TW201732001A - Optical film with an adhesive layer and optical laminate - Google Patents

Abstract

The purpose of the present invention is to provide an optical film with an adhesive layer exhibiting an excellent durability even under a strict durability condition and an optical laminated body comprising the optical film. The solution of the present invention is to provide an optical film with an adhesive layer, wherein the optical film comprises an optical film and an adhesive layer laminated on at least one side of the optical film, and the above adhesive layer is constituted by a reaction product of an adhesive composition comprising (A) (meth)acrylic resin, (B) cross-linking agent, and (C) silane compound, wherein the above (A) (meth)acrylic resin comprises a constitute unit originated from a hydroxyl-containing (meth)acrylate resin represented by the following formula (al) and the following formula (a2).

Description

Optical film and optical laminate with adhesive layer

The present invention relates to an optical film which is excellent in durability and which is used as an adhesive layer for an optical member such as a liquid crystal display device, and an optical laminate including the same.

An optical film represented by a polarizing plate in which a transparent resin film is laminated on one surface or both surfaces of a polarizing plate is widely used as an optical member constituting an image display device such as a liquid crystal display device. An optical film such as a polarizing plate is often used by being bonded to another member (for example, a liquid crystal cell in a liquid crystal display device) via an adhesive layer (see Patent Document 1). Therefore, as an optical film, an optical film in which an adhesive layer of an adhesive layer is provided in advance is known.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-229321

In recent years, liquid crystal display devices have been extended to mobile machine applications represented by smart phones or tablet terminals or vehicle-mounted devices represented by car navigation systems. In such applications, there is a possibility of being exposed to a more severe environment than conventional TV use in the home, and thus the durability of the device is a problem.

Durability is also required in an optical film constituting an adhesive layer such as a liquid crystal display device. In other words, when it is assembled in an adhesive layer such as a liquid crystal display device, it is placed in a high-temperature or high-temperature and high-humidity environment, and sometimes placed in an environment of high temperature and low temperature, and the optical film with an adhesive layer is required to be In such an environment, it is also possible to suppress problems such as floating or peeling of the interface between the adhesive layer and the optical member to which the adhesive layer is bonded, foaming of the adhesive layer, and the like, and it is also required that the optical characteristics are not deteriorated. In particular, in the case where the optical film is a polarizing plate, in order to have a high shrinkage stress in a high temperature environment, the adhesive layer is required to have higher durability than that of a general optical film. Since the demand for durability improvement of the above liquid crystal display device is increased, the durability required for the adhesive layer has recently become very strict.

Accordingly, an object of the present invention is to provide an optical film of an adhesive layer which exhibits excellent durability even under such severe durability conditions, and an optical laminate comprising the same.

The inventors of the present invention have completed the present invention in order to solve the above problems and strive to review the results.

That is, in the present invention, the following are included.

[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 comprises (meth)acrylic resin (A), The reaction product of the binder composition of the crosslinking agent (B) and the decane compound (C), and the (meth)acrylic resin (A) contains the content represented by the following formula (a1) a constituent unit of a hydroxyl group (meth) acrylate, and a constituent unit derived from a hydroxyl group-containing (meth) acrylate represented by the following formula (a2),

(wherein, n represents an integer of 1 to 4, A ¹ represents a hydrogen atom or an alkyl group, X ¹ represents a methylene group which may have a substituent, and when n is 2 or more, the substituents may be the same or different);

(wherein m represents an integer of 5 or more, A ² represents a hydrogen atom or an alkyl group, and X ² represents a methylene group which may have a substituent, and the aforementioned substituents may be the same or different).

[2] The optical film with an adhesive layer as described in [1], which is derived from the formula (a1) with respect to 100 parts by weight of all constituent units constituting the (meth)acrylic resin. The proportion of the constituent unit of the hydroxyl (meth) acrylate is 1.5 to 4.5 parts by weight derived from the formula (a2) The proportion of the constituent unit of the hydroxyl group-containing (meth) acrylate shown is 0.25 to 1.0 part by weight.

