TWI700351B - Optical film with adhesive layer and liquid crystal display device - Google Patents

Abstract

The present invention provides an optical film with adhesive layer and a liquid crystal display device. The optical film with adhesive layer contains an optical film and an adhesive layer laminated thereon. The adhesive layer is formed of an adhesive composition containing 100 parts by weight of a (meth)acrylic resin (A), 0.08 to 2.5 parts by weight of an isocyanate crosslinker (B), a silane compound (C), and a specific ionic compound (D) represented by formula (I), wherein, the (meth)acrylic resin (A) contains a constitution unit derived from an alkyl acrylate (a1) where the glass transition temperature of the homopolymer thereof is less than 0ºC, and a constitution unit derived from an alkyl acrylate (a2) where the glass transition temperature of the homopolymer thereof is 0ºC or more, and has a single peak in the range of weight average molecular weight of 1000 to 2500,000 on a releasing curve of gel permeation chromatography (GPC).

Description

Optical film with adhesive layer and liquid crystal display device

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

An optical film represented by a polarizing plate formed by laminating a transparent resin film on one side or two area layers of a polarizer is widely used as an optical member constituting image display devices such as liquid crystal display devices. Optical film systems such as polarizing plates are often used by bonding to other members (for example, liquid crystal cells in liquid crystal display devices, etc.) via an adhesive layer (for example, refer to Japanese Patent Application Laid-Open No. 2010-229321).

Therefore, as for the optical film, an optical film with an adhesive layer preliminarily provided with an adhesive layer on one side is known. In order to impart antistatic properties, it is also known that the adhesive layer contains an ionic compound.

In recent years, liquid crystal display devices have been extended to smart phones or tablet-type terminals, and portable devices with touch panel functions represented by car navigation systems. In such a touch input type liquid crystal display device, the optical film with the adhesive layer is sometimes used for example by metal wiring. The metal layer of the composition is arranged such that the adhesive layer is interposed by, for example, a resin layer or in direct contact. However, in a structure that combines a metal layer made of a metal material and an adhesive layer containing an ionic compound, the metal layer may corrode in a high temperature and high humidity environment. In the corrosion, the pitting corrosion is particularly problematic when the thickness of the metal layer is thin or the line width of the metal layer is narrow when the metal layer is metal wiring. The metal layer is completely penetrated.

Moreover, in general, durability is required for optical films constituting adhesive layers of liquid crystal display devices and the like. That is, the adhesive layer incorporated in the liquid crystal display device is sometimes placed in a high temperature or high temperature and high humidity environment, or placed in an environment with repeated high and low temperatures, but the optical film system with the adhesive layer requires Even in such an environment, it is possible to suppress the floating or peeling of the interface between the adhesive layer and the optical member to which the adhesive layer is attached, and the foaming of the adhesive layer. In addition, optical properties are also required No difference.

The object of the present invention is to provide an optical film with an adhesive layer that can inhibit corrosion of metal layers such as a metal wiring layer and has excellent durability, and a liquid crystal display device containing the optical film with the adhesive layer.

The present invention provides the following optical film with an adhesive layer, a liquid crystal display device including the optical film with an adhesive layer, and an adhesive composition.

[1] An optical film with an adhesive layer, comprising an optical film and an adhesive layer laminated on at least one surface of the optical film, wherein the adhesive layer is composed of (meth)acrylic resin (A) , Isocyanate-based crosslinking agent (B), silane compound (C), and ionic compound (D) composed of an adhesive composition; the aforementioned (meth)acrylic resin (A) contains homopolymer The glass transition temperature is the structural unit of alkyl acrylate (a1) whose glass transition temperature is less than 0°C, and the structural unit of alkyl acrylate (a2) whose glass transition temperature is derived from homopolymer is above 0°C, and the gel penetrates the color In the layer analysis, the weight average molecular weight on the discharge curve has a single peak in the range of 1,000 to 2.5 million; relative to 100 parts by weight of the (meth)acrylic resin (A), the isocyanate crosslinking agent ( The content of B) is 0.08 to 2.5 parts by weight, and the aforementioned ionic compound (D) is an ionic compound represented by the following formula (I):

In the formula, R ¹ to R ⁸ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an aryl group that may have a substituent, or For heterocyclic groups with substituents, R ¹ to R ⁴ can form a ring with adjacent substituents; R ⁵ to R ⁸ can form a ring with adjacent substituents.

[2] The optical film with an adhesive layer as described in [1], wherein the anion of the ionic compound (D) is a borate anion represented by the following formula (II):

In the formula, R ⁹ to R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, and The heterocyclic group or halogen atom of the substituent can also form a ring with each other with adjacent substituents.

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

[4] The optical film with an adhesive layer as described in any one of [1] to [3], wherein the anion of the ionic compound (D) is tetrakis (pentafluorophenyl) borate anion, And the cation has a heterocyclic structure with a nitrogen atom containing an unsaturated bond.

[5] The optical film with an adhesive layer as described in any one of [1] to [4], wherein the anion of the ionic compound (D) is tetrakis (pentafluorophenyl) borate anion, And the cation is a pyridinium cation represented by the following formula (III):

In the formula, R ¹⁴ to R ¹⁹ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an aryl group that may have a substituent, and The heterocyclic group, hydroxyl group, ether group, carboxyl group, carbonyl group, or halogen atom of the substituent can form a ring with each other with adjacent substituents.

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

[7] The optical film with an adhesive layer as described in any one of [1] to [6], wherein the weight average molecular weight of the (meth)acrylic resin (A) is 500,000 to 2.5 million .

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

[9] The optical film with an adhesive layer according to any one of [1] to [8], wherein the adhesive composition system 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 methacrylic acid The constituent unit of ester monomers.

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

[12] A liquid crystal display device comprising the optical film with the adhesive layer described in any one of [1] to [11].

[13] An adhesive composition comprising a (meth)acrylic resin (A), an isocyanate crosslinking agent (B), a silane compound (C), and an ionic compound (D); wherein the aforementioned (former) Base) acrylic resin (A) is a structural unit containing alkyl acrylate (a1) derived from a homopolymer whose glass transition temperature is less than 0℃, and a homopolymer whose glass transition temperature is above 0℃ The structural unit of alkyl acrylate (a2), and the weight average molecular weight on the discharge curve in the gel permeation chromatography analysis has a single peak in the range of 1000 to 2.5 million; compared to the aforementioned (meth)acrylic resin (A ) 100 parts by weight, the content of the aforementioned isocyanate-based crosslinking agent (B) is 0.08 to 2.5 parts by weight, and the aforementioned ionic compound (D) is an ionic compound represented by the following formula (I):

In the formula, R ¹ to R ⁸ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an aryl group that may have a substituent, or For heterocyclic groups with substituents, R ¹ to R ⁴ can form rings with adjacent substituents; R ⁵ to R ⁸ can form rings with adjacent substituents; the adhesive composition is used to be The formation of an adhesive layer laminated on the metal layer.

According to the present invention, it is possible to provide a Corrosion of the metal layer arranged in such a way that the adhesive layer is adjacent to each other, and an optical film attached to the adhesive layer with excellent durability, and a liquid crystal display device containing the optical film attached to the adhesive layer.

1‧‧‧Optical film with adhesive layer

2‧‧‧Polarizer

3‧‧‧The first resin film

4‧‧‧Second resin film

5, 6, 7, 8,‧‧‧Optical laminate

10‧‧‧Optical film

10a, 10b‧‧‧ Polarizing plate

20‧‧‧Adhesive layer

30‧‧‧Metal layer

40‧‧‧Substrate

50‧‧‧Resin layer

Fig. 1 is a schematic cross-sectional view showing an example of the optical film with an adhesive layer of the present invention.

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

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

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

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

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

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

Fig. 8 is a schematic cross-sectional view showing another example of the layer structure of the optical laminate.

<Optical film with adhesive layer>

Fig. 1 is a schematic cross-sectional view showing an example of the optical film with an adhesive layer of the present invention. As shown in Figure 1, the optical adhesive layer of the present invention The film 1 includes an optical film 10 and an adhesive layer 20 laminated on at least one surface thereof. The adhesive layer 20 is usually directly laminated on the surface of the optical film 10.

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

〔1〕Optical film

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

〔1-1〕 Polarizing plate

2 and 3 are schematic cross-sectional views showing examples of the layer structure of the polarizing plate. The polarizing plate 10a shown in Figure 2 is attached to an area layer of the polarizer 2 The single-sided protective polarizing plate to which the first resin film 3 is attached, and the polarizing plate 10b shown in FIG. 3 is a double-sided protective polarizing plate to which the second resin film 4 is laminated on the other side of the polarizer 2. The first and second resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer or an adhesive layer not shown. The polarizing plates 10a and 10b may include other films or layers other than the first and second resin films 3 and 4.

The polarizer 2 is a film with the following properties: it absorbs linearly polarized light having a vibration surface parallel to its absorption axis, and transmits linearly polarized light having a vibration surface orthogonal to the absorption axis (parallel to the penetration axis), for example, It is possible to use a film in which the aligned dichroic dye has been adsorbed on the polyvinyl alcohol resin film. As the dichroic dye system, iodine or dichroic organic dyes can be used.

The polyvinyl alcohol-based resin can be obtained by saponifying a polyvinyl acetate-based resin. In addition to polyvinyl acetate which is a homopolymer of vinyl acetate, the polyvinyl acetate-based resin may include, for example, a monomer copolymerizable with vinyl acetate and a copolymer of vinyl acetate. Examples of the single system copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth)acrylamide having an ammonium group.

The degree of saponification of the polyvinyl alcohol resin is usually 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin system can be modified. For example, polyvinyl formal or polyvinyl acetal modified by aldehydes can also be used. The average degree of polymerization of the polyvinyl alcohol resin is usually 1,000 to 10,000, preferably 1,500 to 5,000. The average degree of polymerization of the polyvinyl alcohol-based resin can be determined in accordance with JIS K6726.

Usually, a film made of polyvinyl alcohol resin is used As the original film of the polarizer 2. The polyvinyl alcohol-based resin system can be formed into a film by a known method. The thickness of the original roll film is usually 1 to 150 μm, and if the ease of stretching is taken into consideration, it is preferably 10 μm or more.

The polarizer 2 is manufactured by, for example, carrying out the following steps, and finally being dried: a step of uniaxially stretching the original film, a step of dyeing the film with a dichroic pigment to adsorb the dichroic pigment, and treating the film with an aqueous solution of boric acid , And the step of washing the membrane. The thickness of the polarizer 2 is usually 1 to 30 μm. From the viewpoint of thinning the optical film 1 with the adhesive layer, it is preferably 20 μm or less, more preferably 15 μm or less, and still more preferably 10 μm or less.

The polarizer 2 made by adsorbing the aligned dichroic pigment on the polyvinyl alcohol resin film can be performed by 1) using a separate film of the polyvinyl alcohol resin film as the original film, and subjecting the film to uniaxial stretching and In addition to the method of dyeing treatment of dichroic pigments; 2) Coating a coating solution (aqueous solution, etc.) containing polyvinyl alcohol resin on the substrate film and drying it to obtain a polyvinyl alcohol resin After the base film of the layer is stretched, this together with the base film is stretched uniaxially, and the stretched polyvinyl alcohol resin layer is dyed with dichroic pigments, and then the base film is peeled off. . As the base film, a film made of the same thermoplastic resin as the thermoplastic resin that can form the first and second resin films 3 and 4 described later can be used, preferably a polyester-based film such as polyethylene terephthalate. Films composed of resins, polycarbonate resins, cellulose resins such as triacetyl cellulose, cyclic polyolefin resins such as nortzene resins, and polystyrene resins. According to the method of 2) above, it is easy to produce a thin film polarizer 2, for example, it is easy to produce a thickness of 7 Polarizer 2 below μm.

The first and second resin films 3 and 4 can be independently made of optically transparent thermoplastic resins with better light transmittance, such as chain polyolefin resins (polyethylene resins, polypropylene resins, etc.), Polyolefin resins such as cyclic polyolefin resins (nortzene resins, etc.); cellulose resins (cellulose ester resins, etc.); polyester resins (polyethylene terephthalate, polyethylene naphthalate, etc.) Ethylene formate, polybutylene terephthalate, etc.); polycarbonate resin; (meth)acrylic resin; polystyrene resin; polyether ether ketone resin; poly turquoise resin; or this Films composed of mixtures, copolymers, etc. Among them, the first and second resin films 3 and 4 are respectively composed of cyclic polyolefin resins, polycarbonate resins, cellulose resins, polyester resins, and (meth)acrylic resins. The resin selected from the group is preferably composed of resins selected from the group consisting of cellulose resins and cyclic polyolefin resins.

