours. It is about stirring. In order to control the reaction, a monomer or a thermal polymerization initiator may be added continuously or intermittently during the polymerization, or may be added in a state dissolved in an organic solvent. Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propyl alcohol and isopropyl alcohol; acetone, methyl ethyl ketone, and methyl isobutyl ketone. Ketones can be used.

[2-2] Isocyanate-based crosslinking agent (B)
The pressure-sensitive adhesive composition contains an isocyanate-based crosslinking agent (B). By using an isocyanate type crosslinking agent (B) as a crosslinking agent, the metal corrosion resistance and durability of the optical film 1 with an adhesive layer and the optical laminated body containing the same can be improved. An isocyanate type crosslinking agent (B) may be used individually by 1 type, and may use 2 or more types together.

  The isocyanate-based crosslinking agent (B) is a compound having at least two isocyanato groups (—NCO) in the molecule, and specifically, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated. Examples include xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate. The isocyanate-based crosslinking agent (B) is a polyhydric alcohol compound adduct of these isocyanate compounds (for example, adducts of glycerol or trimethylolpropane), isocyanurate, burette type compound, polyether polyol, polyester polyol, acrylic Derivatives such as urethane prepolymer type isocyanate compounds obtained by addition reaction with polyols, polybutadiene polyols, polyisoprene polyols and the like may also be used. Among the above, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate or polyhydric alcohol compound adducts of these isocyanate compounds are preferred, and the optical film 1 with an adhesive layer and the durability of an optical laminate including the same are preferred. From the viewpoint, xylylene diisocyanate or a polyhydric alcohol compound adduct thereof is more preferable.

  Content of isocyanate type crosslinking agent (B) is 0.08-2.5 weight part with respect to 100 weight part of (meth) acrylic-type resin (A), Preferably it is 0.1-2 weight part (for example, 1 part by weight or less). When the content of the isocyanate-based crosslinking agent (B) is in this range, it is advantageous for achieving both the metal corrosion resistance and durability of the optical film 1 with an adhesive layer and an optical laminate including the same.

  The pressure-sensitive adhesive composition may use other crosslinking agents such as epoxy compounds, aziridines, metal chelate compounds, peroxides and the like together with the isocyanate-based crosslinking agent (B). From the viewpoint of metal corrosion resistance and durability of the optical laminate including the same, the pressure-sensitive adhesive composition contains only the isocyanate-based crosslinking agent (B) as a crosslinking agent, and particularly substantially contains a peroxide. Preferably not. Here, “substantially free” means that the content with respect to 100 parts by weight of the (meth) acrylic resin (A) is 0.01 parts by weight or less.

[2-3] Silane compound (C)
The pressure-sensitive adhesive composition contains a silane compound (C). Thereby, the adhesiveness of the adhesive layer 20 and a metal layer, a glass substrate, etc. can be improved. Two or more silane compounds (C) may be used.

  Examples of the silane compound (C) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3 -Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, Examples include 3-methacryloyloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.

  The silane compound (C) can include a silicone oligomer type. A specific example of the silicone oligomer is expressed in the form of a combination of monomers as follows.

3-mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer,
3-mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer,
3-mercaptopropyltriethoxysilane-tetramethoxysilane oligomer,
Mercaptopropyl group-containing oligomers such as 3-mercaptopropyltriethoxysilane-tetraethoxysilane oligomers;
Mercaptomethyltrimethoxysilane-tetramethoxysilane oligomer,
Mercaptomethyltrimethoxysilane-tetraethoxysilane oligomer,
Mercaptomethyltriethoxysilane-tetramethoxysilane oligomer,
Mercaptomethyl 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,
Copolymers containing 3-glycidoxypropyl groups, such as 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer;
3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane oligomer,
3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane oligomer,
3-methacryloyloxypropyltriethoxysilane-tetramethoxysilane oligomer,
3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane oligomer,
3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer,
3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer,
3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer,
Methacryloyloxypropyl group-containing oligomers such as 3-methacryloyloxypropylmethyldiethoxysilane-tetraethoxysilane oligomers;
3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane oligomer,
3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane oligomer,
3-acryloyloxypropyltriethoxysilane-tetramethoxysilane oligomer,
3-acryloyloxypropyltriethoxysilane-tetraethoxysilane oligomer,
3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer,
3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer,
3-acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer,
Acryloyloxypropyl group-containing oligomers such as 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane oligomers;
Vinyltrimethoxysilane-tetramethoxysilane oligomer,
Vinyltrimethoxysilane-tetraethoxysilane oligomer,
Vinyltriethoxysilane-tetramethoxysilane oligomer,
Vinyltriethoxysilane-tetraethoxysilane oligomer,
Vinylmethyldimethoxysilane-tetramethoxysilane oligomer,
Vinylmethyldimethoxysilane-tetraethoxysilane oligomer,
Vinylmethyldiethoxysilane-tetramethoxysilane oligomer,
Vinyl group-containing oligomers such as vinylmethyldiethoxysilane-tetraethoxysilane oligomer;
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,
Amino group-containing copolymers such as 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer.

  Content of the silane compound (C) in an adhesive composition is 0.01-10 weight part normally with respect to 100 weight part of (meth) acrylic-type resin (A), Preferably it is 0.03-5 weight Part, more preferably 0.05 to 2 parts by weight, still more preferably 0.1 to 1 part by weight. When the content of the silane compound (C) is 0.01 parts by weight or more, an effect of improving the adhesion between the pressure-sensitive adhesive layer 20 and the metal layer 30 or the glass substrate is easily obtained. Further, when the content is 10 parts by weight or less, bleeding out of the silane compound (C) from the pressure-sensitive adhesive layer 20 can be suppressed.

[2-4] Ionic compound (D)
The pressure-sensitive adhesive composition contains an ionic compound (D). The ionic compound (D) has the following formula (I):

It is an ionic compound represented by. By using the ionic compound (D), not only the antistatic performance can be imparted to the pressure-sensitive adhesive layer 20, but also excellent metal corrosion resistance and optical durability can be imparted. The pressure-sensitive adhesive composition can contain one or more ionic compounds (D).

In the above formula (I), R ^{1 to} R ⁸ each independently have a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a substituent. Represents an alkynyl group that may be substituted, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent, and R ^{5 to} R ⁸ represent rings between adjacent substituents. It may be formed. When the adjacent substituents form a ring, 1) when two adjacent substituents of R ^{5 to} R ⁸ and the N atom together form a ring structure, 2) R ⁵ The case where three substituents of ˜R ⁸ and an N atom are combined to form an unsaturated ring structure (including an aromatic ring structure) including an unsaturated bond in which the N atom is involved is included. R ^{1 to} R ⁴ may form a ring with adjacent substituents. The case where the adjacent substituents form a ring means that two adjacent substituents among R ^{1 to} R ⁴ and the B atom are combined to form a ring structure.

  The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and specific examples thereof include, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group. Group, dodecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1 -Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group Including a 3-Nitorofenashiru group.