[3] The optical film with an adhesive layer according to [1] or [2], wherein the (meth)acrylic resin contains a constituent unit derived from an alkyl acrylate (a3) derived from an alkyl acrylate. The constituent unit of the ester (a3) contains a constituent unit derived from a homopolymer of an alkyl acrylate (a3-1) having a glass transition temperature of less than 0 ° C, and a glass transition temperature derived from a homopolymer of 0 ° C or higher. The constituent unit of the alkyl acrylate (a3-2).

[4] The optical film of the adhesive layer according to [3], wherein the glass transition temperature derived from the homopolymer is a constituent unit of the alkyl acrylate (a3-1) which is less than 0 ° C, and is derived from The ratio (weight ratio) of the constituent units of the alkyl acrylate (a3-2) having a glass transition temperature of 0 ° C or higher of the homopolymer is (a3-1) / (a3-2) = 20/80 to 95/5.

[5] The optical film with an adhesive layer according to any one of [1] to [4] wherein the weight average molecular weight of the (meth)acrylic resin is 6.0 × 10 ⁵ in terms of polystyrene. 2.5×10 ⁶ .

[6] The optical film with an adhesive layer according to any one of [1] to [5] wherein the crosslinking agent (B) is an aromatic isocyanate compound and/or the aromatic isocyanate compound is passed through a plurality of An adduct of an alcohol compound.

[7] The optical film with an adhesive layer according to any one of [1] to [6] wherein the ratio of the crosslinking agent (B) is relative to the (meth)acrylic resin (A) 100. It is 0.01 to 10 parts by weight in parts by weight.

The optical film with an adhesive layer according to any one of the above aspects, wherein the decane compound (C) is a decane compound represented by the following formula (c1).

(wherein B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms; and -CH ₂ - constituting the alkanediyl group and the alicyclic hydrocarbon group may be substituted into -O - or -CO-, R ¹ represents an alkyl group having 1 to 5 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 5 carbon atoms or a carbon number of 1 to 5 Alkoxy).

[8] [9] The optical film attached to the adhesive layer described in the, B, in the formula (c1) of the alkanediyl group having a carbon number of 1 to 10, R ¹ is alkyl of 1 to 5, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkoxy group having 1 to 5 carbon atoms.

[10] The optical film with an adhesive layer according to any one of [1], wherein the ratio of the decane compound (C) is 100% by weight relative to the (meth)acrylic resin (A). It is 0.01 to 10 parts by weight in parts.

[11] The optical film with an adhesive layer according to any one of [1] to [10] wherein the adhesive layer has a gel fraction of 50 to 95%.

[12] The optical film with an adhesive layer according to any one of [1], wherein the adhesive layer is bonded to a glass substrate at a temperature of 23 ° C and a relative humidity of 50%. Next, the adhesion of the above-mentioned adhesive layer after 24 hours was 0.5 to 10 N/25 mm at a peeling speed of 300 mm/min.

[13] An optical laminate comprising any of [1]~[12] An optical film of the above described adhesive layer.

In the present specification, the term "(meth)acrylic" means acrylic or methacrylic, and the same applies to "(meth)acrylate" or "(meth)acryloyl). Ester or methacrylate, acryl oxime or methacryl oxime.

The optical film with an adhesive layer of the present invention and an optical laminate system comprising the same have excellent durability even under severe durability conditions.

1, 1a, 1b‧‧‧ optical film with adhesive layer

2‧‧‧ polarizer

3‧‧‧1st resin film

4‧‧‧2nd resin film

5, 6, 7, 8, 9‧‧‧ Optical laminates

10‧‧‧Optical film

10a, 10b‧‧‧ polarizing plate

20‧‧‧Adhesive layer

30‧‧‧metal layer

40‧‧‧Substrate

50‧‧‧ resin layer

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

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

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

[Fig. 4] Fig. 4 is a schematic cross-sectional view showing an example of an optical layered body according to the present invention.

[Fig. 5] Fig. 5 is a schematic cross-sectional view showing another example of the optical layered body according to the present invention.

[Fig. 6] Fig. 6 is a schematic cross-sectional view showing still another example of the optical layered body according to the present invention.

[Fig. 7] Fig. 7 is a view showing an optical layered body according to the present invention. A schematic cross-sectional view of another example.