In addition to homopolymers of chain olefins such as polyethylene resins and polypropylene resins, the chain polyolefin resins may also include copolymers composed of two or more chain olefins.

Cyclic polyolefin resin is a general term for resins containing nortzene or tetracyclododecene (alias: dimethanooctahydronaphthalene) or their derivatives as representative examples of cyclic olefins as polymerized units. . Specific examples of cyclic polyolefin resins include: ring-opening (co)polymers of cyclic olefins and their hydrogenated products; addition polymers of cyclic olefins; cyclic olefins such as ethylene, propylene, etc. Copolymers of chain olefins or aromatic compounds with vinyl groups; And modified (co)polymers which are modified with unsaturated carboxylic acid or its derivatives. Among them, a nortzene-based resin using a nortzene-based monomer such as a nortzene-based monomer or a polycyclic nortzene-based monomer as a cyclic olefin is preferred.

The cellulose resin is preferably a cellulose ester resin, that is, partial or complete esterification of cellulose, and examples thereof include acetate, propionate, butyrate, and mixed esters of cellulose. Among them, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, etc. are preferably used.

The polyester resin is generally a resin other than the above-mentioned cellulose ester resin having an ester bond, and is composed of a polycondensate of a polycarboxylic acid or its derivative and a polyol. Specific examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polytrimethylene terephthalate. Esters, poly(propylene naphthalate), poly(cyclohexane dimethyl terephthalate), poly(cyclohexane dimethyl naphthalate).

The polycarbonate resin is a polyester formed by carbonic acid and glycol or bisphenol. Among them, from the viewpoint of heat resistance, weather resistance, and acid resistance, it is preferable to use aromatic polycarbonates having diphenylalkane in the molecular chain. Polycarbonate can be exemplified by 2,2-bis(4-hydroxyphenyl)propane (alias bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl) Phenyl) cyclohexane, 1,1-bis(4-hydroxyphenyl)isobutane, 1,1-bis(4-hydroxyphenyl)ethane and other bisphenol-derived polycarbonates.

The (meth)acrylic resin that can constitute the first and second resin films 3, 4 may be a polymer mainly composed of a methacrylate-derived structural unit (for example, containing 50% by weight or more of the structural unit). It is preferable to copolymerize it with other copolymerization components. The (meth)acrylic resin system may contain two or more types of structural units derived from methacrylate. Examples of the methacrylate series include C ₁ to C ₄ alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate.

Examples of the copolymer component that can be copolymerized with methacrylate include acrylate. The acrylate is preferably a C ₁ to C ₈ alkyl ester of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like. Specific examples of other copolymerization components include unsaturated acids such as (meth)acrylic acid; aromatic vinyl compounds such as styrene, halogenated styrene, α-methylstyrene, and vinyl toluene; (meth)propylene Vinyl cyanide compounds such as nitriles; unsaturated acid anhydrides such as maleic anhydride and citraconic acid anhydride; unsaturated amides such as phenylmaleimide and cyclohexylmaleimide equal to one polymerizable carbon in the molecule- Compounds other than acrylates with carbon double bonds. A compound having two or more polymerizable carbon-carbon double bonds in the molecule can also be used as a copolymerization component. The copolymer component system may use only 1 type, and may use 2 or more types together.

In terms of improving the durability of the film, the (meth)acrylic resin may have a ring structure in the polymer main chain. The ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic imine structure, and a lactone ring structure. Specific examples of the cyclic acid anhydride structure include glutaric anhydride structure and succinic anhydride structure, and specific examples of cyclic anhydride structure include glutaric imine structure, succinimide structure, and lactone ring structure. Specific examples include butyrolactone ring structure and valerolactone ring structure.

The (meth)acrylic resin may contain acrylic rubber particles from the viewpoints of film-forming properties of the film or impact resistance of the film. The so-called acrylic rubber particles are particles that have an elastic polymer mainly composed of acrylate as an essential component, and essentially include, for example, a single layer structure composed of only this elastic polymer, or a single layer structure made of an elastic polymer. Multi-layered constructor. Examples of the elastic polymer include, for example, a crosslinked elastic copolymer obtained by copolymerizing an alkyl acrylate as a main component with other copolymerizable vinyl monomers and crosslinking monomers. Examples of the alkyl acrylates used as the main component of the elastic polymer include C ₁ to C ₈ alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. The carbon number of the alkyl group is preferably 4 or more.

Other vinyl monomer systems that can be copolymerized with alkyl acrylate include, for example, compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methyl methacrylate and the like. Aromatic vinyl compounds such as acrylate and styrene, vinyl cyanide compounds such as (meth)acrylonitrile, etc. The crosslinkable single system includes, for example, a crosslinkable compound having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, examples include ethylene glycol di(meth)acrylate and butane (Meth)acrylate of polyol such as glycol di(meth)acrylate; alkenyl ester of (meth)acrylic acid such as allyl (meth)acrylate; divinylbenzene, etc.

The content of the acrylic rubber particles is preferably at least 5 parts by weight, and more preferably at least 10 parts by weight, relative to 100 parts by weight of the (meth)acrylic resin. If the content of acrylic rubber particles is too large, the surface hardness of the film will decrease. In addition, when the film is surface treated, the surface treatment agent The solvent resistance of organic solvents will decrease. Therefore, 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 first and second resin films 3 and 4 may contain general additives 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.

化合物、氰基(甲基)丙烯酸酯化合物、鎳錯鹽等。 Examples of ultraviolet absorbers include salicylate compounds, benzophenone compounds, benzotriazole compounds, three

Compounds, cyano (meth)acrylate compounds, nickel aluminum salts, etc.

The first and second resin films 3 and 4 may be films that are not stretched or stretched uniaxially or biaxially. The two-axis extension may be simultaneous two-axis extension while extending in two extension directions, or it may be a sequential two-axis extension that extends in a predetermined direction and then extends in other directions. The first resin film 3 and/or the second resin film 4 may be a protective film that serves to protect the polarizer 2, or may be a protective film that also has the optical function of the retardation film described later. The retardation film is an optical film showing optical anisotropy. For example, a film composed of the above-mentioned thermoplastic resin can be stretched (uniaxially stretched or biaxially stretched, etc.), or a liquid crystal layer may be formed on the thermoplastic resin film, thereby forming a retardation with an arbitrary retardation value. membrane.

The first resin film 3 and the second resin film 4 may be films composed of the same thermoplastic resin, or may be films composed of mutually different thermoplastic resins. The first resin film 3 and the second resin film 4 can be added in thickness and The presence or absence of the agent, its type, phase difference characteristics, etc. are the same or different.

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

The thickness of the first resin film 3 and the second resin film 4 is usually 1 to 150 μm, preferably 5 to 100 μm, and more preferably 5 to 60 μm. The thickness is 50 μm or less, and more preferably 30 μm or less. Reducing the thickness of the first and second resin films 3, 4 is for the thinning of the optical film 1 with the adhesive layer and the optical laminate containing it, and even the optical film 1 with the adhesive layer or the liquid crystal of the optical laminate. The thinning of the display device is advantageous.

Especially for small and medium-sized polarizing plates such as smartphones or tablet-type terminals, in terms of thin film requirements, thinner ones with a thickness of 30μm or less are often used as the first resin film 3 and/or 2. Resin film 4. However, such a polarizer has a weak force to suppress the shrinkage force of the polarizer 2, and the durability is likely to be insufficient. According to the present invention, even when such a polarizing plate is used as the optical film 10, an adhesive layer-attached optical film 1 with good durability and an optical laminate containing the same can be provided. The durability of the adhesive layer-attached optical film 1 and the optical laminate means that the adhesive layer 20 can be restrained from adjoining to the adhesive layer 20 under conditions such as high temperature environment, high temperature and high humidity environment, repeated high temperature and low temperature environment, etc. The properties of the adhesive layer 20 such as the floating or peeling of the interface of the optical member, and the foaming of the adhesive layer 20.

Also, from the point of view of thinning the polarizing plate, it is as The polarizing plate 10a shown in FIG. 2 is advantageous in a configuration in which a resin film is arranged on only one side of the polarizer 2. At this time, the adhesive layer 20 is usually directly attached to the other side of the polarizer 2 to form the adhesive layer-attached optical film 1 (refer to FIG. 4). In the case of the polarizing plate constructed in this way, the problem of the degradation of the optical performance of the polarizing plate under a high temperature and high humidity environment due to the ionic compound contained in the adhesive layer 20 is particularly significant. According to the present invention, even when such a polarizing plate is used as the optical film 10, it is possible to provide an adhesive layer-attached optical film 1 having good optical durability (a property that can inhibit the deterioration of optical characteristics) and the optical film 1 containing the same. Optical laminate.

The first and second resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer or an adhesive layer. The adhesive system for forming the adhesive layer can use an aqueous adhesive or an active energy ray curable adhesive.

Examples of the aqueous adhesive system include an adhesive composed of a polyvinyl alcohol-based resin aqueous solution, an aqueous two-component urethane-based emulsion adhesive, and the like. Among them, an aqueous adhesive composed of a polyvinyl alcohol-based resin aqueous solution is suitably used. In addition to polyvinyl alcohol homopolymers obtained by saponifying polyvinyl acetate homopolymers of vinyl acetate, polyvinyl alcohol resins can also be used to combine vinyl acetate and vinyl acetate. Copolymerized copolymers of other monomers are saponified to obtain polyvinyl alcohol-based copolymers, or modified polyvinyl alcohol-based polymers obtained by partially modifying the hydroxyl groups. The aqueous adhesive system may contain crosslinking agents such as aldehyde compounds, epoxy compounds, melamine compounds, methylol compounds, isocyanate compounds, amine compounds, and polyvalent metal salts.

When using water-based adhesive, it is better to attach polarizer 2 After the first and second resin films 3 and 4, in order to remove the water contained in the aqueous adhesive, a step of drying is performed. After the drying step, an aging step for aging may be set, for example, at a temperature of about 20 to 45°C.

The active energy ray curable adhesive refers to an adhesive that is cured by irradiating active energy rays such as ultraviolet rays or electron beams. Examples include curable compositions containing polymerizable compounds and photopolymerization initiators, and photoreactive adhesives. The curable composition of resin, the curable composition containing binder resin and photoreactive crosslinking agent, etc. Preferably, it is an ultraviolet curable adhesive. Examples of the polymerizable compound system include photopolymerizable monomers such as photocurable epoxy monomers, photocurable (meth)acrylic monomers, and photocurable urethane monomers; or light-derived monomers. Oligomers of polymerizable monomers. Examples of the photopolymerization initiator include those containing active species that generate neutral radicals, anionic radicals, and cationic radicals by irradiation with active energy rays. Active energy ray curable adhesives containing polymerizable compounds and photopolymerization initiators can be preferably used: curable compositions containing photocurable epoxy monomers and photocationic polymerization initiators, or photocurable A curable composition of a reactive (meth)acrylic monomer and a photoradical polymerization initiator, or a mixture of these curable compositions.

When using an active energy ray curable adhesive, after bonding the polarizer 2 and the first and second resin films 3, 4, a drying step is performed as needed, and then the active energy ray is irradiated to make the active energy The curing step of the linear curing adhesive. The light source of the active energy ray is not particularly limited, but it is preferably ultraviolet light with a luminous distribution below the wavelength of 400nm. Specifically, low-pressure mercury lamps, medium-pressure mercury lamps, and high-pressure mercury lamps can be used. Pressure mercury lamp, ultra-high pressure mercury lamp, chemical lamp, black light lamp, microwave excited mercury lamp, metal halide lamp, etc.

When the polarizer 2 and the first and second resin films 3, 4 are bonded together, the bonding surface of at least any one of these may be subjected to surface activation treatments such as saponification treatment, corona treatment, and plasma treatment. When laminating the resin film on both sides of the polarizer 2, the adhesive used for laminating these resin films may be the same type of adhesive or a different type of adhesive.

The polarizing plates 10a, 10b may further contain other films or layers. Specific examples thereof include a brightness enhancement film, an anti-glare film, an anti-reflection film, a diffusion film, a light-concentrating film, and an adhesive layer, a coating layer, and a protective film other than the adhesive layer 20 in addition to the retardation film described later. The protective film is a film used for the purpose of protecting the surface of the optical film 10, such as a polarizing plate, from scratches or stains. After the optical film 1 with an adhesive layer is attached to, for example, the metal layer 30, it is peeled and removed As a general rule.