  The alkenyl group which may have a substituent 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 is preferably an alkynyl group having 2 to 10 carbon atoms, and specific examples thereof include, for example, an ethynyl group, a propynyl group, and a propargyl group.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and specific examples thereof include, for example, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, and 9-anthryl. Group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl Group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl Group, aseantrirenyl group, phenalenyl group, fluorenyl group, anthryl group, biantraceni Group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetra A phenylenyl group, a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl group are included.

  As the heterocyclic group which may have a substituent, an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom is preferable, and specific examples thereof include, for example, thienyl group, benzo [ b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group Imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquinolyl group, quinolyl Group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, syn Linyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, Isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinocridinyl group A thioxanthryl group.

  The alkyl group which may have the above 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 substituent Specific examples of the substituent capable of substituting the hydrogen atom of the heterocyclic group which may be used include, for example, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group, ethoxy group, t-butoxy group and the like Alkoxy groups such as phenoxy group, p-tolyloxy group, etc .; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, vinyloxycarbonyl group, aryloxycarbonyl group; acetoxy group, propionyloxy group , Acyloxy groups such as benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, Acyl groups such as tacryloyl group and methoxalyl group; alkylsulfanyl groups such as methylsulfanyl group and t-butylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; alkyl such as methylamino group and cyclohexylamino group Amino group; dialkylamino group such as dimethylamino group, diethylamino group, morpholino group, piperidino group; arylamino group such as phenylamino group, p-tolylamino group; methyl group, ethyl group, t-butyl group, dodecyl group, etc. Alkyl group: phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group and other aryl groups; hydroxyl group, carboxyl group, sulfonamide group, formyl group, mercapto group, sulfo group, mesyl group Group, p Toluenesulfonyl group, amino group, nitro group, nitroso group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfonium Contains a mil group and a triphenylphenacylphosphoniumyl group.

  Of the above substituents, preferred substituents are electron-withdrawing substituents. By substituting with an electron-attracting substituent, the ionic compound is generally easily dissociated and the antistatic ability can be enhanced. Specific examples of the electron withdrawing substituent include a halogen atom, a cyano group, a carboxyl group, a nitro group, a nitroso group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, and a trialkyl. Ammonium group, amide group, perfluoroalkyl group, perfluoroalkylthio group, perfluoroalkylcarbonyl group, sulfonamide group, 4-cyanophenyl group are included.

R ^{1 to} R ⁴ are each independently preferably an alkyl group which may have a substituent or an aryl group which may have a substituent. R ^{5 to} R ⁸ are each independently preferably an alkyl group which may have a substituent or an aryl group which may have a substituent. Alternatively, preferably three substituents of R ^{5 to} R ⁸ together with the N atom form an unsaturated ring structure (including an aromatic ring structure) containing an unsaturated bond.

Among these, R ^{1 to} R ⁴ are preferably aryl groups which may have a substituent, and the anion of the ionic compound (D) is represented by the following formula (II):

The borate anion represented by the formula is more preferable. In said formula (II), R < ⁹ > -R < ¹³ > has a hydrogen atom, the alkyl group which may have a substituent, the alkenyl group which may have a substituent, and a substituent each independently. An alkynyl group which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or a halogen atom, wherein adjacent substituents form a ring; Also good.

The alkyl group which may have the above 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 substituent Specific examples of the substituent capable of substituting the hydrogen atom of the heterocyclic group which may be used may be the same as the specific examples of R ^{1 to} R ^{8 in} the above formula (I). From the viewpoint of antistatic performance, metal corrosion resistance and optical durability of the ionic compound (D), R ^{9 to} R ¹³ are preferably all halogen atoms, and more preferably all fluorine atoms. In this case, the anion represented by the above formula (II) is a tetrakis (pentafluorophenyl) borate anion.

  From the viewpoint of antistatic performance, the cation of the ionic compound (D) is an unsaturated bond such as pyridinium cation, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, pyrazolium cation, and pyrazolinium cation. It is preferable that it is a cation which has a nitrogen atom containing heterocyclic structure containing a pyridinium cation, especially the following formula (III):

It is more preferable that it is the pyridinium cation represented by these. In the above formula (III), R ^{14 to} R ¹⁹ each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or 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; Adjacent substituents may form a ring.

The pyridinium cation represented by the formula (III) is preferably an N-substituted pyridinium cation. In this case, R ¹⁴ is preferably an alkyl group which may have a substituent, and more preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Preferably carbon number is 1-16. R ^{15 to} R ¹⁹ are each independently preferably a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a hydroxyl group, or a halogen atom, more preferably a hydrogen atom or carbon. It is a linear alkyl group of number 1-20.

The ionic compound (D) is a borate anion in which the anion is represented by the above formula (II) from the viewpoint of antistatic performance and the metal corrosion resistance of the optical film 1 with an adhesive layer and an optical laminate including the same. The cation is preferably a cation having a nitrogen atom-containing heterocyclic structure containing an unsaturated bond, the anion is a tetrakis (pentafluorophenyl) borate anion, and the cation is a nitrogen atom-containing heterocyclic ring containing an unsaturated bond More preferably, the cation has a structure, the anion is a tetrakis (pentafluorophenyl) borate anion, the cation is more preferably a pyridinium cation represented by the above formula (III), and the anion is tetrakis (pentafluoro). phenyl) and borate anion, cation R ¹⁴ is 1 to carbon atoms And particularly preferably a straight-chain or branched or cyclic alkyl group of 0 pyridinium cation represented by the formula (III).

  The content of the ionic compound (D) in the pressure-sensitive adhesive composition is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 100 parts by weight of the (meth) acrylic resin (A). -8 parts by weight, more preferably 0.3-5 parts by weight, and particularly preferably 0.5-3 parts by weight. When the content of the ionic compound (D) is 0.1 parts by weight or more, it is advantageous for improving the antistatic performance, and when it is 10 parts by weight or less, the optical film 1 with an adhesive layer and It is advantageous for the metal corrosion resistance and durability of the optical laminate.

  The pressure-sensitive adhesive composition can be used in combination with the ionic compound (D) represented by the above formula (I) and other antistatic agents, but the optical film 1 with a pressure-sensitive adhesive layer and an optical laminate comprising the same From the standpoint of metal corrosion resistance, the pressure-sensitive adhesive composition preferably contains only the ionic compound (D) represented by the above formula (I) as an antistatic agent.

[2-5] Other components The pressure-sensitive adhesive composition comprises a solvent, a crosslinking catalyst, an ultraviolet absorber, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, light scattering fine particles, and the like. One or more agents can be contained. In addition, it is also useful to blend an ultraviolet curable compound into the pressure-sensitive adhesive composition, form an pressure-sensitive adhesive layer, and then cure by irradiating with ultraviolet rays to form a harder pressure-sensitive adhesive layer. Examples of the crosslinking catalyst include amine compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resin, and melamine resin.