[Fig. 8] Fig. 8 is a schematic cross-sectional view showing still another example of the optical layered body according to the present invention.

<Optical film with adhesive layer>

The optical film with an adhesive layer of the present invention comprises an optical film and an adhesive layer laminated on at least one side of the optical film.

Fig. 1 is a schematic cross-sectional view showing an example of an optical film with an adhesive layer according to the present invention. The optical film 1 with an adhesive layer shown in Fig. 1 is an optical film of the optical film 10 and the single-layer adhesive layer 20 of the optical film. The adhesive layer 20 is usually directly laminated on the surface of the optical film 10, and is formed by a reaction of an adhesive composition containing a (meth)acrylic resin (A), a crosslinking agent (B), and a decane compound (C). The composition of things. The adhesive layer 20 may also be laminated on both sides of the optical film.

[1] Optical film

The optical film 10 constituting the optical film 1 with an adhesive layer can be various optical films (films having optical characteristics) that can be incorporated in an image display device such as a liquid crystal display device. The optical film 10 may have a single layer structure (for example, a polarizing film, a retardation film, a brightness enhancement film, an anti-glare film, an anti-reflection film, a diffusion film, an optical functional film such as a light-harvesting film, etc.), or may have a multilayer structure ( For example, a polarizing plate, a phase difference plate, etc.). The optical film 10 is preferably a polarizing plate, a polarizing plate, a phase difference plate or a retardation film, and particularly preferably a polarizing plate or a polarizing plate. In addition, in this specification, The optical film system means a film that functions to display an image (display screen, etc.) (for example, a film that functions to enhance the visibility of an image). In the present specification, the polarizing plate means a resin film or a resin layer of at least one area of the polarizing plate, and the phase difference plate means a resin film or a resin layer of at least one area of the retardation film.

[1-1] Polarizer

2 and 3 are schematic cross-sectional views showing an example of a layer configuration of a polarizing plate. The polarizing plate 10a shown in Fig. 2 is a single-sided protective polarizing plate in which a first resin film 3 is laminated on one area of the polarizing plate 2 (or laminated), and the polarizing plate 10b shown in Fig. 3 is a polarizing plate. The other surface of the second surface of the second resin film 4 is further laminated (or laminated) to protect the polarizing plate. 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). Further, 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 having a property of absorbing linear polarized light having a vibrating surface parallel to its absorption axis and penetrating a linearly polarized light having a vibrating surface orthogonal to the absorption axis (parallel to the transmission axis), for example, A film obtained by adsorbing a dichroic dye to a polyvinyl alcohol resin film. Examples of the dichroic dye include iodine or a dichroic organic dye.

The polyvinyl alcohol-based resin can be obtained by saponifying a polyvinyl acetate-based resin. Examples of the polyvinyl acetate-based resin include polyvinyl acetate which is a homopolymer of vinyl acetate, and a monomer copolymerizable with vinyl acetate (for example, an unsaturated carboxylic acid, an olefin, a vinyl ether, or not). A copolymer of saturated sulfonic acid, (meth)acrylamide having an ammonium group, and the like, and a copolymer of vinyl acetate.

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

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

The polarizer 2 is, for example, a step of uniaxially stretching a green film, a step of dyeing a film with a dichroic dye to adsorb the dichroic dye, a step of treating the film with a boric acid aqueous solution, and washing the film. The steps are finally dried and manufactured. The thickness of the polarizing plate 2 is usually 1 to 30 μm, and is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less from the viewpoint of thinning of the optical film 1 to which the adhesive layer is attached.