The protective film usually consists of a base film and an adhesive layer laminated on it. The base film can be made of thermoplastic resins such as polyolefin resins such as polyethylene resins and polypropylene resins; polyester resins such as polyethylene terephthalate or polyethylene naphthalate; polycarbonate resins ; (Meth) acrylic resin and so on.

〔1-2〕Phase difference plate

The retardation film contained in the retardation plate is an optical film exhibiting optical anisotropy as described above, and can be a stretched film obtained by stretching a resin film composed of the following resin to about 1.01 to 6 times. The resin is : Except for the thermoplastic resins exemplified above as those that can be used for the first and second resin films 3 and 4 In addition, for example, polyvinyl alcohol-based resin, polyarylate-based resin, polyimide-based resin, polyether-based resin, polyvinylidene fluoride/polymethyl methacrylate-based resin, liquid crystal polyester-based resin, Saponified ethylene-vinyl acetate copolymer, polyvinyl chloride resin, etc. Among them, a polycarbonate resin film, a cyclic olefin resin film, a (meth)acrylic resin film, or a cellulose resin film is preferably stretched uniaxially or biaxially. In addition, in this specification, a zero retardation film is also included in the retardation film (however, it can also be used as a protective film). In addition, films called uniaxial retardation films, wide viewing angle retardation films, low photoelasticity retardation films, and the like can also be suitably used as retardation films.

The retardation value of zero means the retardation film face R _e and R _th retardation value in the thickness direction are both -15 to 15nm of the film. This retardation film can be suitably used in an IPS mode liquid crystal display device. R _e in-plane retardation value and the thickness direction retardation value R _th lines are preferably 10 to 10nm, more preferably 5 to are based 5nm. Plane retardation value herein called the R _e value of 590nm and a thickness direction retardation R _th value based on the wavelength.

R _e in-plane retardation value and the thickness direction retardation value R _th line are defined by the following _{formula: R e = (n x -n} y) × d R th = [(n x + n y) / 2-n z ]×d. In the formula, n _x is the refractive index in the slow axis direction (x-axis direction) in the film plane, and n _y is the refractive index in the fast axis direction (y-axis direction orthogonal to the x-axis in the plane) in the film plane, n _z is the refractive index in the thickness direction of the film (the z-axis direction perpendicular to the film surface), and d is the thickness of the film.

The zero retardation film can be used, for example, from polyolefin resins such as cellulose resins, chain polyolefin resins and cyclic polyolefin resins, polyethylene terephthalate resins, or (meth)acrylic resins. Resin film composed of resin. In particular, in terms of easy control and easy acquisition of the retardation value, a cellulose resin, a polyolefin resin, or a (meth)acrylic resin can be suitably used.

In addition, a film that exhibits optical anisotropy by coating/alignment of a liquid crystal compound or a film that exhibits optical anisotropy by coating an inorganic layered compound can also be used as a retardation film. Such retardation films include those called temperature-compensated retardation films, and they are formed by obliquely aligned rod-shaped liquid crystals sold by JX Nippon Oil Nippon Energy Co., Ltd. under the trade name "NH film" Film, a film made of obliquely aligned disc-shaped liquid crystals sold under the trade name "WV Film" by Fuji Film Co., Ltd., completely sold under the brand name "VAC Film" by Sumitomo Chemical Co., Ltd. The two-axis alignment type membrane, the two-axis alignment type membrane also sold by Sumitomo Chemical Co., Ltd. under the brand name "new VAC film", etc.

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

(2) Adhesive layer

The adhesive layer 20 laminated on at least one surface of the optical film 10 is composed of a (meth)acrylic resin (A), an isocyanate crosslinking agent (B), a silane compound (C), and an ionic compound (D) The adhesive composition. In the adhesive composition, the (meth)acrylic resin (A) is composed of homopolymer-derived alkyl acrylate (a1) whose glass transition temperature is less than 0°C The unit and the structural unit of alkyl acrylate (a2) whose glass transition temperature from homopolymer is above 0°C, and the weight average molecular weight on the discharge curve in GPC analysis (GPC) is 1000 to 2.5 million There is a single peak in the range of. The content of the isocyanate-based crosslinking agent (B) is 0.08 to 2.5 parts by weight relative to 100 parts by weight of the aforementioned (meth)acrylic resin (A).

The ionic compound (D) is an ionic compound represented by the following formula (I).

(In the formula, R ¹ to R ⁸ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, or A heterocyclic group which may have a substituent; R ⁵ to R ⁸ can form a ring with each other with adjacent substituents).

According to the adhesive layer 20 composed of the above-mentioned adhesive composition, even when the adhesive layer 20 is disposed on a substrate composed of a metal layer, the corrosion of the metal layer can be suppressed, and the adhesion of the adhesive can be improved. The durability of the layered optical film 1 and the optical laminate containing it. Furthermore, according to the adhesive layer 20 composed of the above-mentioned adhesive composition, the optical film 1 with the adhesive layer and the optical laminate containing this, even if the adhesive layer 20 is directly attached to the polarizer 2 The finished structure can also show good optical durability. Hereinafter, the property of suppressing the corrosion of the metal layer is also referred to as "metal corrosion resistance".

The thickness of the adhesive layer 20 is usually 2 to 40 μm, from the viewpoints of durability of the adhesive layer-attached optical film 1 and the optical laminate containing the same, and the reworkability of the adhesive layer-attached optical film 1 , Preferably 5 to 30 μm, more preferably 10 to 25 μm. Moreover, if the thickness of the adhesive layer 20 is 10 μm or more, the followability of the adhesive layer 20 to the dimensional change of the optical film 10 is good, and if it is 25 μm or less, the reworkability becomes good.

The adhesive layer 20 preferably has a storage elastic modulus of 0.1 to 5 MPa in a temperature range of 23 to 80°C. Thereby, the durability of the optical film 1 with the adhesive layer and the optical laminate containing it can be improved more effectively. "The storage elastic modulus of 0.1 to 5 MPa in the temperature range of 23 to 80°C" means that the storage elastic modulus is within the above range at any temperature in this range. The storage elastic modulus usually decreases with the increase of temperature, so if the storage elastic modulus at 23℃ and 80℃ falls within the above range, it can be regarded as the temperature in this range, and the storage elastic modulus in the above range is displayed. . The storage elastic modulus of the adhesive layer 20 can be measured using a commercially available viscoelastic measuring device such as a viscoelastic measuring device "DYNAMIC ANALYZER RDA II" manufactured by REOMETRIC.

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

A polymer or copolymer containing a structural unit derived from a (meth)acrylic monomer as a main component (preferably containing 50% by weight or more). Specific examples of (meth)acrylic monomers are monomers having (meth)acrylic groups such as alkyl (meth)acrylates, and (meth)acrylic resins (A) contain homopolymers The glass transition temperature Tg is the structural unit of alkyl acrylate (a1) whose Tg is less than 0℃, and the alkyl acrylate (a2) whose Tg is derived from homopolymer is above 0℃ The resin constituting the unit. Thereby, the metal corrosion resistance and durability of the optical film 1 with the adhesive layer and the optical laminate containing the same can be improved. The Tg system of the homopolymer of alkyl acrylate can adopt the value of literature such as Polymer Handbook (Wiley-Interscience).

Specific examples of alkyl acrylate (a1) include: ethyl acrylate, n- and iso-propyl acrylate, n- and iso-butyl acrylate, n-pentyl acrylate, n- and iso-hexyl acrylate, acrylic acid N-heptyl, n- and iso-octyl acrylate, 2-ethylhexyl acrylate, n- and isononyl acrylate, n- and iso-decyl acrylate, n-dodecyl acrylate and other alkyl groups Alkyl acrylate with carbon number of about 2-12. Other specific examples of the alkyl acrylate (a1) include, for example, a substituent-containing alkyl acrylate in which the alkyl group of the alkyl acrylate has a carbon number of 2 to 12 or so. The substituent of the substituent-containing alkyl acrylate is a group substituted for the 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 it is preferably a linear or branched alkyl group.

The alkyl acrylate (a1) system 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 the followability and reworkability of the adhesive layer 20 of the optical film 1 with the adhesive layer to the optical film 10, the alkyl acrylate (a1) preferably contains n-butyl acrylate.

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

The alkyl acrylate (a2) system may use only 1 type, and may use 2 or more types together. Among them, from the viewpoint of metal corrosion resistance and durability, alkyl acrylate (a2) preferably contains methyl acrylate, cyclohexyl acrylate, isobornyl acrylate, etc., and more preferably contains methyl acrylate .

From the viewpoint of the metal corrosion resistance and durability of the optical film 1 with the adhesive layer and the optical laminate containing the same, in 100 parts by weight of the total constituent units constituting the (meth)acrylic resin (A), ( The content of the structural unit derived from alkyl acrylate (a2) in the meth)acrylic resin (A) is preferably at least 10 parts by weight, more preferably at least 15 parts by weight, and even more preferably at least 20 parts by weight, especially It is preferably 25 parts by weight or more. Moreover, from the viewpoint of the followability and reworkability of the adhesive layer 20 to the optical film 10, 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 50 parts by weight or less.

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

1) Monomers with polar functional groups.

Monosystems with polar functional groups can include, for example, (methyl) propylene with substituents such as hydroxyl, carboxyl, substituted or unsubstituted amino groups, and heterocyclic groups such as epoxy groups. Enoic acid ester. Specifically, the system includes, for example, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-(2-(meth)acrylate Hydroxyethoxy) ethyl ester, 2-chloro-2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, diethylene glycol mono(meth)acrylate, etc. Monomers with hydroxyl groups; acryloylmorpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, vinyl pyridine, methyl tetrahydrofuran (meth)acrylate, caprolactone modified tetrahydrofuran acrylic acid Monomers with heterocyclic groups such as methyl ester, 3,4-epoxycyclohexyl methyl (meth)acrylate, glycidyl (meth)acrylate, 2,5-dihydrofuran; (methyl) Monomers with substituted or unsubstituted amino groups such as aminoethyl acrylate, N,N-dimethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylate; (methyl) ) Monomers with carboxyl groups such as acrylic acid and carboxyethyl (meth)acrylate. Among them, monomers having a hydroxyl group are preferred, and (meth)acrylates having a hydroxyl group are more preferred in terms of the reactivity of the (meth)acrylic resin (A) with the crosslinking agent.

The (meth)acrylate having a hydroxyl group and the monomer having the above-mentioned other polar functional groups may be contained together, but from the viewpoint of preventing the release force of the separation membrane that can be laminated on the outer surface of the adhesive layer 20 from being increased, It is preferable that the monomer having an amine group is not substantially contained. In addition, from the viewpoint of improving the corrosion resistance to ITO, it is preferable that the monomer having a carboxyl group is not substantially contained. The fact that it is not substantially contained here means that the total constituent unit constituting the (meth)acrylic resin (A) is 0.1 parts by weight or less in 100 parts by weight.

2) Acrylic amide monomer.

For example, N-methylol acrylamide, N-(2-hydroxyethyl) acrylamide, N-(3-hydroxypropyl) acrylamide, and N-(4-hydroxybutyl) acrylamide can be suitably used. amine, N-(5-hydroxypentyl) acrylamide, N-(6-hydroxyhexyl) acrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, N-iso Propyl acrylamide, N-(3-dimethylaminopropyl) acrylamide, N-(1,1-dimethyl-3-oxobutyl) acrylamide, N-[2 -(2-Pendant oxy-1-imidazolidinyl)ethyl)propenamide, 2-propenylamino-2-methyl-1-propanesulfonic acid, N-(methoxymethyl)propene Amide, N-(ethoxymethyl)acrylamide, N-(propoxymethyl)acrylamide, N-(1-methylethoxymethyl)acrylamide, N-(1 -Methylpropoxymethyl)acrylamide, N-(2-methylpropoxymethyl)acrylamide [alias: N-(isobutoxymethyl)acrylamide], N-( Butoxymethyl)acrylamide, N-(1,1-dimethylethoxymethyl)acrylamide, N-(2-methoxyethyl)acrylamide, N-(2- Ethoxyethyl) propylene amide, N-(2-propoxyethyl) propylene amide, N-[2-(1-methylethoxy) ethyl] propylene amide, N-[2 -(1-Methylpropoxy)ethyl]acrylamide, N-[2-(2-methylpropoxy)ethyl]acrylamide [alias: N-(2-isobutoxyethyl) Yl)acrylamide], N-(2-butoxyethyl)acrylamide, N-[2-(1,1-dimethylethoxy)ethyl]acrylamide, etc. Among them, N-(methoxymethyl)acrylamide, N-(ethoxymethyl)acrylamide, N-(propoxymethyl)acrylamide, N-(butoxymethyl) Yl)acrylamide, N-(2-methylpropoxymethyl)acrylamide.