  The pressure-sensitive adhesive composition can contain a rust inhibitor capable of enhancing the metal corrosion resistance of the optical film 1 with a pressure-sensitive adhesive layer and an optical laminate including the same. Examples of rust inhibitors include triazole compounds such as benzotriazole compounds and other triazole compounds; thiazole compounds such as benzothiazole compounds and other thiazole compounds; benzylimidazole compounds and other imidazole compounds. Imidazole compounds; Imidazoline compounds; Quinoline compounds; Pyridine compounds; Pyrimidine compounds; Indole compounds; Amine compounds; Urea compounds; Sodium benzoates; Benzyl mercapto compounds; You can list it.

  However, according to the present invention, since sufficient metal corrosion resistance can be obtained without containing a rust inhibitor, the content of the rust inhibitor is preferably as small as possible. In particular, the pressure-sensitive adhesive composition preferably does not substantially contain a triazole-based compound as a rust inhibitor, and more preferably does not substantially contain a rust inhibitor selected from the above compound group. Here, “substantially free” means that the content with respect to 100 parts by weight of the (meth) acrylic resin (A) is 0.01 parts by weight or less.

[3] Configuration and production method of optical film with pressure-sensitive adhesive layer The optical film 1 with pressure-sensitive adhesive layer includes an optical film 10 and a pressure-sensitive adhesive layer 20 laminated on at least one surface thereof (FIG. 1). The adhesive layer 20 may be laminated on both surfaces of the optical film 10. Usually, the pressure-sensitive 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, a primer layer is formed on the bonding surface of the optical film 10 and / or the bonding surface of the pressure-sensitive adhesive layer 20, or surface activation treatment, for example, plasma treatment, It is preferable to perform a corona treatment or the like, and it is more preferable to perform a corona treatment.

  When the optical film 10 is a single-sided protective polarizing plate as shown in FIG. 2, the pressure-sensitive adhesive layer 20 is preferably on the polarizer surface, that is, the surface of the polarizer 2 opposite to the first resin film 3. Are directly laminated. When the optical film 10 is a double-sided protective polarizing plate as shown in FIG. 3, the pressure-sensitive adhesive layer 20 may be laminated on the outer surface of either the first or second resin film 3, 4. May be laminated.

  An antistatic layer may be separately provided between the optical film 10 and the pressure-sensitive adhesive layer 20, but the pressure-sensitive adhesive layer 20 of the present invention can provide excellent antistatic properties by the pressure-sensitive adhesive layer alone, so that It is preferable not to have an antistatic layer between the optical film 10 and the pressure-sensitive adhesive layer 20 from the viewpoint of thinning the laminate and simplifying the laminate production process.

  The optical film 1 with an adhesive layer may include a separate film (release film) laminated on the outer surface of the adhesive layer 20. This separate film is usually peeled and removed when the pressure-sensitive adhesive layer 20 is used (for example, when laminated on the metal layer 30). The separate film is, for example, one having a release treatment such as silicone treatment applied to the surface on which the pressure-sensitive adhesive layer 20 of a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyarate is formed. Can do.

  The optical film 1 with the pressure-sensitive adhesive layer is obtained by dissolving or dispersing each component constituting the pressure-sensitive adhesive composition in a solvent to obtain a solvent-containing pressure-sensitive adhesive composition, and then applying and drying this onto the surface of the optical film 10. And can be obtained by forming the pressure-sensitive adhesive layer 20. Moreover, the optical film 1 with an adhesive layer forms the adhesive layer 20 on the mold release process surface of a separate film like above, and laminates | transfers this adhesive layer 20 on the surface of the optical film 10 (transfer). Can also be obtained.

<Optical laminate>
4 and 5 are schematic cross-sectional views showing examples of the layer configuration of the optical laminate according to the present invention. In one embodiment, the optical laminate according to the present invention includes an optical film 1 with an adhesive layer and a metal layer 30 laminated on the adhesive layer 20 side, as shown in FIGS. 4 and 5. . The optical laminate 5 shown in FIG. 4 is an example using the polarizing plate 10a shown in FIG. 2 as the optical film 10, and the optical laminate 6 shown in FIG. 5 has the polarizing plate 10b shown in FIG. It is an example used as the optical film 10. In the optical laminates 5 and 6 shown in FIGS. 4 and 5, the optical film 1 with an adhesive layer is laminated on the metal layer 30 so that the adhesive layer 20 is in direct contact with the metal layer 30. According to the present invention, corrosion of the metal layer 30 can be effectively suppressed even in the optical layered body configured such that the pressure-sensitive adhesive layer 20 directly contacts the metal layer 30 as described above.

  FIG. 6 is a schematic sectional view showing another example of the layer structure of the optical layered body according to the present invention. In another embodiment, the optical layered body according to the present invention is such that the pressure-sensitive adhesive layer 20 of the pressure-sensitive adhesive layered optical film 1 is formed on the metal layer 30 via the resin layer 50 as in the optical layered body 7 shown in FIG. Are stacked. The pressure-sensitive adhesive layer 20 is in direct contact with the resin layer 50. Also in the optical layered body 7, corrosion of the metal layer 30 can be effectively suppressed. The resin layer 50 disposed between the pressure-sensitive adhesive layer 20 and the metal layer 30 may be, for example, a cured product layer of a curable resin. As the curable resin that can form the resin layer 50, a known resin can be used, and examples thereof include those described in JP-A-2009-217037.

  FIG. 7 is a schematic cross-sectional view showing another example of the layer configuration of the optical layered body according to the present invention. In still another embodiment, the optical layered body according to the present invention may not have the metal layer 30 like the optical layered body 8 shown in FIG. In this case, the adhesive layer 20 of the optical film 1 with an adhesive layer is laminated | stacked on the board | substrate 40, for example. The substrate 40 is, for example, a glass substrate as will be described later.

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

  The metal layer 30 may be, for example, a metal oxide layer such as ITO. However, the optical film 1 with an adhesive layer according to the present invention has particularly good corrosion resistance against a single metal or an alloy. It is preferable that the layer 30 includes a single metal composed of the above metal element and / or an alloy containing two or more of the above metal elements. However, the optical layered body may have a transparent electrode layer made of a metal oxide such as ITO together with such a metal layer 30.

  The form (for example, thickness) and preparation method of the metal layer 30 are not particularly limited, and may be a metal foil, and may be formed by a vacuum deposition method, a sputtering method, an ion plating method, an ink jet printing method, or a gravure printing method. However, it is preferably a metal layer formed by sputtering, ink jet printing, or gravure printing, and more preferably a metal layer formed by sputtering. In the metal layer and metal foil formed by sputtering, the former tends to have poorer corrosion resistance. However, according to the optical laminate according to the present invention, the metal layer formed by sputtering is also good. Excellent metal corrosion resistance. 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. Furthermore, when the metal layer 30 is a metal wiring layer, the metal wiring of the metal wiring layer usually has a line width of 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 layered body according to the present invention exhibits good metal corrosion resistance even for such a thin metal layer 30 and a metal layer 30 made of fine metal wiring. In particular, even when the metal wiring has a thickness of 3 μm or less and a line width of 10 μm or less, or even when it has a thickness of 3 μm or less and a line width of 10 μm or less and is formed by a sputtering method, corrosion, You can suppress food.