The polarizer 2 obtained by adsorbing a dichroic dye to a polyvinyl alcohol-based resin film is a single film using a single film of a polyvinyl alcohol-based resin film, and the film is subjected to uniaxial stretching treatment and two colors. In addition to the method of dyeing the dye, 2) a coating liquid (aqueous solution or the like) containing a polyvinyl alcohol-based resin is applied to the base film, and dried to obtain polyethylene After the base film of the enol-based resin layer, the base film is uniaxially stretched, and the stretched polyvinyl alcohol-based resin layer is subjected to a dyeing treatment of the dichroic dye, and then the base film is peeled off and removed. Also available. As the base film, a film containing a thermoplastic resin similar to the thermoplastic resin which can constitute the first and second resin films 3 and 4 to be described later can be used, and it is preferable to contain a polyester such as polyethylene terephthalate. A film such as a cellulose resin such as a polycarbonate resin or a polycarbonate resin such as triethyl fluorenyl cellulose or a cyclic polyolefin resin such as a decene-based resin or a polystyrene resin. According to the method of the above 2), the production of the polarizer 2 of the film is facilitated, and for example, the production of the polarizer 2 having a thickness of 7 μm or less is also facilitated.

Each of the first and second resin films 3 and 4 may independently comprise a thermoplastic resin which is translucent and preferably optically transparent, for example, a chain polyolefin resin (polyethylene resin, polypropylene resin, etc.) Polyolefin resin such as a cyclic polyolefin resin (such as a decene-based resin); a cellulose resin (such as a cellulose ester resin); a polyester resin (polyethylene terephthalate or poly). Ethylene naphthalate, polybutylene terephthalate, etc.; polycarbonate resin (for example, polycarbonate derived from bisphenol such as 2,2-bis(4-hydroxyphenyl)propane) (meth)acrylic resin; polystyrene resin; polyetheretherketone resin; polyfluorene-based resin, or a mixture of these, a copolymer, or the like. Among these, the first and second resin films 3 and 4 are preferably made of a cyclic polyolefin resin, a polycarbonate resin, a cellulose resin, a polyester resin, and (meth)acrylic acid. A film composed of a resin or the like is particularly preferably a film composed of a cellulose resin or a cyclic polyolefin resin.

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

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

The cellulose resin is preferably a cellulose ester resin, that is, a part or a complete ester of cellulose, and examples thereof include cellulose acetate, propionate, tyrosate, and a mixed ester thereof. Among these, triethylenesulfonyl cellulose, diethyl acetoxy cellulose, cellulose acetate propionate, cellulose acetate butyrate, and the like are preferable.

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

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

The (meth)acrylic resin which can constitute the first and second resin films 3 and 4 can be a polymer mainly composed of a constituent unit derived from methacrylate (for example, 50% by weight or more). It is a copolymer in which other copolymerization components are copolymerized.

The (meth)acrylic resin may contain two or more constituent units derived from methacrylate. Examples of the methacrylate include C ₁ to C ₄ alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate.

As a copolymerization component copolymerizable with a methacrylate, an acrylate is mentioned. The acrylate is preferably a C ₁ -C ₈ alkyl ester of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate. Specific examples of the other copolymerization component include unsaturated acids such as (meth)acrylic acid; aromatic vinyl compounds such as styrene, halogenated styrene, α-methylstyrene, and vinyltoluene; and (meth)acrylonitrile. Ethylene-based cyanide compounds; unsaturated anhydrides such as maleic anhydride and citraconic anhydride; unsaturated quinone imines such as phenyl maleimide and cyclohexylmaleimine have one polymerizable carbon in the molecule - A compound other than an acrylate of a carbon double bond. A compound having two or more polymerizable carbon-carbon double bonds in the molecule may also be used as the copolymerization component. The copolymerization component can be used singly or in combination of two or more.

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

The (meth)acrylic resin may contain acrylic rubber particles from the viewpoint of film formability of the film, impact resistance of the film, and the like. The acrylic rubber particles are particles in which an elastic polymer mainly composed of an acrylate is used as an essential component, and a single layer structure including substantially only the elastic polymer or a multilayer structure in which an elastic polymer is used as one layer is used. By. Examples of the elastic polymer include a crosslinked elastic copolymer in which an alkyl acrylate is used as a main component and copolymerized with another vinyl monomer and a crosslinkable monomer copolymerizable therein. Examples of the alkyl acrylate which is a 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 alkyl group preferably has 4 or more carbon atoms.