3) Methacrylate, that is, the ester of methacrylic acid.

For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, lauryl methacrylate and other linear alkyl groups of methacrylic acid Esters; branched alkyl esters of methacrylic acid such as isobutyl methacrylate, 2-ethylhexyl methacrylate, iso-octyl methacrylate, etc.; isobornyl methacrylate, methacrylic acid Cyclohexyl methacrylate, dicyclopentyl methacrylate, cyclododecyl methacrylate, methylcyclohexyl methacrylate, trimethylcyclohexyl methacrylate, tert-butylcyclohexyl methacrylate , Cyclohexylphenyl methacrylate and other alicyclic alkyl esters of methacrylic acid; 2-methoxyethyl methacrylate, ethoxymethyl methacrylate and other alkoxyalkyl methacrylates; Aralkyl methacrylate such as benzyl methacrylate; 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-(2-methacrylate) Hydroxyethoxy) ethyl ester, 2-chloro-2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monomethacrylate and other methacrylic acid with hydroxyl groups Alkyl esters; aminoethyl methacrylate, N,N-dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, etc. Methacrylic acid with substituted or unsubstituted amino groups Alkyl ester of methacrylate; 2-phenoxyethyl methacrylate, 2-(2-phenoxyethoxy) ethyl methacrylate, (meth)acrylic acid ethylene oxide modified nonylphenol ester , 2-(o-phenylphenoxy)ethyl methacrylate and other methacrylic acid esters with phenoxyethyl groups.

4) Methacrylamide-based monomers.

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

5) Styrenic monomer.

Such as styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl benzene Alkylstyrenes such as ethylene, heptylstyrene, and octylstyrene; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodostyrene; nitrostyrene; acetyl Styrene; Methoxystyrene; Divinylbenzene, etc.

6) Vinyl monomers.

For example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate and other fatty acid vinyl esters; vinyl chloride, vinyl bromide and other vinyl halide; vinyl chloride and other vinyl halide ; Vinylpyridine, vinylpyrrolidone, vinylcarbazole and other nitrogen-containing aromatic vinyl; butadiene, isoprene, chloroprene and other conjugated diene monomers; acrylonitrile, methpropylene Unsaturated nitriles such as nitrile.

7) A monomer having a plurality of (meth)acrylic groups in the molecule.

For example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethylene Glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate is equal to 2 ( Meth)acrylic monomers; trimethylolpropane tri(meth)acrylate is equal to monomers with 3 (meth)acrylic groups in the molecule.

As mentioned above, from the viewpoint of durability and metal corrosion resistance of the optical film 1 with the adhesive layer and the optical laminate containing it, the (meth)acrylic resin (A) is derived from (meth)acrylic acid In addition to the structural unit of the alkyl ester, it is preferable to include a structural unit derived from a monomer having a polar functional group. The single system having a polar functional group is preferably a (meth)acrylate-based monomer having a polar functional group, and a monomer having a hydroxyl group is more preferable. In 100 parts by weight of the total structural units constituting the (meth)acrylic resin (A), the content of the structural unit derived from the monomer having a polar functional group is preferably 0.1 to 10 parts by weight, more preferably 0.25 to 5 parts by weight, still more preferably 0.5 to 5 parts by weight.

Also, from the viewpoint of the heavy workability of the adhesive layer-attached optical film 1, the (meth)acrylic resin (A) is preferably derived from methacrylate (ester of methacrylic acid) or methacrylic acid. The content of structural units of methacrylic monomers such as amine monomers is small. Specifically, the content of the structural units is preferable in 100 parts by weight of the total structural units constituting the (meth)acrylic resin (A) It is 10 parts by weight or less, more preferably 5 parts by weight or less, and still more preferably does not substantially contain the structural unit (0.1 parts by weight or less).

The (meth)acrylic resin (A) is preferably one having a single peak in the weight average molecular weight Mw range of 1,000 to 2.5 million on the discharge curve in gel permeation chromatography (GPC). The number of peaks in this range is 1 and the (meth)acrylic resin (A) containing the structural units derived from alkyl acrylates (a1) and (a2) is used as the adhesive layer 20 of the matrix polymer. It is advantageous to improve the durability of the optical film 1 with the adhesive layer and the optical laminate containing this. When the number of peaks in the range of Mw is 2 or more, sufficient durability cannot be obtained.

When the number of peaks of the GPC discharge curve in the range of Mw 1000 to 2.5 million is obtained, the discharge curve is obtained according to the GPC measurement conditions described in the item of the embodiment. "Having a single peak" in the above range of the obtained discharge curve means that there is only one maximum value in the range of Mw 1000 to 2.5 million. In this specification, in the GPC discharge curve, the spectrum peak is defined as an S/N ratio of 30 or more.

(Meth) acrylic resin (A) is preferably obtained by GPC The standard polystyrene conversion Mw is in the range of 500,000 to 2.5 million, more preferably in the range of 600,000 to 2 million. If the Mw is more than 500,000, it is advantageous to improve the metal corrosion resistance and durability of the adhesive layer-attached optical film 1 and the optical laminate containing the same, and it also improves the adhesive layer-attached optical film 1 Tendency to heavy work. In addition, if Mw is 2.5 million or less, the followability of the adhesive layer 20 to the dimensional change of the optical film 10 becomes good. The molecular weight distribution represented by the ratio Mw/Mn of the weight average molecular weight Mw and the number average molecular weight Mn is usually 2-10. The Mw and Mn of the (meth)acrylic resin (A) were determined in accordance with the GPC measurement conditions described in the section of Examples.

When the (meth)acrylic resin (A) is dissolved in ethyl acetate to form a solution with a concentration of 20% by weight, the viscosity at 25°C is preferably 20Pa‧s or less, preferably 0.1 to 7Pa‧s For better. The viscosity in such a range is advantageous for improving the durability of the adhesive layer-attached optical film 1 and the optical laminate containing the same, or for the reworkability of the adhesive layer-attached optical film 1. The above-mentioned 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. The Tg in such a range is beneficial to the improvement of the metal corrosion resistance and durability of the optical film 1 with the adhesive layer and the optical laminate containing this.

The adhesive composition system may also contain two or more (meth)acrylic resins belonging to the (meth)acrylic resin (A). In addition, the adhesive composition system may contain another (meth)acrylic resin different from the (meth)acrylic resin (A). However, from the optical film 1 with the adhesive layer From the viewpoint of the metal corrosion resistance and durability of the optical laminate containing this, the content of (meth)acrylic resin (A) is preferably 70 in the total of all (meth)acrylic resins. The weight% or more, more preferably 80 weight% or more, and even more preferably 90 weight% or more, the adhesive composition is particularly preferably containing only (meth)acrylic resin (A) as the matrix polymer.

The (meth)acrylic resin (A) or other (meth)acrylic resins that can be used in combination as needed can be known by, for example, solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, etc. Method to manufacture. In the production of (meth)acrylic resins, polymerization initiators are generally used. About 0.001 to 5 parts by weight of the polymerization initiator is used with respect to 100 parts by weight of all monomers that can be used for the production of (meth)acrylic resin. In addition, the (meth)acrylic resin system can be produced by a method of polymerizing active energy rays such as ultraviolet rays.

As the polymerization initiator system, a thermal polymerization initiator, a photopolymerization initiator, or the like can be used. Examples of the photopolymerization initiator include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone. Examples of thermal polymerization initiators 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-methylpropionate), 2,2'-azobis(2-hydroxymethylpropionitrile) and other azo compounds; lauryl peroxide Oxide, tertiary butyl hydroperoxide, benzyl peroxide, tertiary butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, diperoxydicarbonate Propyl ester, tert-butyl peroxyneodecanoate, tert-butyl peroxytrimethyl acetate, (3,5,5-trimethylhexyl) peroxide And other organic peroxides; potassium persulfate, ammonium persulfate, hydrogen peroxide and other inorganic peroxides. In addition, a redox-based initiator that uses a peroxide and a reducing agent in combination can also be used as a polymerization initiator.

Regarding the method for producing the (meth)acrylic resin, among the methods shown above, the solution polymerization method is preferred. An example of the solution polymerization method is to mix the used monomers and organic solvents, add a thermal polymerization initiator in a nitrogen environment, and stir for 3 to 15 hours at about 40 to 90°C, preferably about 50 to 80°C about. In order to control the reaction, the monomer and the thermal polymerization initiator may be continuously or intermittently added to the polymerization, or added in a state of being dissolved in an organic solvent. For organic solvents, for example, aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropanol; acetone, methyl ethyl ketone, methyl isopropyl Ketones such as butyl ketone.

〔2-2〕Isocyanate-based crosslinking agent (B)

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

The isocyanate-based crosslinking agent (B) is a compound having at least two isocyanate groups (-NCO) in the molecule, and specific examples include toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, Xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate Cyanate ester, triphenylmethane triisocyanate, etc. In addition, the isocyanate-based crosslinking agent (B) may be polyol compound adducts of these isocyanate compounds (for example, adducts of glycerol or trimethylolpropane), trimeric isocyanate compounds, biuret-type compounds, and Derivatives such as urethane prepolymer type isocyanate compounds that have addition reaction with polyether polyol or polyester polyol, acrylic polyol, polybutadiene polyol, polyisoprene polyol, etc. . Among the above, particularly preferred are toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, or polyol compound adducts of these isocyanate compounds, from the adhesive layer-attached optical film 1 and containing this From the viewpoint of durability of the optical laminate, xylylene diisocyanate or its polyol compound adduct is more preferable.

The content of the isocyanate-based crosslinking agent (B) is 0.08 to 2.5 parts by weight, preferably 0.1 to 2 parts by weight (for example, 1 part by weight or less) relative to 100 parts by weight of the (meth)acrylic resin (A). When the content of the isocyanate-based crosslinking agent (B) is within this range, it is advantageous for the coexistence of the metal corrosion resistance and durability of the optical film 1 with the adhesive layer and the optical laminate containing the same.

The adhesive composition system can use isocyanate-based cross-linking agent (B) and other cross-linking agents, such as epoxy compounds, aziridine compounds, metal chelate compounds, peroxides, etc., but from the attached From the viewpoint of the metal corrosion resistance and durability of the optical film 1 of the adhesive layer and the optical laminate containing the same, the adhesive composition contains only the isocyanate-based crosslinking agent (B) as the crosslinking agent, especially substantially It is better not to contain peroxide. Here, substantially free means relative to (meth)acrylic resin (A) The content of 100 parts by weight is 0.01 parts by weight or less.

〔2-3〕Silane compound (C)

The adhesive composition contains a silane compound (C). Thereby, the adhesion between the adhesive layer 20 and the metal layer or glass substrate can be improved. Two or more silane compounds (C) can also be used.

The silane compound (C) system includes, for example, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl ginseng (2-methoxyethoxy) silane, 3-glycidoxy propyl trimethoxy Silane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethyl Silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methylpropene Glyoxypropyltrimethoxysilane, 3-hydrothiopropyltrimethoxysilane, etc.

The silane compound (C) may contain polysiloxane oligomer type. If specific examples of polysiloxane oligomers are indicated in the form of combinations of monomers, they are as follows.