  The metal layer 30 can be, for example, a metal wiring layer (that is, 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 into a predetermined shape. An example when the metal layer 30 is a metal wiring layer is shown in FIG. In the optical laminate shown in FIG. 8, the resin layer 50 may be omitted. When the pressure-sensitive adhesive layer 20 is laminated on the patterned metal layer 30, the pressure-sensitive adhesive 20 may have a portion that is not in contact with the metal layer 30. The metal layer 30 may be a continuous film containing the above metal or alloy.

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

  As shown in FIGS. 4 and 5, for example, the metal layer 30 which is a metal wiring layer may be formed on the substrate 40, and in this case, the optical laminate according to the present invention includes the substrate 40. be able to. Formation of the metal layer 30 on the substrate 40 can be performed by sputtering, for example. The substrate 40 can 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 for the glass substrate include soda lime glass, low alkali glass, non-alkali glass, and the like. The metal layer 30 may be formed on the entire surface of the substrate 40 or may be formed on a part thereof. When the metal layer 30 is formed on a part of the surface of the substrate 40, such as when the patterned metal layer 30 is formed on the substrate 40, a part of the pressure-sensitive adhesive layer 20 is, for example, a substrate made of glass. 40, but the pressure-sensitive adhesive layer 20 in the optical laminate according to the present invention is also excellent in adhesion to glass. Therefore, the optical laminate and a liquid crystal display device including the same are as follows: The durability in such a case is also excellent.

  The optical laminated bodies 5 and 6 can be obtained by bonding the optical film 1 with an adhesive layer through the adhesive layer 20 on the metal layer 30 (or the resin layer). After the optical film 1 with the pressure-sensitive adhesive layer 1 and the metal layer 30 are pasted to produce an optical laminate, the optical film 1 with the pressure-sensitive adhesive layer 1 is peeled off from the metal layer 30 in the case of any problems. A so-called reworking operation may be required in which the optical film 1 with an adhesive layer is reattached to the metal layer 30. The optical film 1 with a pressure-sensitive adhesive layer according to the present invention is excellent in reworkability because fogging, adhesive residue, and the like hardly occur on the surface of the metal layer 30 after peeling from the metal layer 30. According to the optical film 1 with an adhesive layer according to the present invention, good reworkability can be exhibited even when the surface on which the adhesive layer 20 is bonded is not the metal layer 30 but a glass substrate or an ITO layer.

<Liquid crystal display device>
The liquid crystal display device according to the present invention includes the optical film 1 with an adhesive layer according to the present invention, and more typically includes the optical laminate. The liquid crystal display device according to the present invention can suppress the corrosion of the metal layer 30 and exhibits good durability.

  The liquid crystal display device according to the present invention is preferably a touch input type liquid crystal display device having a touch panel function. The touch input type liquid crystal display device includes a touch input element including a liquid crystal cell and a backlight. The configuration of the touch panel may be any conventionally known method such as an out-cell type, an on-cell type, an in-cell type, and the operation method of the touch panel is a resistive film type, a capacitive type (surface type capacitive type, projection type) Any known method such as a capacitance method may be used. The optical film 1 with an adhesive layer according to 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. The driving method of the liquid crystal cell may be any conventionally known method such as a TN method, a VA method, an IPS method, a multi-domain method, and an OCB method. In the liquid crystal display device according to the present invention, the substrate 40 included in the optical layered body can be a substrate (typically a glass substrate) included in the liquid crystal cell.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these examples. Hereinafter, the parts and% representing the amount used and the content are based on weight unless otherwise specified.

<Production Example 1: Production of (meth) acrylic resin (A-1) for pressure-sensitive adhesive layer>
In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirrer, a monomer having the composition shown in Table 1 (the numerical values in Table 1 are parts by weight) was mixed with 81.8 parts of ethyl acetate. The resulting solution was charged. After the air in the reaction vessel was replaced with nitrogen gas, the internal temperature was set to 60 ° C. Thereafter, a solution in which 0.12 part of azobisisobutyronitrile was dissolved in 10 parts of ethyl acetate was added. After maintaining at the same temperature for 1 hour, while maintaining the internal temperature at 54 to 56 ° C., ethyl acetate was continuously introduced into the reaction vessel at an addition rate of 17.3 parts / hr so that the polymer concentration was approximately 35%. Added. After maintaining the internal temperature at 54 to 56 ° C. until 12 hours have elapsed from the start of addition of ethyl acetate, ethyl acetate was added to adjust the polymer concentration to 20%, and (meth) acrylic resin ( An ethyl acetate solution of A-1) was obtained. The weight average molecular weight Mw of the (meth) acrylic resin (A-1) was 1.39 million, and the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn was 5.32. In the gel permeation chromatography (GPC) discharge curve, the component of Mw 1.39 million showed a single peak, and no other peak was observed in the range of Mw 1000 to 2.5 million.

<Production Example 2: Production of (meth) acrylic resin (A-2) for pressure-sensitive adhesive layer>
A reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer and a stirrer was charged with a solution obtained by mixing a monomer having the composition shown in Table 1 with 81.8 parts of ethyl acetate. After the air in the reaction vessel was replaced with nitrogen gas, the internal temperature was set to 60 ° C. Thereafter, a solution in which 0.03 part of azobisisobutyronitrile was dissolved in 10 parts of ethyl acetate was added. A copolymer and a monomer having a weight average molecular weight Mw of 1,000,000 are allowed to react for 4 to 5 hours until the conversion rate becomes 75% while maintaining the internal temperature at 54 to 56 ° C. And a mixed solution was obtained. Next, 200 parts of toluene and 0.2 part of azobisisobutyronitrile were added, and the reaction was further continued for 6 hours until the conversion rate reached 100%, and a (meth) acrylic resin having a glass transition temperature Tg of −7 ° C. ( A solution of A-2) was obtained. The (meth) acrylic resin (A-2) does not contain a polymer having a molecular weight of less than 150,000, a high molecular weight component (A-2-1) having a Mw of 1,000,000, and a polymer having a molecular weight of 150,000 or more. Not contained, it contained a low molecular weight component (A-2-2) having a Mw of 25,000. The high molecular weight component (A-2-1) and the low molecular weight component (A-2-2) show two independent peaks in the GPC emission curve, and the area ratio of both is (A-2- 1) / (A-2-2) = 75/25. No other peaks other than these were observed in the range of Mw 1000 to 2.5 million.

<Production Example 3: Production of (meth) acrylic resin (A-3) for pressure-sensitive adhesive layer>
An ethyl acetate solution of (meth) acrylic resin (A-3) was obtained in the same manner as in Production Example 1 except that the monomer composition was as shown in Table 1 (resin concentration: 20%). ). The (meth) acrylic resin (A-3) had a weight average molecular weight Mw of 141,000 and Mw / Mn of 4.71. In the GPC emission curve, the component having Mw of 141,000 showed a single peak, and no other peak was observed in the range of Mw of 1,000 to 2,500,000.