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

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

The first and second resin films 3 and 4 may contain a usual additive in the technical field of the present invention. Examples of the additive include an ultraviolet absorber, an infrared absorber, an organic dye, a pigment, an inorganic dye, an antioxidant, an antistatic agent, a surfactant, a lubricant, a dispersant, a heat stabilizer, and the like. Examples of the ultraviolet absorber include a salicylate compound, a benzophenone compound, a benzotriazole compound, and the like. A compound, a cyano (meth) acrylate compound, a nickel salt or the like.

Each of the first and second resin films 3 and 4 may be a film that is not stretched or a film that is uniaxially or biaxially stretched. The first resin film 3 and/or the second resin film 4 may be a protective film that functions as a protective polarizer 2, or may be a protective film having an optical function such as a retardation film to be described later. another Further, the first resin film 3 and the second resin film 4 may be the same or different films.

Further, the first resin film 3 and/or the second resin film 4 may have a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, and an antistatic layer on the outer surface (the surface opposite to the polarizer 2). Surface treatment layer (coating) such as antifouling layer and conductive layer. The thickness of each of the first resin film 3 and the second resin film 4 may be usually 1 to 150 μm, preferably 5 to 100 μm (for example, 5 to 60 μm), more preferably 50 μm or less (for example, 1 to 40 μm), and further preferably 30 μm or less (for example, 5 to 25 μm).

In particular, in a small-sized ortho-polarized polarizing plate such as a smart phone or a tablet terminal, a thinner one having a thickness of 30 μm or less is often used as the first resin film 3 and/or the second resin film. 4. However, such a polarizing plate is weak in suppressing the contraction force of the polarizing plate 2, and the durability is likely to be insufficient. Even in the case where such a polarizing plate is used as the optical film 10, the optical film 1 with an adhesive layer of the present invention has good durability. In addition, in the present specification, the durability of the optical film 1 and the optical layered body with the adhesive layer refers to, for example, a high-temperature environment, a high-temperature and high-humidity environment, a high-temperature and low-temperature reversal environment, and the like, and the adhesive can be suppressed. The characteristics of the floating or peeling of the interface between the layer 20 and the optical member adjacent thereto (sometimes referred to as peeling resistance), and the inability to suppress the problem of foaming of the adhesive layer 20 (sometimes referred to as foaming resistance) Sex). Further, in the present invention, the agglomeration resistance is a property of suppressing aggregation damage (or breakage) of the adhesive layer.

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

The water-based adhesive agent is a conventional water-based adhesive (for example, an adhesive containing a polyvinyl alcohol-based resin aqueous solution, an aqueous two-liquid urethane-based latex adhesive, an aldehyde compound, an epoxy compound, or a melamine-based compound, A crosslinking agent such as a methylol compound, an isocyanate compound, an amine compound or a polyvalent metal salt). Among these, a water-based adhesive containing a polyvinyl alcohol-based resin aqueous solution can be suitably used. Further, when the water-based adhesive is used, after the polarizer 2 and the first and second resin films 3 and 4 are bonded together, it is preferred to perform a drying step for removing water contained in the aqueous adhesive. . After the drying step, a ripening step of aging at a temperature of, for example, about 20 to 45 ° C may be provided.

The active energy ray-curable adhesive agent is an adhesive which is cured by irradiation with an active energy ray such as an ultraviolet ray or an electron beam, and examples thereof include a curable composition containing a polymerizable compound and a photopolymerization initiator, and a photoreaction. The curable composition of the resin, the curable composition containing the binder resin and the photoreactive crosslinking agent, and the like are preferably an ultraviolet curable adhesive.

When the active energy ray-curable adhesive is used, after the polarizer 2 is bonded to the first and second resin films 3 and 4, a drying step is performed as needed, and then the active energy is applied by irradiating the active energy ray. A hardening step of hardening the wire hardener. The light source of the active energy ray is not particularly limited, and is preferably an ultraviolet ray having a light-emitting distribution at a wavelength of 400 nm or less.

The polarizer 2 and the first and second resin films 3 and 4 are introduced. In the method of bonding, the bonding surface of at least one of these may be subjected to a surface activation treatment such as saponification treatment, corona treatment or plasma treatment. In the case where the resin film is bonded to both surfaces of the polarizing film 2, the adhesive for bonding the resin films may be the same kind of adhesive or a different type of adhesive.