3-Hydroxythiopropyltrimethoxysilane-tetramethoxysilane oligomer, 3-hydrothiopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-hydrothiopropyltri Ethoxysilane-tetramethoxysilane oligomer, 3-hydrothiopropyl triethoxysilane-tetraethoxysilane oligomer and other oligomers containing hydrogensulfanyl propyl group; hydrogensulfide group Methyltrimethoxysilane-tetramethoxysilane oligomer, thiomethyltrimethoxysilane-tetraethoxysilane oligomer, Thiomethyltriethoxysilane-tetramethoxysilane oligomer, thiomethyltriethoxysilane-tetraethoxysilane oligomer, etc. containing thiomethyl oligomers ; 3-glycidoxypropyl trimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyl trimethoxysilane-tetraethoxysilane copolymer, 3-epoxypropylene Oxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyl Methyldimethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-glycidoxypropyl Methyldiethoxysilane-tetramethoxysilane copolymer, 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer, etc. contain 3-glycidoxypropyl Base copolymer; 3-methacryloxypropyl trimethoxysilane-tetramethoxysilane oligomer, 3-methacryloxypropyl trimethoxysilane-tetraethoxysilane oligomer Polymer, 3-methacryloxypropyltriethoxysilane-tetramethoxysilane Oligomer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane Oligomer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-methacryloxypropylmethyldiethoxysilane -Tetramethoxysilane oligomer, 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane oligomer and other oligomers containing methacryloxypropyl group ; 3-propenyloxypropyl trimethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropyl trimethoxysilane-tetraethoxysilane oligomer, 3-propenyloxysilane Propyltriethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropyl triethoxysilane-tetraethoxysilane oligomer, 3-propenyloxypropylmethyl Dimethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-propenyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, 3-propenyloxypropylmethyldiethoxysilane-tetraethoxysilane oligomer, etc. Oligomers containing acryloxypropyl groups; vinyl trimethoxysilane-tetramethoxysilane oligomers, vinyl trimethoxysilane-tetraethoxysilane oligomers, vinyl triethoxy Silane-tetramethoxysilane oligomer, vinyl triethoxysilane-tetraethoxysilane oligomer, vinyl methyl dimethoxysilane-tetramethoxysilane oligomer, vinyl methyl Dimethoxysilane-tetraethoxysilane oligomer, vinylmethyldiethoxysilane-tetramethoxysilane oligomer, vinylmethyldiethoxysilane-tetraethoxysilane oligomer Oligomers and other vinyl-containing oligomers; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-Aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethyldimethyl Oxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethyl Oxysilane copolymer, 3-aminopropylmethyl diethoxysilane-tetraethoxysilane copolymer and other copolymers containing amine groups.

Relative to (meth)acrylic resin (A) 100 weight Parts, the content of the silane compound (C) in the adhesive composition is usually 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, and still more preferably 0.1 to 1 parts by weight . If the content of the silane compound (C) is 0.01 parts by weight or more, it is easy to obtain the effect of improving the adhesion between the adhesive layer 20 and the metal layer 30 or the glass substrate. Moreover, if the content is 10 parts by weight or less, the bleed out of the silane compound (B) from the adhesive layer 20 can be suppressed.

〔2-4〕Ionic compound (D)

The adhesive composition system contains an ionic compound (D). The ionic compound (D) is an ionic compound represented by the following formula (I):

By using the ionic compound (D), not only antistatic properties can be imparted to the adhesive layer 20, but also excellent metal corrosion resistance and optical durability can be imparted. The adhesive composition system may contain one or more ionic compounds (D).

In the above formula (I), R ¹ to R ⁸ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, and an optionally substituted aromatic group. A group or a heterocyclic group which may have a substituent, R ⁵ to R ⁸ can form a ring with each other with adjacent substituents. The case where adjacent substituents form a ring with each other includes: 1) the case where two adjacent substituents among R ⁵ to R ⁸ form a ring structure together with the N atom; 2) the case of R ⁵ to R ⁸ Three substituents and N atoms together form an unsaturated ring structure (including aromatic ring structure) containing an unsaturated bond in which the N atom participates. In addition, R ¹ to R ⁴ can form a ring with each other by adjacent substituents. The case where adjacent substituents form a ring with each other means that two adjacent substituents among R ¹ to R ⁴ form a ring structure together with the B atom.

The alkyl group that may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and specific examples thereof include, for example, methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, and dodecyl , Octadecyl, isopropyl, isobutyl, second butyl, tertiary butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, benzyl Acetomethyl, 1-naphthylmethyl, 2-naphthylmethyl, 4-methylthiobenzylmethyl, 4-phenylthiobenzylmethyl, 4-dimethyl Aminobenzyl methyl, 4-cyanobenzyl methyl, 4-methylbenzyl methyl, 2-methylbenzyl methyl, 3-fluorobenzyl methyl, 3- Trifluoromethylbenzylmethyl, 3-nitrobenzylmethyl.

The alkenyl group which may have a substituent is preferably an alkenyl group having a carbon number of 2 to 10, and specific examples thereof include, for example, 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 that may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and specific examples thereof include, for example, phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 9 -Phenanthryl, 1-pyrenyl, 5-fused tetraphenyl, 1-indenyl, 2-azulenyl (2-azulenyl), 9-phenanthryl, triphenyl, bitetraphenyl, o-, m -, and p-tolyl, xylyl, o-, m-, and p-cumyl, mesityl, pentalenyl, binaphthyl, Ditrinaphthyl, bitetranaphthyl, hexaheptatrienyl, biphenylene, dicyclopentadienyl (indacenyl), fluoranthene, acenaphthyl, benzoacenaphthyl, propylene naphthyl (phenalenyl), phenalenyl, anthracenyl, bianthryl, bitrianthryl, bitetraanthryl, anthraquinone, phenanthryl, triphenylenyl, pyrenyl, triphenylenyl, fused four Phenyl, pleiadenyl (pleiadenyl), acenaryl, perylene, pentaphenyl, pentaphenyl, tetraphenylenyl, hexaphenyl, hexaphenyl Phenyl, rubicenyl, coronenyl, naphthylene, isocondensed heptaphenyl, condensed heptaphenyl, pyranthrenyl, ovalenyl.

噻基、2H-吡咯基、吡咯基、咪唑基、吡唑基、吡啶基、吡

基、嘧啶基、嗒

基、吲

基(indolizinyl)、異吲哚基、3H-吲哚基、吲哚基、1H-吲唑基、嘌呤基、4H-喹

基、異喹啉基、喹啉基、呔

基、

啶基(naphthyridinyl)、喹

啉基、喹唑啉基、噌啉基(cinnolinyl)、喋啶基、4aH-咔唑基、咔唑基、β-咔啉基、啡啶基、吖啶基、呸啶基、啡啉基、啡

基、啡呻

基(phenarsazinyl)、異噻唑基、啡噻

基、異

唑基、呋吖基(furazanyl)、啡

基、異

基(isochromanyl)、

基、吡咯啶基、吡咯啉基、咪唑啶基、咪唑啉基、吡唑啶基、吡唑啉基、哌啶基、哌

基、吲哚啉基、異吲哚啉基、奎寧 環基(quinuclidinyl)、嗎啉基、噻噸酮基。 The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples thereof include, for example, a thienyl group and a benzo[b]thienyl group. , Naphtho[2,3-b]thienyl, thioanthranyl, furanyl, piperanyl, isobenzofuranyl, benzopiperanyl, xanthenyl (xanthenyl), phenanthrene

Thioyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrrolyl

Base, pyrimidinyl, ta

Base, ind

Indolizinyl, isoindolyl, 3H-indolyl, indolyl, 1H-indazolyl, purinyl, 4H-quine

Group, isoquinolyl, quinolyl, ketone

base,

Naphthyridinyl, quine

Linyl, quinazolinyl, cinnolinyl, pteridine, 4aH-carbazolyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, pyridinyl, phenanthrinyl ,coffee

Base, brown

Phenarsazinyl, isothiazolyl, phenarsazinyl

Base, different

Azolyl, furazanyl, phenanthrene

Base, different

Base (isochromanyl),

Group, pyrrolidinyl, pyrrolinyl, imidazolinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperidinyl, piper

Group, indolinyl, isoindolinyl, quinuclidinyl, morpholinyl, thioxanthone.

The above-mentioned alkyl group which may have a substituent, alkenyl group which may have a substituent, alkynyl group which may have a substituent, an aryl group which may have a substituent, and a substituent which may be substituted by the hydrogen atom of the heterocyclic group which may have a substituent Specific examples of the group include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; phenoxy, p-tolyloxy, etc. Alkoxycarbonyl groups such as aryloxy, methoxycarbonyl, butoxycarbonyl, phenoxycarbonyl, vinyloxycarbonyl, and aryloxycarbonyl; acetyloxy, propionyloxy, benzyloxy Acetyloxy and other acyloxy groups; Acetyl, benzyl, isobutyryl, acryloyl, methacryloyl, methacryloyl, etc.; methylthio, tertiary butylthio Alkylthio groups; arylthio groups such as phenylthio and p-tolylthio; alkylamino groups such as methylamino groups and cyclohexylamino groups; dimethylamino groups, diethylamino groups, N -Dialkylamino groups such as morpholinyl and N-hexahydropyridyl; arylamino groups such as phenylamino and p-tolylamino; methyl, ethyl, tertiary butyl, dodecyl and other alkanes Group; aryl groups such as phenyl, p-tolyl, xylyl, cumyl, naphthyl, anthracenyl, phenanthryl, etc.; hydroxyl, carboxyl, sulfonamide, methionyl, sulfhydryl, sulfonic acid , Toluenesulfonyl, p-toluenesulfonyl, amine, nitro, nitroso, cyano, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphinico, phosphine Amino group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium group, dimethylsulfoniumyl, triphenylbenzylmethylphosphonium group.

Among the above-mentioned substituents, preferred substituents are electron withdrawing substituents. By substituting electron-withdrawing substituents, general ionic compounds become easy to dissociate, which can improve antistatic performance. Electron withdrawing substituents Specific examples include halogen atom, cyano group, carboxyl group, nitro group, nitroso group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, trialkylammonium Group, amide group, perfluoroalkyl group, perfluoroalkylthio group, perfluoroalkylcarbonyl group, sulfonamide group, 4-cyanophenyl group.

Preferably, R ¹ to R ⁴ are each independently an optionally substituted alkyl group or an optionally substituted aryl group. Preferably, R ⁵ to R ⁸ are each independently an optionally substituted alkyl group or an optionally substituted aryl group. Alternatively, it is preferable that three substituents among R ⁵ to R ⁸ form an unsaturated ring structure (including an aromatic ring structure) containing an unsaturated bond together with the N atom.

Among them, R ¹ to R ^{4 are} preferably aryl groups that may have substituents, and the anion of the ionic compound (D) is more preferably the borate anion represented by the following formula (II):

In the above formula (II), R ⁹ to R ¹³ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, and an optionally substituted aromatic group. A group, a heterocyclic group which may have a substituent, or a halogen atom can form a ring with each other with adjacent substituents.

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

From the viewpoint of antistatic performance, the cation of the ionic compound (D) is pyridinium cation, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, pyrazolium cation, pyrazolium cation, etc. A cation having a heterocyclic structure containing a nitrogen atom containing an unsaturated bond is preferred, and a pyridinium cation, wherein the pyridinium cation represented by the following formula (III) is more preferred:

In the above formula (III), R ¹⁴ to R ¹⁹ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, and an optionally substituted aromatic group. A group, a heterocyclic group that may have a substituent, a hydroxyl group, an ether group, a carboxyl group, a carbonyl group, or a halogen atom can form a ring with each other with adjacent substituents.

The pyridinium cation represented by the above 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. The carbon number is preferably 1-16. R ¹⁵ to R ¹⁹ are independent, preferably a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbons, a hydroxyl group, or a halogen atom, and more preferably a hydrogen atom or a carbon number of 1 to 20 is a linear alkyl group.

From the viewpoint of antistatic performance and the metal corrosion resistance of the optical film 1 with the adhesive layer and the optical laminate containing the same, the ionic compound (D) is preferably an anion represented by the above formula (II) Borate anion and the cation is a cation having a heterocyclic structure containing a nitrogen atom containing an unsaturated bond, and more preferably an anion is a tetrakis (pentafluorophenyl) borate anion and the cation is a cation having a nitrogen atom containing an unsaturated bond The cation of the heterocyclic structure is more preferably the tetrakis (pentafluorophenyl) borate anion and the cation is the pyridinium cation represented by the above formula (III), and the more preferable the cation is the tetrakis (pentafluorophenyl) boric acid The salt anion and the cation is the pyridinium cation represented by the above formula (III) in which R ¹⁴ is a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms.

Relative to 100 parts by weight of the (meth)acrylic resin (A), the content of the ionic compound (D) in the adhesive composition is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 8 parts by weight, and still more It is preferably 0.3 to 5 parts by weight, and particularly preferably 0.5 to 3 parts by weight. The content of the ionic compound (D) of 0.1 parts by weight or more is beneficial to the improvement of antistatic performance, and 10 parts by weight or less is beneficial to the metal corrosion resistance of the optical film 1 with the adhesive layer and the optical laminate containing the same. Durability.

The adhesive composition can be used in combination with the ionic compound (D) represented by the above formula (I) and an antistatic agent other than this, but from the adhesive layer of the optical film 1, and the optical laminate containing the metal resistant Corrosiveness In terms of point, the adhesive composition preferably contains only the ionic compound (D) represented by the above formula (I) as an antistatic agent.