  In the above production example, the weight average molecular weight Mw and the number average molecular weight Mn are 4 columns of “TSKgel XL” manufactured by Tosoh Corporation and “Shodex GPC KF-” manufactured by Showa Denko KK as a column in the GPC apparatus. 802 "is connected in series, a total of five are connected in series, tetrahydrofuran is used as the eluent, sample concentration is 5mg / mL, sample introduction amount is 100μL, temperature is 40 ° C, flow rate is 1mL / min. It was measured by. The conditions for obtaining the GPC emission curve were also the same.

  The glass transition temperature Tg is measured using a differential scanning calorimeter (DSC) “EXSTAR DSC6000” manufactured by SII Nano Technology Co., Ltd., under a nitrogen atmosphere, a measurement temperature range of −80 to 50 ° C., and a heating rate of 10 ° C./min. Measured under conditions.

  The composition of the monomer in each production example (the numerical values in Table 1 are parts by weight) and the number of peaks in the range of Mw 1000 to 2.5 million on the GPC emission curve (indicated as “GPC peak number” in Table 1) Are summarized in Table 1.

Abbreviations in the column of “monomer composition” in Table 1 mean the following monomers.
BA: butyl acrylate (glass transition temperature of homopolymer: −54 ° C.),
MA: methyl acrylate (glass transition temperature of homopolymer: 10 ° C.),
HEA: 2-hydroxyethyl acrylate.

<Examples 1-2 and Comparative Examples 1-7>
(1) Preparation of pressure-sensitive adhesive composition The ethyl acetate solution (resin concentration: 20%) of the (meth) acrylic resin obtained in the above production example is shown in Table 2 with respect to 100 parts of the solid content of the solution. The isocyanate cross-linking agent (B), silane compound (C), and ionic compound (D) are mixed in the amounts (parts by weight) shown in Table 2, and ethyl acetate is added so that the solid content concentration becomes 14%. Thus, a pressure-sensitive adhesive composition was obtained. The compounding amount of each compounding component shown in Table 2 is the number of parts by weight as an active ingredient contained therein when the product used contains a solvent or the like.

The details of each compounding component shown in abbreviations in Table 2 are as follows.
(Isocyanate-based crosslinking agent)
B-1: Ethyl acetate solution (solid content concentration 75%) of trimethylolpropane adduct of xylylene diisocyanate, trade name “Takenate D-110N” obtained from Mitsui Chemicals, Inc.

(Silane compound)
C-1: 3-glycidoxypropyltrimethoxysilane, trade name “KBM403” obtained from Shin-Etsu Chemical Co., Ltd.

(Ionic compound)
D-1: N-methylpyridinium tetrakis (pentafluorophenyl) borate,
D-2: N-decylpyridinium tetrakis (pentafluorophenyl) borate,
D-3: N-octyl-4-methylpyridinium hexafluorophosphate,
D-4: N-methylpyridinium bis (fluorosulfonyl) imide.

(2) Production of pressure-sensitive adhesive layer Each pressure-sensitive adhesive composition prepared in the above (1) was separated from a polyethylene terephthalate film subjected to a release treatment [trade name “PLR-382051 obtained from Lintec Corporation]. ]] Was applied using an applicator so that the thickness after drying was 20 μm, and dried at 100 ° C. for 1 minute to prepare an adhesive layer (adhesive sheet).

(3) Production of optical film with pressure-sensitive adhesive layer (P-1) Polyvinyl alcohol film having an average degree of polymerization of about 2400, a saponification degree of 99.9 mol%, and a thickness of 60 μm [trade name “Kuraray Vinylon VF manufactured by Kuraray Co., Ltd.” -PE # 6000 "] is immersed in pure water at 37 ° C, and then an aqueous solution containing iodine and potassium iodide (iodine / potassium iodide / water (weight ratio) = 0.04 / 1.5 / 100). Soaked at 30 ° C. Then, it was immersed at 56.5 ° C. in an aqueous solution containing potassium iodide and boric acid (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100). The film was washed with pure water at 10 ° C. and then dried at 85 ° C. to obtain a polarizer having a thickness of about 23 μm in which iodine was adsorbed and oriented on polyvinyl alcohol. Stretching was mainly performed in the iodine staining and boric acid treatment steps, and the total stretching ratio was 5.3 times.

  A transparent protective film [trade name “KC2UA” manufactured by Konica Minolta Opto Co., Ltd.] made of a 25 μm-thick triacetyl cellulose film is placed on one side of the obtained polarizer with an adhesive made of an aqueous solution of a polyvinyl alcohol resin. And pasted. Next, a zero retardation film [trade name “ZEONOR” manufactured by Nippon Zeon Co., Ltd.] made of a cyclic polyolefin resin having a thickness of 23 μm is formed on the surface opposite to the triacetyl cellulose film in the polarizer. A bonded polarizing plate was produced through an adhesive made of an aqueous resin solution. Next, after the corona discharge treatment for improving adhesion is performed on the surface of the zero retardation film opposite to the surface in contact with the polarizer, it is opposite to the separate film of the pressure-sensitive adhesive layer prepared in (2) above. After laminating the side surface (the pressure-sensitive adhesive layer surface) with a laminator, the film was cured for 7 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain an optical film with a pressure-sensitive adhesive layer (P-1).

(4) Production of optical film with pressure-sensitive adhesive layer (P-2) Polyvinyl alcohol film having an average polymerization degree of about 2400, a saponification degree of 99.9 mol%, and a thickness of 30 μm [trade name “Kuraray Vinylon VF manufactured by Kuraray Co., Ltd.” -PE # 3000 "] is immersed in pure water at 37 ° C, and then an aqueous solution containing iodine and potassium iodide (iodine / potassium iodide / water (weight ratio) = 0.04 / 1.5 / 100). Soaked at 30 ° C. Then, it was immersed at 56.5 ° C. in an aqueous solution containing potassium iodide and boric acid (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100). The film was washed with pure water at 10 ° C. and then dried at 85 ° C. to obtain a polarizer having a thickness of about 12 μm in which iodine was adsorbed and oriented on polyvinyl alcohol. Stretching was mainly performed in the iodine staining and boric acid treatment steps, and the total stretching ratio was 5.3 times.

  A transparent protective film [trade name “KC2UA” manufactured by Konica Minolta Opto Co., Ltd.] made of a 25 μm-thick triacetyl cellulose film is placed on one side of the obtained polarizer with an adhesive made of an aqueous solution of a polyvinyl alcohol resin. To form a polarizing plate. Subsequently, the surface opposite to the separate film of the pressure-sensitive adhesive layer prepared in the above (2) (pressure-sensitive adhesive layer surface) was bonded to the surface opposite to the surface where the protective film of the polarizer was bonded using a laminator. Thereafter, the film was cured for 7 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain an optical film with a pressure-sensitive adhesive layer (P-2).