The polarizing plates 10a, 10b may further comprise other films or layers. Specific examples thereof include a retardation film to be described later, and a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, a light concentrating film, an adhesive layer other than the adhesive layer 20, a coating layer, a protective film, and the like. The protective film is a film that is used for the purpose of protecting the surface of the optical film 10 such as a polarizing plate from damage or contamination. Conventionally, the optical film 1 with the adhesive layer is bonded to, for example, a metal layer or a substrate, and then peeled off. Remove.

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

[1-2] phase difference plate

The retardation film included in the retardation film is an optical film exhibiting optical anisotropy as described above, and can be exemplified by being contained in the first and second resin films 3 and 4 Other than the thermoplastic resin, for example, a polyvinyl alcohol resin, a polyarylate resin, a polyimide resin, a polyether oxime resin, a polyvinylidene fluoride/polymethyl methacrylate resin, Liquid crystal polyester resin, ethylene-vinyl acetate copolymer saponified product, A stretched film obtained by stretching a resin film composed of a polyvinyl chloride resin or the like to about 1.01 to 6 times. Among these, a stretched film in which a polycarbonate resin film, a cyclic olefin resin film, a (meth)acrylic resin film, or a cellulose resin film is uniaxially stretched or biaxially stretched is preferred. . Further, in the present specification, the zero retardation film is also included in the retardation film (however, it can also be used as a protective film). In addition, a film called a uniaxial retardation film, a wide viewing angle retardation film, or a low photoelasticity retardation film can also be used as a retardation film.

The retardation value of zero means the retardation film plane R _e and R _th retardation value in the thickness direction are both films of -15 ~ 15nm. This retardation film is suitable for use in an IPS mode liquid crystal display device. The in-plane phase difference R _e and the thickness direction phase difference R _{th are} preferably -10 to 10 nm, and more preferably -5 to 5 nm. Here, the in-plane phase difference value R _e and the thickness direction phase difference value R _th are values at a wavelength of 590 nm.

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

R _th = [(n _x + n _y )/2 - n _z ] × d.

Where n _x is the refractive index of the slow axis direction (x-axis direction) in the film plane, and n _y is the refraction of the phase axis direction in the film plane (the y-axis direction orthogonal to the x-axis in the plane) rate, n _z is the refractive index of the film thickness direction (z-axis direction perpendicular to the film surface), d is the thickness of the film.

In the zero retardation film, for example, a polyolefin tree including a cellulose resin, a chain polyolefin resin, and a cyclic polyolefin resin can be used. A resin film of a fat, a polyethylene terephthalate resin or a (meth)acrylic resin. Specifically, a cellulose resin, a polyolefin resin, or a (meth)acrylic resin is preferably used because it is easy to adjust the phase difference.

In addition, a film which exhibits optical anisotropy by application/alignment of a liquid crystal compound or a film which exhibits optical anisotropy by application of an inorganic layered compound can also be used as a retardation film. In the case of such a retardation film, there is a temperature-compensated retardation film, and the rod-shaped liquid crystal sold by JX Nippon Mining ENERGY Co., Ltd. under the trade name "NH film" is obliquely aligned. Membrane, a film made of a disc-shaped liquid crystal sold by Fuji FILM (shares) under the trade name "WV film", and a full pair sold by Sumitomo Chemical Co., Ltd. under the trade name "VAC film" A shaft alignment type film, a biaxial alignment type film which is sold under the trade name "new VAC film" by Sumitomo Chemical Co., Ltd., and the like. Further, the resin film laminated on at least one surface of the retardation film may be, for example, the above protective film.

[2] Adhesive layer

The adhesive layer (the aforementioned adhesive layer 20) laminated on at least one side of the optical film of the present invention is an adhesive comprising a (meth)acrylic resin (A), a crosslinking agent (B), and a decane compound (C). The reaction product of the composition is composed of.

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

The (meth)acrylic resin (A) is a constituent unit derived from a (meth)acrylic monomer as a main component (preferably, it contains 50% by weight) The polymer or copolymer of the above) comprises a constituent unit derived from a hydroxyl group-containing (meth) acrylate represented by the following formulas (a1) and (a2).