〔2-5〕Other ingredients

The adhesive composition can contain one or two additives such as solvents, crosslinking catalysts, ultraviolet absorbers, weather stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, and light scattering fine particles. More than species. In addition, an ultraviolet curable compound can also be formulated in the adhesive composition to form an adhesive layer and then irradiate ultraviolet rays to harden it to form a harder adhesive layer. The crosslinking catalyst system can include, for example, hexamethylene diamine, ethylene diamine, polyethylene imine, hexamethylene tetramine, diethylene triamine, triethylene tetramine, isophorone diamine, trimethylene Amine compounds such as diamines, polyamine-based resins and melamine resins.

The adhesive composition may contain an anti-corrosion agent for improving the metal corrosion resistance of the optical film 1 to which the adhesive layer is attached and the optical laminate containing this. Examples of antiseptic agents include triazole-based compounds such as benzotriazole-based compounds and other triazole-based compounds; thiazole-based compounds such as benzothiazole-based compounds and other thiazole-based compounds; benzylimidazole-based compounds, and others Imidazole-based compounds such as imidazole-based compounds; imidazoline-based compounds; quinoline-based compounds; pyridine-based compounds; pyrimidine-based compounds; indole-based compounds; amine-based compounds; urea-based compounds; sodium benzoate; Compound; di-second butyl sulfide; and diphenyl sulfene.

However, according to the present invention, sufficient metal corrosion resistance can be obtained even if the rust inhibitor is not contained, so the content of the rust inhibitor is preferably as small as possible. In particular, the adhesive composition system does not contain substantially The triazole compound of the rust inhibitor is preferable, and it is more preferable that it does not substantially contain a rust inhibitor selected from the above-mentioned compound group. Here, it means that the content is 0.01 parts by weight or less relative to 100 parts by weight of the (meth)acrylic resin (A).

[3] The composition and manufacturing method of optical film with adhesive layer

The optical film 1 with an adhesive layer includes an optical film 10 and an adhesive layer 20 laminated on at least one surface of the optical film 10 (Figure 1). It can also be applied to the double-area adhesive layer 20 of the optical film 10. Generally, the adhesive layer 20 is directly laminated on the surface of the optical film 10. When the adhesive layer 20 is provided on the surface of the optical film 10, it is preferable to form a primer layer on the bonding surface of the optical film 10 and/or the bonding surface of the adhesive layer 20, or subject to surface activation treatment such as electric For pulp treatment, corona treatment, etc., corona treatment is better.

When the optical film 10 is a single-sided protective polarizer as shown in Figure 2, it is usually on the side of the polarizer, that is, the side of the polarizer 2 opposite to the first resin film 3, and it is preferable to directly laminate the adhesive layer 20 . When the optical film 10 is a double-sided protective polarizing plate as shown in Figure 3, the adhesive layer 20 may be layered outside any one of the first and second resin films 3, 4, or may be layered outside of both剂层20。 Agent layer 20.

An antistatic layer can be additionally provided between the optical film 10 and the adhesive layer 20, but the adhesive layer 20 of the present invention can provide excellent antistatic properties to the adhesive layer alone, so it is a thin film or laminate of the optical laminate In terms of simplification of the manufacturing steps, it is preferable that there is no antistatic layer between the optical film 10 and the adhesive layer 20.

Optical film 1 with adhesive layer can also contain laminated layers A separation film (release film) on the outer surface of the adhesive layer 20. The separation film is usually peeled off when the adhesive layer 20 is used (for example, when it is laminated on the metal layer 30). The separation membrane can be, for example, polysilicon is applied to the surface of a film composed of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate, etc., where the adhesive layer 20 will be formed. Oxygen treatment plasma processor.

The adhesive layer-attached optical film 1 can be formed by dissolving or dispersing the components constituting the adhesive composition in a solvent to form a solvent-containing adhesive composition, and then coating it on the surface of the optical film 10 and drying it. The adhesive layer 20 is formed. In addition, the optical film 1 with the adhesive layer can be made by forming the adhesive layer 20 on the release treatment surface of the separation film in the same manner as described above, and laminating (transferring) the adhesive layer 20 on the surface of the optical film 10 Got.

<Optical Laminate>

4 and 5 are schematic cross-sectional views showing an example of the layer structure of the optical laminate of the present invention. In one embodiment, as shown in FIGS. 4 and 5, the optical laminate system of the present invention includes an optical film 1 with an adhesive layer and a metal layer 30 laminated on the adhesive layer 20 side. The optical laminate 5 shown in Fig. 4 uses the polarizing plate 10a shown in Fig. 2 as an example of the optical film 10, and the optical laminate 6 shown in Fig. 5 uses the polarizing plate 10b shown in Fig. 3 as an example An example of the optical film 10. In the optical laminates 5 and 6 shown in FIGS. 4 and 5, the adhesive layer-attached optical film 1 is laminated on the metal layer 30 such that the adhesive layer 20 directly contacts the metal layer 30. According to the present invention, even in such an optical laminate in which the adhesive layer 20 directly contacts the metal layer 30, the corrosion of the metal layer 30 can be effectively suppressed.

Fig. 6 is a schematic cross-sectional view showing another example of the layer structure of the optical laminate of the present invention. In another embodiment, the optical laminate system of the present invention is the optical laminate 7 shown in FIG. 6, and the adhesive layer 20 of the adhesive layer-attached optical film 1 is laminated on the metal layer 30 with the resin layer 50 interposed therebetween. The adhesive layer 20 directly contacts the resin layer 50. Even in such an optical laminate 7, corrosion of the metal layer 30 can be effectively suppressed. The resin layer 50 disposed between the adhesive layer 20 and the metal layer 30 may be, for example, a cured layer of curable resin. A known curable resin system that can form the resin layer 50 can be used, and examples thereof include those described in JP 2009-217037 A.

Fig. 7 is a schematic cross-sectional view showing another example of the layer structure of the optical laminate of the present invention. In still another embodiment, the optical laminate system of the present invention is the optical laminate 8 shown in FIG. 7, and the metal layer 30 may not be provided. At this time, the adhesive layer 20 of the optical film 1 with the adhesive layer is laminated on the substrate 40, for example. The substrate 40 is, for example, a glass substrate as described later.

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

The metal layer 30 can be a metal oxide layer such as ITO. However, the adhesive layer-attached optical film 1 of the present invention is particularly good in corrosion resistance to metal monomers or alloys, so the metal layer 30 contains metal monomers composed of the above-mentioned metal elements and/or contains two types Alloys of the above-mentioned metal elements are preferred. However, the optical build-up system may also have such a metal layer 30 and a transparent electrode layer made of metal oxide such as ITO.

The form (for example, thickness, etc.) or preparation method of the metal layer 30 is not particularly limited. In addition to metal foil, it may also be vacuum evaporation, sputtering, ion plating, inkjet printing, or gravure. It is formed by a printing method, but preferably a metal layer formed by sputtering, inkjet printing, or gravure printing, and more preferably a metal layer formed by sputtering. Among the metal layers and metal foils formed by sputtering, the former tends to have poor corrosion resistance. However, the optical laminate according to the present invention has good resistance even to the metal layers formed by sputtering. Corrosive metal. The thickness of the metal layer 30 is generally 3 μm or less, preferably 1 μm or less, and more preferably 0.8 μm or less. In addition, 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 line width of the metal wiring of the metal wiring layer is usually 10 μm or less, preferably 5 μm or less, and more preferably 3 μm or less. In addition, the line width of the metal wiring is usually 0.01 μm or more, preferably 0.1 μm or more, and more preferably 0.5 μm or more. Even for such a thin metal layer 30 or a metal layer 30 composed of thin wire metal wiring, the optical laminated system of the present invention still shows good metal corrosion resistance. In particular, even if the metal wiring has a thickness of 3 μm or less and a line width of 10 μm or less, or a thickness of 3 μm or less and a line width of 10 μm or less, and is formed by a sputtering method, the corrosion can be suppressed. Is to suppress pitting corrosion.

The metal layer 30 may be, for example, a metal wiring layer (that is, an electrode layer) of a touch input element included in a touch input liquid crystal display device. At this time, the metal layer 30 is generally patterned into a predetermined shape. An example when the metal layer 30 is a metal wiring layer is shown in FIG. 8. In the optical laminate shown in FIG. 8, the resin layer 50 can be omitted. When the adhesive layer 20 is laminated on the patterned metal layer 30, the adhesive 20 may have a portion that does not touch the metal layer 30. The metal layer 30 may be a continuous film containing the aforementioned metals or alloys.

In addition, the metal layer 30 may have a single-layer structure, or a multilayer structure of two or more layers. The metal layer of the multilayer structure includes, for example, a metal-containing layer (metal mesh, etc.) having a three-layer structure represented by molybdenum/aluminum/molybdenum.

As shown in FIGS. 4 and 5, a metal layer 30 such as a metal wiring layer may be formed on the substrate 40. In this case, the optical laminate system of the present invention may include this substrate 40. The formation of the metal layer 30 on the substrate 40 can be performed by, for example, sputtering. The substrate 40 may be a transparent substrate constituting a liquid crystal cell included in the touch input device. The substrate 40 is preferably a glass substrate. The material of the glass substrate can include, for example, soda lime glass, low-alkali glass, and alkali-free glass. The metal layer 30 may be formed on the entire surface of the substrate 40 or may be formed on a part of it. When the patterned metal layer 30 is formed on the substrate 40, it is equal to a part of the surface of the substrate 40. When the metal layer 30 is formed, a part of the adhesive layer 20 is in direct contact with the substrate 40 made of glass, for example. The adhesive layer 20 in the optical laminate of the invention is also excellent in adhesion to glass, so the optical laminate and the liquid crystal display device equipped with the optical laminate are in such a situation The durability is also excellent.

The optical film 1 with the adhesive layer on the metal layer 30 (or the above-mentioned resin layer) is bonded with the adhesive layer 20 therebetween to obtain the optical laminates 5 and 6. After bonding the optical film 1 with the adhesive layer and the metal layer 30 to make an optical laminate, if there is any problem, sometimes it is necessary to peel the optical film 1 with the adhesive layer from the metal layer 30, and then separate the other The optical film 1 with the adhesive layer is reattached to the metal layer 30, which is the so-called heavy work. The optical film 1 with an adhesive layer of the present invention hardly generates fogging or residual adhesive on the surface of the metal layer 30 after peeling from the metal layer 30, and has excellent reworkability. According to the optical film 1 with an adhesive layer of the present invention, when the surface of the adhesive layer 20 is not a metal layer 30 but a glass substrate or an ITO layer, it can also show good reworkability.

<Liquid crystal display device>

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

The liquid crystal display device of the present invention is preferably a touch input liquid crystal display device with a touch panel function. The touch input type liquid crystal display device is equipped with a touch input element containing a liquid crystal unit and a backlight. The structure of the touch panel can be any method known in the past, such as out-cell, on-cell in-cell, in-cell in-cell, etc. Moreover, the operation method of the touch panel can be a resistive film method, Any conventionally known methods such as the electrostatic capacitance method (surface capacitance method, projection capacitance method). Adhesion of the present invention The optical film 1 of the agent layer can be arranged on the viewing side of the touch input element (liquid crystal cell), on the backlight side, or on both sides. The driving method of the liquid crystal cell may be any conventionally known method such as TN method, VA method, IPS method, multi-domain method, and OCB method. In the liquid crystal display device of the present invention, the substrate 40 included in the optical laminate may be a substrate (typically a glass substrate) included in the above-mentioned liquid crystal cell.

[Example]

Hereinafter, examples and comparative examples are shown to explain the present invention more specifically, but the present invention is not limited to these examples. Hereinafter, the parts and% indicating the usage amount, content, and% are based on weight unless otherwise stated.

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

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, a solution obtained by mixing monomers with the composition shown in Table 1 (the value in Table 1 is parts by weight) and 81.8 parts of ethyl acetate was added. After replacing the air in the reaction vessel with nitrogen, the internal temperature was set to 60°C. Then, the solution which melt|dissolved 0.12 part of azobisisobutyronitrile in 10 parts of ethyl acetate was added. After maintaining the same temperature for 1 hour, the internal temperature was maintained at 54 to 56°C, and ethyl acetate was continuously added into the reaction vessel at an addition rate of 17.3 parts/Hr so that the polymer concentration became about 35%. After 12 hours from the start of the addition of ethyl acetate, the internal temperature was maintained at 54 to 56°C, and ethyl acetate was added to adjust the polymer concentration to 20% to obtain (meth)acrylic resin ( A-1) The ethyl acetate solution. (Meth) acrylic resin (A-1) weight average molecular weight Mw is 1.39 million, weight The ratio Mw/Mn of the average molecular weight Mw and the number average molecular weight Mn was 5.32. In the discharge curve of Gel Permeation Chromatography (GPC), the component with Mw 1.39 million shows a single peak, and no other peaks are seen in the range of Mw from 1000 to 2.5 million.