(5) Evaluation of metal corrosion resistance of optical film with pressure-sensitive adhesive layer The optical film with pressure-sensitive adhesive layer (P-1) prepared in (3) above was cut into a test piece having a size of 20 mm × 50 mm, and a metal layer It stuck to the metal layer side of the attached glass substrate through the adhesive layer. As the glass substrate with a metal layer, a glass substrate (manufactured by Geomat Co., Ltd.) in which a metal aluminum layer having a thickness of about 500 nm was laminated on the alkali-free glass surface by sputtering. The obtained optical layered body was stored in an oven at a temperature of 60 ° C. and a relative humidity of 90% for 500 hours, and then the state of the metal layer where the optical film with the pressure-sensitive adhesive layer was adhered was illuminated from the back side of the glass substrate. Was observed from the surface of the polarizing plate through a magnifying glass (loupe), and pitting corrosion (generation of holes having a diameter of 0.1 mm or more and capable of transmitting light) was evaluated according to the following criteria. The results are shown in Table 3.

4: The number of pitting corrosion generated 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 to 5.
2: The number of pitting corrosion generated on the surface of the metal layer is 6 or more.
1: Numerous pitting corrosion has occurred on the entire surface of the metal layer, and white turbidity has also occurred.

(6) Durability evaluation of optical film with pressure-sensitive adhesive layer The optical film with pressure-sensitive adhesive layer (P-1) prepared in (3) above is 200 mm × 150 mm so that the stretching axis direction of the polarizing plate is the long side. It cut | judged to the magnitude | size, the separate film was peeled, and the exposed adhesive layer surface was bonded to the glass substrate. The test piece (the optical film with the pressure-sensitive adhesive layer to which the glass substrate was attached) obtained by attaching the obtained glass substrate was placed in an autoclave at a temperature of 50 ° C. and a pressure of 5 kg / cm ² (490.3 kPa) for 20 minutes. Pressurized. A non-alkali glass product name “Eagle XG” manufactured by Corning was used for the glass substrate. About the obtained optical laminated body, the following 3 types of durability tests were implemented.

[Durability test]
A heat resistance test that is maintained for 750 hours under dry conditions at a temperature of 85 ° C
-Moisture and heat resistance test held for 750 hours in an environment of temperature 60 ° C and relative humidity 90%,
A heat shock resistance (HS) test in which an operation of holding for 30 minutes under a drying condition at a temperature of 85 ° C. and then holding for 30 minutes under a drying condition at a temperature of −40 ° C. is one cycle, and this is repeated for 400 cycles.

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

4: No change in appearance such as floating, peeling, foaming, etc.
3: Almost no change in appearance such as floating, peeling, foaming, etc.
2: Appearance changes such as floating, peeling and foaming are slightly noticeable.
1: Appearance changes such as floating, peeling, foaming, etc. are noticeable.

(7) Reworkability evaluation of optical film with pressure-sensitive adhesive layer The optical film with pressure-sensitive adhesive layer (P-1) produced in the above (3) was cut into a test piece having a size of 25 mm × 150 mm. The separator was peeled off from the test piece, and the pressure-sensitive adhesive surface was attached to a glass substrate. The test piece (the optical film with the pressure-sensitive adhesive layer to which the glass substrate was attached) obtained by attaching the obtained glass substrate was placed in an autoclave at a temperature of 50 ° C. and a pressure of 5 kg / cm ² (490.3 kPa) for 20 minutes. Pressurized. Next, it is stored in an oven at 50 ° C. for 48 hours. Further, in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%, the optical film is peeled off from the test piece together with the adhesive layer in a 180 ° direction at a speed of 300 mm / min. did. The state of the glass substrate surface after peeling was observed and evaluated according to the following criteria. The results are shown in Table 3.

4: No fogging or the like is observed on the surface of the glass substrate.
3: Almost no fogging is observed on the surface of the glass substrate.
2: Cloudiness etc. are recognized on the surface of the glass substrate,
1: The remainder of an adhesive layer is recognized on the surface of a glass substrate.

(8) Evaluation of color loss of optical film with pressure-sensitive adhesive layer The optical film with pressure-sensitive adhesive layer (P-2) produced in (4) above was cut into a size of 30 mm × 30 mm, and the separation film was peeled off to expose it. The obtained adhesive layer surface was bonded to a glass substrate. A non-alkali glass product name “Eagle XG” manufactured by Corning was used for the glass substrate. About the obtained optical laminated body, MD transmittance and TD transmittance in a wavelength range of 380 to 780 nm were measured using a spectrophotometer with an integrating sphere [product name “V7100” manufactured by JASCO Corporation] Calculates single transmittance and polarization degree at wavelength, and further corrects visibility by JIS Z 8701: 1999 "Color display method-XYZ color system and X ₁₀ Y ₁₀ Z ₁₀ color system" with 2 field of view (C light source) The visibility corrected single transmittance (Ty) and the visibility corrected polarization degree (Py) before the durability test were obtained. In addition, the optical laminated body was set to the spectrophotometer with an integrating sphere so that the triacetyl cellulose film side of the polarizing plate may be the detector side and light may enter from the glass substrate side.

The single transmittance and the degree of polarization are respectively expressed by the following formulas:
Single transmittance (λ) = 0.5 × (Tp (λ) + Tc (λ))
Polarization degree (λ) = 100 × (Tp (λ) −Tc (λ)) / (Tp (λ) + Tc (λ))
Defined by Tp (λ) is the transmittance (%) of the optical laminate measured in the relationship between the linearly polarized light having the incident wavelength λ (nm) and parallel Nicol, and Tc (λ) is the incident wavelength λ (nm). It is the transmittance | permeability (%) of the optical laminated body measured by the relationship between linearly polarized light and crossed Nicols.

  Next, the optical laminate was placed in a humid heat environment with a temperature of 80 ° C. and a relative humidity of 90% for 24 hours, and further placed in an environment with a temperature of 23 ° C. and a relative humidity of 60% for 24 hours. Was used to determine Ty and Py after the durability test. Thereafter, Py and Ty before the test were subtracted from the Py and Ty after the test, respectively, to calculate the amount of change before and after the durability test, and the amount of change in polarization degree (ΔPy) and the amount of change in single transmittance (ΔTy) were obtained. ΔPy is shown in Table 3.

<Production Example 4: Production of (meth) acrylic resin (A-1) for pressure-sensitive adhesive layer>
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, a monomer having the composition shown in Table 4 (the values in Table 4 are parts by weight) was mixed with 81.8 parts of ethyl acetate. The resulting solution was charged. After the air in the reaction vessel was replaced with nitrogen gas, the internal temperature was set to 60 ° C. Thereafter, a solution in which 0.12 part of azobisisobutyronitrile was dissolved in 10 parts of ethyl acetate was added. After maintaining at the same temperature for 1 hour, while maintaining the internal temperature at 54 to 56 ° C., ethyl acetate was continuously introduced into the reaction vessel at an addition rate of 17.3 parts / hr so that the polymer concentration was approximately 35%. Added. After maintaining the internal temperature at 54 to 56 ° C. until 12 hours have elapsed from the start of addition of ethyl acetate, ethyl acetate was added to adjust the polymer concentration to 20%, and (meth) acrylic resin ( An ethyl acetate solution of A-1) was obtained. The weight average molecular weight Mw of the (meth) acrylic resin (A-1) was 1.39 million, and the ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn was 5.32. In the gel permeation chromatography (GPC) discharge curve, the component of Mw 1.39 million showed a single peak, and no other peak was observed in the range of Mw 1000 to 2.5 million.

  In the above production example, the weight average molecular weight Mw and the number average molecular weight Mn are 4 columns of “TSKgel XL” manufactured by Tosoh Corporation and “Shodex GPC KF-” manufactured by Showa Denko KK as a column in the GPC apparatus. 802 "is connected in series, a total of five are connected in series, tetrahydrofuran is used as the eluent, sample concentration is 5mg / mL, sample introduction amount is 100μL, temperature is 40 ° C, flow rate is 1mL / min. It was measured by. The conditions for obtaining the GPC emission curve were also the same.

  The glass transition temperature Tg is measured using a differential scanning calorimeter (DSC) “EXSTAR DSC6000” manufactured by SII Nano Technology Co., Ltd., under a nitrogen atmosphere, a measurement temperature range of −80 to 50 ° C., and a heating rate of 10 ° C./min. Measured under conditions.

  Monomer composition in Production Example 4 (the numerical values in Table 4 are parts by weight), and the number of peaks in the range of Mw 1000 to 2.5 million on the GPC emission curve (indicated as “GPC peak number” in Table 4) Are summarized in Table 4.

Abbreviations in the column of “Monomer composition” in Table 4 mean the following monomers.
BA: butyl acrylate (glass transition temperature of homopolymer: −54 ° C.),
MA: methyl acrylate (glass transition temperature of homopolymer: 10 ° C.),
HEA: 2-hydroxyethyl acrylate.

<Examples 3-4, Comparative Examples 8-9>
(1) Preparation of pressure-sensitive adhesive composition The ethyl acetate solution (resin concentration: 20%) of the (meth) acrylic resin obtained in Production Example 4 is shown in Table 5 with respect to 100 parts of the solid content of the solution. Isocyanate-based crosslinking agent (B), silane compound (C), and ionic compound (D) are mixed in the amounts (parts by weight) shown in Table 5, and ethyl acetate is added so that the solid content concentration becomes 14%. Thus, a pressure-sensitive adhesive composition was obtained. The compounding quantity of each compounding component shown in Table 5 is the number of parts by weight as an active ingredient contained therein when the product used contains a solvent or the like.

Details of each compounding component shown in abbreviations in Table 5 are as follows.
(Isocyanate-based crosslinking agent)
B-1: Ethyl acetate solution (solid content concentration 75%) of trimethylolpropane adduct of xylylene diisocyanate, trade name “Takenate D-110N” obtained from Mitsui Chemicals, Inc.

(Silane compound)
C-1: 3-glycidoxypropyltrimethoxysilane, trade name “KBM403” obtained from Shin-Etsu Chemical Co., Ltd.

(Ionic compound)
D-2: N-decylpyridinium tetrakis (pentafluorophenyl) borate,
D-3: N-octyl-4-methylpyridinium hexafluorophosphate,
D-4: N-methylpyridinium bis (fluorosulfonyl) imide.

(2) Production of pressure-sensitive adhesive layer Each pressure-sensitive adhesive composition prepared in the above (1) was separated from a polyethylene terephthalate film subjected to a release treatment [trade name “PLR-382051 obtained from Lintec Corporation]. ]] Was applied using an applicator so that the thickness after drying was 20 μm, and dried at 100 ° C. for 1 minute to prepare an adhesive layer (adhesive sheet).

(3) Production of optical film with pressure-sensitive adhesive layer (P-1) Polyvinyl alcohol film having an average degree of polymerization of about 2400, a saponification degree of 99.9 mol%, and a thickness of 60 μm [trade name “Kuraray Vinylon VF manufactured by Kuraray Co., Ltd.” -PE # 6000 "] is immersed in pure water at 37 ° C, and then an aqueous solution containing iodine and potassium iodide (iodine / potassium iodide / water (weight ratio) = 0.04 / 1.5 / 100). Soaked at 30 ° C. Then, it was immersed at 56.5 ° C. in an aqueous solution containing potassium iodide and boric acid (potassium iodide / boric acid / water (weight ratio) = 12 / 3.6 / 100). The film was washed with pure water at 10 ° C. and then dried at 85 ° C. to obtain a polarizer having a thickness of about 23 μm in which iodine was adsorbed and oriented on polyvinyl alcohol. Stretching was mainly performed in the iodine staining and boric acid treatment steps, and the total stretching ratio was 5.3 times.

  A transparent protective film [trade name “KC2UA” manufactured by Konica Minolta Opto Co., Ltd.] made of a 25 μm-thick triacetyl cellulose film is placed on one side of the obtained polarizer with an adhesive made of an aqueous solution of a polyvinyl alcohol resin. And pasted. Next, a zero retardation film [trade name “ZEONOR” manufactured by Nippon Zeon Co., Ltd.] made of a cyclic polyolefin resin having a thickness of 23 μm is formed on the surface opposite to the triacetyl cellulose film in the polarizer. A bonded polarizing plate was produced through an adhesive made of an aqueous resin solution. Next, after the corona discharge treatment for improving adhesion is performed on the surface of the zero retardation film opposite to the surface in contact with the polarizer, it is opposite to the separate film of the pressure-sensitive adhesive layer prepared in (2) above. After laminating the side surface (the pressure-sensitive adhesive layer surface) with a laminator, the film was cured for 7 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain an optical film with a pressure-sensitive adhesive layer (P-1).

(4) Metal corrosion resistance evaluation of optical film with pressure-sensitive adhesive layer (4-1) In the case of Example 3 and Comparative Example 8 The optical film with pressure-sensitive adhesive layer (P-1) prepared in (3) above was 20 mm. It cut | judged to the test piece of a magnitude | size of * 50 mm, and affixed on the metal layer side of the glass substrate with a metal layer through the adhesive layer. As the glass substrate with a metal layer, a glass substrate (manufactured by Geomat Co., Ltd.) in which a metal copper layer having a thickness of about 500 nm was laminated on the alkali-free glass surface by sputtering. The obtained optical layered body was stored in an oven at a temperature of 60 ° C. and a relative humidity of 90% for 120 hours, and then the state of the metal layer where the optical film with the adhesive layer was attached was illuminated from the back side of the glass substrate. Was applied through the magnifying glass from the surface of the polarizing plate, and pitting corrosion (generation of holes having a diameter of 0.1 mm or more and capable of transmitting light) was evaluated according to the following criteria. The results are shown in Table 6.