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

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, a solution obtained by mixing monomers with the composition shown in Table 1 and 81.8 parts of ethyl acetate was added. After replacing the air in the reaction vessel with nitrogen, the internal temperature was set to 60°C. Thereafter, a solution obtained by dissolving 0.03 part of azobisisobutyronitrile in 10 parts of ethyl acetate was added. After keeping at the same temperature for 1 hour, keep the internal temperature at 54 to 56°C, and at the same time make it react for 4 to 5 hours until the conversion rate becomes 75%, to obtain a copolymer and monomer with a weight average molecular weight Mw of 1 million mixture. Then, 200 parts of toluene and 0.2 parts of azobisisobutyronitrile were added, and the reaction was further allowed to react for 6 hours until the conversion rate became 100%, and a (meth)acrylic resin (A-) having a glass transition temperature Tg of -7°C was obtained. 2) Solution. (Meth) acrylic resin (A-2) contains: high molecular weight components (A-2-1) that do not contain polymers with a molecular weight of less than 150,000 and Mw of 1 million, and do not contain those with a molecular weight of 150,000 or more Polymer and low molecular weight component with Mw of 25,000 (A-2-2). The high-molecular-weight component (A-2-1) and the low-molecular-weight component (A-2-2) are in the GPC discharge curve, showing two independent peaks. The area ratio of the two is (A-2-1 )/(A-2-2)=75/25. No other peaks can be seen in the range of Mw 1000 to 2.5 million.

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

Except that the composition of the monomers was as shown in Table 1, the same procedure was followed as in Production Example 1, and an ethyl acetate solution (resin concentration: 20%) of (meth)acrylic resin (A-3) was prepared. The weight average molecular weight Mw of the (meth)acrylic resin (A-3) was 1.41 million, and Mw/Mn was 4.71. In the discharge curve of GPC, the component of Mw 1.41 million shows a single peak, and in the range of Mw 1000 to 2.5 million, no other peaks can be seen.

In the above manufacturing example, the weight average molecular weight Mw and the number average molecular weight Mn are used in the GPC device. The 4 "TSKgel XL" manufactured by Tosoh Corporation and the "Shodex GPC KF-802" manufactured by Showa Denko Corporation 1 A total of 5 roots are connected in series as the column, and tetrahydrofuran is used as the eluent. The measurement is measured by standard polystyrene conversion under the conditions of sample concentration 5mg/mL, sample introduction amount 100μL, temperature 40℃, and flow rate 1mL/min. . The conditions for preparing the discharge curve of GPC are also the same.

The glass transition temperature Tg was measured using a differential scanning calorimeter (DSC) "EXSTAR DSC6000" manufactured by SII Nanotechnology Co., Ltd. in a nitrogen atmosphere under the conditions of a measurement temperature range of -80 to 50°C and a temperature increase rate of 10°C/min.

The composition of the monomers in each manufacturing example (the values in Table 1 are parts by weight), and the number of peaks in the range of Mw from 1000 to 2.5 million on the GPC discharge curve (labeled as "GPC peak number" in Table 1 ) Is compiled in Table 1.

The abbreviations in the column of "monomer composition" in Table 1 mean the following monomers.

BA: Butyl acrylate (Glass transition temperature of homopolymer: -54℃), MA: Methyl acrylate (Glass transition temperature of homopolymer: 10℃), HEA: 2-hydroxyethyl acrylate.

<Examples 1 to 2, Comparative Examples 1 to 7>

(1) Preparation of adhesive composition

In the ethyl acetate solution (resin concentration: 20%) of the (meth)acrylic resin obtained in the above production example, with respect to 100 parts of the solid content of the solution, the isocyanate-based crosslinking agent shown in Table 2 ( B), the silane compound (C), and the ionic compound (D) were mixed in the amounts (parts by weight) shown in Table 2, and then ethyl acetate was added so that the solid content concentration became 14% to prepare an adhesive Composition. When the product used contains a solvent, etc., the blending amount of each blending ingredient shown in Table 2 is the weight part of the active ingredient contained therein.

The details of the ingredients shown in Table 2 by abbreviations are as follows.

(Isocyanate-based crosslinking agent)

B-1: The ethyl acetate solution of the trimethylolpropane adduct of xylylene diisocyanate (solid content 75%), taken from Mitsui Chemicals Co., Ltd. under the trade name "Takenate D-110N".

(Silane compound)

C-1: 3-Glycidoxypropyltrimethoxysilane, which is the trade name "KBM403" of Confidence Yue Chemical Industry Co., Ltd.

(Ionic compound)

D-1: N-methylpyridinium (pentafluorophenyl) borate, D-2: N-decylpyridinium (pentafluorophenyl) borate, D-3: N-octyl-4 -Methylpyridinium hexafluorophosphate, D-4: N-methylpyridinium bis(fluorosulfonyl)imine.

(2) Making the adhesive layer

Use an applicator on the release treatment surface of the separation membrane [trade name "PLR-382051" from Lintec Co., Ltd.] composed of polyethylene terephthalate membrane subjected to release treatment Each adhesive composition prepared in (1) was applied so that the thickness after drying became 20 μm, and dried at 100° C. for 1 minute to prepare an adhesive layer (adhesive sheet).

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

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

A transparent protective film composed of a 25μm thick triacetyl cellulose film (made by Konica Minolta Opto) is laminated on one side of the obtained polarizer with an adhesive composed of an aqueous solution of a polyvinyl alcohol-based resin. The product name "KC2UA"]. Then, the surface of the polarizer opposite to the triacetyl cellulose film is formed by bonding a 23μm thick cyclic polyolefin resin via an adhesive composed of an aqueous solution of a polyvinyl alcohol resin. Zero retardation film [trade name of Japan Zeon (stock) system "ZEONOR"] to make a polarizing plate. Then, the surface of the zero retardation film on the opposite side to the surface adjacent to the polarizer is subjected to corona discharge treatment to improve adhesion, and then the adhesive produced in (2) above is bonded by a laminator After the layer is on the opposite side of the separation film (adhesive layer), it is aged for 7 days under the conditions of a temperature of 23°C and a relative humidity of 65% to prepare an optical film (P-1) with an adhesive layer.

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

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

A transparent protective film composed of a 25μm thick triacetyl cellulose film (made by Konica Minolta Opto) is laminated on one side of the obtained polarizer with an adhesive composed of an aqueous solution of a polyvinyl alcohol-based resin. The product name "KC2UA"] is used to make polarizing plates. Then, on the opposite side of the polarizer and the side where the protective film is attached, use a laminator to bond the side of the adhesive layer (2) on the opposite side of the separation film (adhesive layer) , It is aged for 7 days under the conditions of temperature 23℃ and relative humidity 65% to prepare optical film with adhesive layer (P-2).

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

Cut the optical film with adhesive layer (P-1) produced in (3) above into a test piece with a size of 20mm×50mm, and affix it to the metal layer of the glass substrate with metal layer through the adhesive layer side. The glass substrate with a metal layer is a glass substrate (manufactured by Geomatec) in which a metal aluminum layer with a thickness of about 500 nm is laminated on the surface of alkali-free glass by sputtering. After storing the obtained optical laminate in an oven at a temperature of 60°C and a relative humidity of 90% for 500 hours, light was irradiated from the back of the glass substrate and the optical film with the adhesive layer attached was observed from the surface of the polarizer through a magnifying glass. The state of part of the metal layer was evaluated on the basis of the following criteria for pitting corrosion (the generation of holes with a diameter of 0.1 mm or more that can penetrate light). The results are shown in Table 3.

4: The number of pitting corrosion generated on the surface of the metal layer is less than 2. 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 More than one, 1: Multiple pitting corrosion occurs on the entire surface of the metal layer, and also white turbidity.

(6) Durability evaluation of optical film with adhesive layer

The optical film (P-1) with the adhesive layer produced in (3) above is cut into a size of 200mm×150mm so that the extension axis direction of the polarizer becomes the long side, and the separation film is peeled off to bond the exposed adhesive The agent layer is attached to the glass substrate. The obtained glass substrate-attached test piece (optical film attached with the adhesive layer of the glass substrate) was pressurized in an autoclave at a temperature of 50° C. and a pressure of 5 kg/cm ² (490.3 kPa) for 20 minutes. The glass substrate uses the brand name "Eagle XG" of alkali-free glass manufactured by Corning. For the obtained optical laminate, the following three durability tests were performed.

[Durability test]

‧Heat resistance test for 750 hours under dry conditions at a temperature of 85℃, ‧Heat and heat resistance test for 750 hours under an environment with a temperature of 60℃ and 90% relative humidity, ‧Hold for 30 minutes under dry conditions at a temperature of 85℃ , And then keep the operation for 30 minutes under the dry condition of -40℃ as 1 cycle, and repeat the heat shock (HS) test of 400 cycles.

Visually observe the optical laminate after each test, visually observe the presence or absence of appearance changes such as floating, peeling, and foaming of the adhesive layer, and evaluate durability based on the following evaluation criteria. The results are shown in Table 3.

4: No appearance changes such as floating, peeling, and foaming are visible at all; 3: No appearance changes such as floating, peeling, and foaming are hardly visible; 2: Appearance changes such as floating, peeling, and foaming are slightly noticeable, 1 : Appearance changes such as floating, peeling, and foaming are clearly seen.

(7) Evaluation of heavy workability of optical film with adhesive layer

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

4: No fogging, etc. can be seen on the surface of the glass substrate. 3: No fogging, etc. can be seen on the surface of the glass substrate. 2: Fogging can be seen on the surface of the glass substrate. 1: On the surface of the glass substrate. The residue of the adhesive layer can be seen on the surface.

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

The optical film (P-2) with the adhesive layer produced in (4) above is cut into a size of 30mm×30mm, the separation film is peeled off, and the exposed adhesive layer is attached to the glass substrate. The glass substrate uses the brand name "Eagle XG" of alkali-free glass manufactured by Corning. For the obtained optical laminate, use a spectrophotometer with an integrating sphere [product name "V7100" manufactured by JASCO Corporation) to measure the MD transmittance and TD transmittance in the wavelength range of 380 to 780 nm Calculate the transmittance and polarization of the monomer in each wavelength, and further use the 2 degree field of view (C light source) in JIS Z 8701: 1999 "Color display method-XYZ color system and X ₁₀ Y ₁₀ Z ₁₀ color system" ) Perform visual sensitivity correction to obtain the single transmittance (Ty) of visual sensitivity correction and the degree of polarization (Py) of visual sensitivity correction before the endurance test. In addition, the optical multilayer system uses the triacetyl cellulose film side of the polarizer as the detector side, and installs a spectrophotometer with integrating sphere so that light is incident from the glass substrate side.

The monomer transmittance and polarization are determined by the following formulas Meaning: monomer transmittance (λ)=0.5×(Tp(λ)+Tc(λ)) Polarization (λ)=100×(Tp(λ)-Tc(λ))/(Tp(λ)+ Tc(λ))Tp(λ) is the transmittance (%) of the optical laminate measured with the incident wavelength λ(nm) linearly polarized light and parallel polarized light (parallel nicol). Tc(λ) is based on The transmittance (%) of the optical laminate measured by the relationship between the incident wavelength λ (nm) of linearly polarized light and crossed nicol.

Then, the optical laminate was placed in a hot and humid environment at a temperature of 80°C and a relative humidity of 90% for 24 hours, and then placed in an environment at a temperature of 23°C and a relative humidity of 60% for 24 hours. The same as before the endurance test Method to obtain Ty and Py after endurance test. After that, subtract the Py and Ty before the test from the Py and Ty after the test to calculate the change before and after the endurance test, and obtain the change in polarization degree (△Py) and the change in monomer transmittance (△Ty) ). Table 3 shows ΔPy.

<Production Example 4: Production of (meth)acrylic resin (A-1) for adhesive layer>

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, a solution obtained by mixing monomers with the composition shown in Table 4 (the value in Table 4 is parts by weight) and 81.8 parts of ethyl acetate was added. After replacing the air in the reaction vessel with nitrogen, the internal temperature was set to 60°C. Then, the solution which melt|dissolved 0.12 part of azobisisobutyronitrile in 10 parts of ethyl acetate was added. After maintaining the same temperature for 1 hour, the internal temperature was maintained at 54 to 56°C, and ethyl acetate was continuously added into the reaction vessel at an addition rate of 17.3 parts/Hr so that the polymer concentration became about 35%. After 12 hours have passed since the addition of ethyl acetate, the internal temperature was maintained at 54 to 56°C, Ethyl acetate was added to adjust the polymer concentration to 20%, and an ethyl acetate solution of (meth)acrylic resin (A-1) was prepared. The weight average molecular weight Mw of the (meth)acrylic resin (A-1) is 1.39 million, and the ratio Mw/Mn of the weight average molecular weight Mw and the number average molecular weight Mn is 5.32. In the discharge curve of Gel Permeation Chromatography (GPC), the component with Mw 1.39 million shows a single peak, and no other peaks are seen in the range of Mw from 1000 to 2.5 million.