(4-2) In the case of Example 4 and Comparative Example 9 The optical film with adhesive layer (P-1) produced in (3) above was cut into a test piece having a size of 20 mm × 50 mm, and a metal layer was attached. It stuck to the metal layer side of the glass substrate through the adhesive layer. For the glass substrate with a metal layer, a glass substrate (manufactured by Geomat Co., Ltd.) in which a silver alloy (alloy containing silver and palladium and copper, APC) layer having a thickness of about 500 nm is laminated on an alkali-free glass surface by sputtering. used. The obtained optical layered body was stored in an oven at a temperature of 60 ° C. and a relative humidity of 90% for 500 hours, and then the state of the metal layer where the optical film with the pressure-sensitive adhesive layer was adhered was illuminated from the back side of the glass substrate. Was applied through the magnifying glass from the surface of the polarizing plate, and pitting corrosion (generation of holes having a diameter of 0.1 mm or more and capable of transmitting light) was evaluated according to the following criteria. The results are shown in Table 6.

4: The number of pitting corrosion generated 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 to 5.
2: The number of holes generated on the surface of the metal layer is 6 or more,
1: Numerous pitting corrosion has occurred on the entire surface of the metal layer, and white turbidity has also occurred.

  DESCRIPTION OF SYMBOLS 1 Optical film with an adhesive layer, 2 Polarizer, 3 1st resin film, 4 2nd resin film, 5, 6, 7, 8 Optical laminated body, 10 Optical film, 10a, 10b Polarizing plate, 20 Adhesive layer, 30 metal layers, 40 substrates, 50 resin layers.

Claims (15)

An optical film, and an adhesive layer laminated on at least one surface thereof,
The pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive composition containing a (meth) acrylic resin (A), an isocyanate-based crosslinking agent (B), a silane compound (C), and an ionic compound (D),
The (meth) acrylic resin (A) includes a structural unit derived from an alkyl acrylate (a1) having a glass transition temperature of a homopolymer of less than 0 ° C., and an alkyl acrylate having a glass transition temperature of the homopolymer of 0 ° C. or more ( a (meth) acrylic resin containing a structural unit derived from a2) and having a single peak in the weight average molecular weight range of 1000 to 2.5 million on the discharge curve in gel permeation chromatography;
Content of the said isocyanate type crosslinking agent (B) is 0.08-2.5 weight part with respect to 100 weight part of said (meth) acrylic-type resins (A),
The ionic compound (D) has the following formula (I):

(In the formula, R ^{1 to} R ⁸ may each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. A good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, wherein R ^{1 to} R ⁴ form a ring with adjacent substituents; R ^{5 to} R ⁸ may form a ring with adjacent substituents.
An optical film with an adhesive layer, which is an ionic compound represented by: The anion of the ionic compound (D) is represented by the following formula (II):

(In the formula, R ^{9 to} R ¹³ may each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. It represents a good alkynyl group, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, or a halogen atom, and adjacent substituents may form a ring. )
The optical film with an adhesive layer according to claim 1, which is a borate anion represented by:   The optical film with an adhesive layer according to claim 1, wherein the anion of the ionic compound (D) is a tetrakis (pentafluorophenyl) borate anion.   The optical film with an adhesive layer according to claim 1, wherein the anion of the ionic compound (D) is a tetrakis (pentafluorophenyl) borate anion, and the cation has a nitrogen atom-containing heterocyclic structure containing an unsaturated bond. . The anion of the ionic compound (D) is a tetrakis (pentafluorophenyl) borate anion, and the cation is represented by the following formula (III):

(In the formula, R ^{14 to} R ¹⁹ may each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Represents a good alkynyl group, optionally substituted aryl group, optionally substituted heterocyclic group, hydroxyl group, ether group, carboxyl group, carbonyl group, or halogen atom, adjacent substitution A group may form a ring.)
The optical film with an adhesive layer according to claim 1, which is a pyridinium cation represented by the formula:   The said (meth) acrylic-type resin (A) is an optical film with an adhesive layer of any one of Claims 1-5 containing the structural unit derived from the monomer which has a hydroxyl group.   The optical film with an adhesive layer according to any one of claims 1 to 6, wherein the (meth) acrylic resin (A) has a weight average molecular weight of 500,000 to 2,500,000.   The said adhesive composition is an optical film with an adhesive layer of any one of Claims 1-7 which does not contain a peroxide substantially.   The said adhesive composition is an optical film with an adhesive layer of any one of Claims 1-8 which does not contain a triazole type compound substantially.   The said (meth) acrylic-type resin (A) is an optical film with an adhesive layer of any one of Claims 1-9 which does not contain the structural unit derived from a methacrylate-type monomer substantially. The optical film includes a polarizer made of a polyvinyl alcohol-based resin dyed with iodine,
The said adhesive layer is an optical film with an adhesive layer of any one of Claims 1-10 laminated | stacked directly on the said polarizer.   The liquid crystal display device containing the optical film with an adhesive layer of any one of Claims 1-11. Including (meth) acrylic resin (A), isocyanate crosslinking agent (B), silane compound (C), and ionic compound (D),
The (meth) acrylic resin (A) includes a structural unit derived from an alkyl acrylate (a1) having a glass transition temperature of a homopolymer of less than 0 ° C., and an alkyl acrylate having a glass transition temperature of the homopolymer of 0 ° C. or more ( a (meth) acrylic resin containing a structural unit derived from a2) and having a single peak in the weight average molecular weight range of 1000 to 2.5 million on the discharge curve in gel permeation chromatography;
Content of the said isocyanate type crosslinking agent (B) is 0.08-2.5 weight part with respect to 100 weight part of said (meth) acrylic-type resins (A),
The ionic compound (D) has the following formula (I):

(In the formula, R ^{1 to} R ⁸ may each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. A good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, wherein R ^{1 to} R ⁴ form a ring with adjacent substituents; R ^{5 to} R ⁸ may form a ring with adjacent substituents.
An ionic compound represented by
The adhesive composition used for formation of the adhesive layer laminated | stacked on a metal layer. Including an optical film and an adhesive layer laminated on at least one surface of the optical film, and an optical film with an adhesive layer for bonding onto a metal layer via the adhesive layer,
The pressure-sensitive adhesive layer is
Including (meth) acrylic resin (A), isocyanate crosslinking agent (B), silane compound (C), and ionic compound (D),
The (meth) acrylic resin (A) includes a structural unit derived from an alkyl acrylate (a1) having a glass transition temperature of a homopolymer of less than 0 ° C., and an alkyl acrylate having a glass transition temperature of the homopolymer of 0 ° C. or more ( a (meth) acrylic resin containing a structural unit derived from a2) and having a single peak in the weight average molecular weight range of 1000 to 2.5 million on the discharge curve in gel permeation chromatography;
Content of the said isocyanate type crosslinking agent (B) is 0.08-2.5 weight part with respect to 100 weight part of said (meth) acrylic-type resins (A),
The ionic compound (D) has the following formula (I):

(In the formula, R ^{1 to} R ⁸ may each independently have a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. A good alkynyl group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, wherein R ^{1 to} R ⁴ form a ring with adjacent substituents; R ^{5 to} R ⁸ may form a ring with adjacent substituents.
An ionic compound represented by:
The optical film with an adhesive layer formed from an adhesive composition.   The optical laminated body containing the optical film with an adhesive layer of any one of Claims 1-10, and the metal layer laminated | stacked on the adhesive layer side of this optical film with an adhesive layer.

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