In the above manufacturing example, the weight average molecular weight Mw and the number average molecular weight Mn are used in the GPC device. The 4 "TSKgel XL" manufactured by Tosoh Corporation and the "Shodex GPC KF-802" manufactured by Showa Denko Corporation 1 A total of 5 roots are connected in series as the column, and tetrahydrofuran is used as the eluent. The measurement is measured by standard polystyrene conversion under the conditions of sample concentration 5mg/mL, sample introduction amount 100μL, temperature 40℃, and flow rate 1mL/min. . The conditions for preparing the discharge curve of GPC are also the same.

The glass transition temperature Tg was measured using a differential scanning calorimeter (DSC) "EXSTAR DSC6000" manufactured by SII Nanotechnology Co., Ltd. in a nitrogen atmosphere under the conditions of a measurement temperature range of -80 to 50°C and a temperature increase rate of 10°C/min.

The composition of the monomer in Production Example 4 (the values in Table 4 are parts by weight), and the number of peaks in the range of Mw 1,000 to 2.5 million on the GPC discharge curve (labeled as "GPC peak number" in Table 4) ) Is summarized in Table 4.

The abbreviations in the column of "monomer composition" in Table 4 mean the following monomers.

BA: butyl acrylate (the glass transition temperature of homopolymer: -54°C), MA: methyl acrylate (the glass transition temperature of homopolymer: 10°C), HEA: 2-hydroxyethyl acrylate.

<Examples 3 to 4, Comparative Examples 8 to 9>

(1) Preparation of adhesive composition

In the ethyl acetate solution (resin concentration: 20%) of the (meth)acrylic resin obtained in Production Example 4, with respect to 100 parts of the solid content of the solution, the isocyanate-based crosslinking agent shown in Table 5 ( B), the silane compound (C), and the ionic compound (D) were mixed in the amounts (parts by weight) shown in Table 5, and then ethyl acetate was added so that the solid content concentration became 14% to prepare an adhesive Composition. When the product used contains a solvent, etc., the blending amount of each blending ingredient shown in Table 5 is the weight part of the effective ingredient contained therein.

The details of each compounding component represented by abbreviations in Table 5 are as follows.

(Isocyanate-based crosslinking agent)

B-1: An ethyl acetate solution of the trimethylolpropane adduct of xylylene diisocyanate (solid content 75%), taken from Mitsui Chemicals Co., Ltd. under the trade name "Takenate D-110N".

(Silane compound)

C-1: 3-Glycidoxypropyltrimethoxysilane, which is the trade name "KBM403" of Confidence Yue Chemical Industry Co., Ltd.

(Ionic compound)

D-2: N-decylpyridinium (pentafluorophenyl) borate, D-3: 1-octyl-4-methylpyridinium hexafluorophosphate, D-4: N-methylpyridinium Bis(fluorosulfonyl)imine.

(2) Making the adhesive layer

At the release point of the separation membrane [trade name "PLR-382051" from Lintec (stock)] composed of polyethylene terephthalate membrane subjected to release treatment For surface treatment, each adhesive composition prepared in (1) was applied with an applicator so that the thickness after drying became 20 μm, and dried at 100° C. for 1 minute to prepare an adhesive layer (adhesive sheet).

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

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

A transparent protective film composed of a 25μm thick triacetyl cellulose film (made by Konica Minolta Opto) is laminated on one side of the obtained polarizer with an adhesive composed of an aqueous solution of a polyvinyl alcohol-based resin. The product name "KC2UA"]. Then, the surface of the polarizer opposite to the triacetyl cellulose film is formed by bonding a 23μm thick cyclic polyolefin resin via an adhesive composed of an aqueous solution of a polyvinyl alcohol resin. The zero retardation film [trade name "ZEONOR" manufactured by Japan Zeon Co., Ltd.] to produce polarizing plates. Then, the surface of the zero retardation film on the opposite side to the surface adjacent to the polarizer is subjected to corona discharge treatment to improve adhesion, and then the adhesive produced in (2) above is bonded by a laminator After the layer and the separation membrane are on the opposite side (adhesive layer), set the temperature at 23℃ and phase After maturing for 7 days under the condition of humidity of 65%, an optical film with adhesive layer (P-1) is prepared.

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

(4-1) Example 3 and Comparative Example 8

Cut the optical film with adhesive layer (P-1) produced in (3) above into a test piece measuring 20mm×50mm, and attach it to the metal layer of the glass substrate with metal layer through the adhesive layer side. The glass substrate with a metal layer is a glass substrate (manufactured by Geomatec) in which a metal copper layer with a thickness of about 500 nm is laminated on the surface of alkali-free glass by sputtering. After storing the obtained optical laminate in an oven at a temperature of 60°C and a relative humidity of 90% for 120 hours, light was irradiated from the back of the glass substrate, and the optical film with the adhesive layer attached was observed from the surface of the polarizer through a magnifying glass. The state of part of the metal layer was evaluated on the basis of the following criteria for pitting corrosion (the generation of holes with a diameter of 0.1 mm or more that can penetrate light). The results are shown in Table 6.

(4-2) Example 4 and Comparative Example 9

Cut the optical film with adhesive layer (P-1) produced in (3) above into a test piece of 20mm×50mm, and affix it to the metal layer of the glass substrate with metal layer through the adhesive layer side. The glass substrate with a metal layer is used on the surface of the alkali-free glass by sputtering to deposit a silver alloy (with silver as the main component, and an alloy containing palladium and copper, APC) layer with a thickness of about 500nm (Geomatec) system). After storing the obtained optical laminate in an oven at a temperature of 60°C and a relative humidity of 90% for 500 hours, light is irradiated from the back of the glass substrate and observed from the surface of the polarizing plate through a magnifying glass. The state of the metal layer of the part of the optical film of the agent layer was evaluated on the basis of the following criteria for pitting (the generation of holes with a diameter of 0.1 mm or more that can penetrate light). The results are shown in Table 6.

4: The number of pitting corrosion generated on the surface of the metal layer is less than 2. 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 More than one, 1: Multiple pitting corrosion occurs on the entire surface of the metal layer, and also white turbidity.

1‧‧‧Optical film with adhesive layer

10‧‧‧Optical film

20‧‧‧Adhesive layer

Claims (15)

An optical film with an adhesive layer comprising an optical film and an adhesive layer laminated on at least one surface of the optical film, wherein the adhesive layer is composed of (meth)acrylic resin (A), isocyanate Crosslinking agent (B), silane compound (C), and ionic compound (D) composed of adhesive composition; the aforementioned (meth)acrylic resin (A) contains glass transfer derived from homopolymer The structural unit of alkyl acrylate (a1) whose temperature is less than 0℃, and the structural unit of alkyl acrylate (a2) whose glass transition temperature from homopolymer is above 0℃, and gel permeation chromatography analysis The weight average molecular weight on the discharge curve has a single peak in the range of 1000 to 2.5 million; relative to 100 parts by weight of the aforementioned (meth)acrylic resin (A), the content of the aforementioned isocyanate-based crosslinking agent (B) is 0.08 To 2.5 parts by weight, the aforementioned ionic compound (D) is an ionic compound represented by the following formula (I):

In the formula, R ¹ to R ⁸ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an aryl group that may have a substituent, or For heterocyclic groups with substituents, R ¹ to R ⁴ can form a ring with adjacent substituents; R ⁵ to R ⁸ can form a ring with adjacent substituents. The optical film with adhesive layer as described in the first item of the scope of patent application, wherein the anion of the aforementioned ionic compound (D) is the borate anion represented by the following formula (II):

In the formula, R ⁹ to R ¹³ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, and The heterocyclic group or halogen atom of the substituent can also form a ring with each other with adjacent substituents. The optical film with an adhesive layer as described in claim 1, wherein the anion of the ionic compound (D) is tetrakis (pentafluorophenyl) borate anion. The optical film with an adhesive layer as described in claim 1, wherein the anion of the aforementioned ionic compound (D) is a tetrakis (pentafluorophenyl) borate anion, and the cation has an unsaturated bond The structure of a heterocyclic ring containing a nitrogen atom. The optical film with an adhesive layer as described in claim 1, wherein the anion of the aforementioned ionic compound (D) is tetrakis (pentafluorophenyl) borate anion, and the cation is the following formula (III) Pyridium cation shown:

In the formula, R ¹⁴ to R ¹⁹ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an aryl group that may have a substituent, and The heterocyclic group, hydroxyl group, ether group, carboxyl group, carbon group, or halogen atom of the substituent can form a ring with each other with adjacent substituents. The optical film with an adhesive layer as described in claim 1, wherein the (meth)acrylic resin (A) contains a structural unit derived from a monomer having a hydroxyl group. The optical film with an adhesive layer as described in the first item of the patent application, wherein the weight average molecular weight of the (meth)acrylic resin (A) is 500,000 to 2.5 million. The optical film with an adhesive layer described in the first item of the scope of patent application, wherein the adhesive composition is substantially free of peroxide. The optical film with an adhesive layer as described in the first item of the patent application, wherein the adhesive composition system does not substantially contain a triazole compound. The optical film with an adhesive layer as described in claim 1, wherein the (meth)acrylic resin (A) does not substantially contain a structural unit derived from a methacrylate monomer. The optical film with an adhesive layer as described in claim 1, wherein the optical film includes a polyvinyl alcohol-based resin dyed with iodine In the formed polarizer, the adhesive layer is directly laminated on the polarizer. A liquid crystal display device includes the optical film with an adhesive layer described in any one of items 1 to 11 in the scope of the patent application. An adhesive composition comprising (meth)acrylic resin (A), isocyanate crosslinking agent (B), silane compound (C), and ionic compound (D); wherein, the aforementioned (meth)acrylic acid Resin (A) is a structural unit containing alkyl acrylate (a1) derived from a homopolymer with a glass transition temperature of less than 0°C, and alkyl acrylate derived from a homopolymer with a glass transition temperature of 0°C or higher The structural unit of (a2), and the weight average molecular weight on the discharge curve in the gel permeation chromatography analysis has a single peak in the range of 1000 to 2.5 million; relative to the 100 weight of the aforementioned (meth)acrylic resin (A) The content of the aforementioned isocyanate-based crosslinking agent (B) is 0.08 to 2.5 parts by weight, and the aforementioned ionic compound (D) is an ionic compound represented by the following formula (I):

In the formula, R ¹ to R ⁸ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an aryl group that may have a substituent, or For heterocyclic groups with substituents, R ¹ to R ⁴ can form rings with adjacent substituents; R ⁵ to R ⁸ can form rings with adjacent substituents; the adhesive composition is used to be The formation of an adhesive layer laminated on the metal layer. An optical film with an adhesive layer, comprising an optical film and an adhesive layer laminated on at least one surface of the optical film, and used for bonding to a metal layer via the adhesive layer, wherein, the aforementioned The adhesive layer is formed of an adhesive composition containing (meth)acrylic resin (A), isocyanate crosslinking agent (B), silane compound (C), and ionic compound (D), the aforementioned (A) Base) acrylic resin (A) is a structural unit containing alkyl acrylate (a1) derived from a homopolymer whose glass transition temperature is less than 0℃, and a homopolymer whose glass transition temperature is above 0℃ The structural unit of alkyl acrylate (a2), and the weight average molecular weight on the discharge curve in the gel permeation chromatography analysis has a single peak in the range of 1000 to 2.5 million; compared to the aforementioned (meth)acrylic resin (A ) 100 parts by weight, the content of the aforementioned isocyanate-based crosslinking agent (B) is 0.08 to 2.5 parts by weight, and the aforementioned ionic compound (D) is an ionic compound represented by the following formula (I):

In the formula, R ¹ to R ⁸ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, an aryl group that may have a substituent, or For heterocyclic groups with substituents, R ¹ to R ⁴ can form a ring with adjacent substituents; R ⁵ to R ⁸ can form a ring with adjacent substituents. An optical laminate comprising the optical film with an adhesive layer described in any one of items 1 to 10 in the scope of patent application, and a metal layer laminated on the adhesive layer side of the optical film with the adhesive layer .

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