(wherein, n represents an integer of 1 to 4, A ¹ represents a hydrogen atom or an alkyl group, X ¹ represents a methylene group which may have a substituent, and when n is 2 or more, the substituents may be the same or different)

(wherein, m represents an integer of 5 or more, A ² represents a hydrogen atom or an alkyl group, and X ² represents a methylene group which may have a substituent, and the aforementioned substituents may be the same or different)

In other words, the (meth)acrylic resin (A) of the present invention has a hydroxyalkyl group having a different carbon chain length (n and m) in the side chain, and is estimated to be in the adhesive layer (reaction product of the adhesive composition). The crosslinking density between the (meth)acrylic resins can be optimized. By optimizing the cross-linking density, an adhesive layer having excellent balance between hardness and softness (or having an optimum hardness) can be formed, so that durability can be improved, and peeling of the interface can be effectively suppressed even in a high-temperature environment. (or float) and foaming. Further, even if a strong shrinkage stress is generated, the adhesive layer can effectively alleviate the stress, so that whitening accompanying shrinkage of the optical film (for example, a deflecting plate) can be prevented. Furthermore, by optimizing the crosslink density, reworkability can also be improved (peeling) Detached).

In the formula (a1) and the formula (a2), X ¹ and X ² represent a methylene group which may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), and an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, and a a C _1-10 alkyl group such as a tributyl group, a pentyl group or a hexyl group, preferably a C _1-6 alkyl group, more preferably a C _1-3 alkyl group, a cycloalkyl group (cyclopentyl group, a cyclohexyl group, etc.), Aryl [phenyl, alkylphenyl (tolyl, xylyl), etc.], aralkyl (benzyl or the like), alkoxy (e.g., methoxy, ethoxy, etc. C _1-4 alkoxy) a polyoxyalkylene group (e.g., dioxetylethyl), a cycloalkoxy group (e.g., a C _5-10 cycloalkoxy group such as a cyclohexyloxy group), an aryloxy group (e.g., a phenoxy group, etc.), An aralkoxy group (e.g., benzyloxy group, etc.), an alkylthio group (e.g., a C _1-4 alkylthio group such as a methylthio group or an ethylthio group), a cycloalkylthio group (e.g., a cyclohexylthio group, etc.), an aromatic sulfur A group (e.g., a thiophenoxy group or the like), an aralkylthio group (e.g., a benzylthio group), a mercapto group (e.g., an ethenyl group), a nitro group, a cyano group, or the like. Among these, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or the like is preferable, and an alkyl group (for example, a methyl group or an ethyl group) is particularly preferable.

Each of A ¹ and A ² represents a hydrogen atom or an alkyl group, and the alkyl group may be an alkyl group (preferably a methyl group or the like) exemplified in X ¹ and X ² .

In the formula (a1), n represents an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 2. Further, in the formula (a2), m is an integer of 5 or more (for example, an integer of 5 to 20), preferably 5 to 15 (for example, an integer of 5 to 11), more preferably 5 to 9 (for example, 5 to 7) The integer), especially good 5. Further, m may be an even number of 5 or more (for example, 6, 8, 10, 12, etc.), or may be an odd number of 5 or more (for example, 5, 7, 9, 11, etc.).

Specific examples of the hydroxyl group-containing (meth) acrylate (a1) include 1-hydroxymethyl (meth)acrylate, 1-hydroxyethyl (meth)acrylate, and 1-hydroxyglycol (meth)acrylate. a 1-hydroxy C _1-8 alkyl (meth)acrylate such as an ester, 1-hydroxybutyl (meth)acrylate or 1-hydroxypentyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, 2-hydroxyhexyl (meth)acrylate, etc. (Meth)acrylic acid 2 - Hydroxy C _2-9 alkyl ester; 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 3-hydroxypentyl (meth)acrylate, 3-hydroxy (meth)acrylate 3-hydroxy C _3-10 alkyl (meth)acrylate such as hexyl ester or 3-hydroxyheptyl (meth)acrylate; 4-hydroxybutyl (meth)acrylate; 4-hydroxypentyl (meth)acrylate , 4-hydroxy C _4-11 alkyl (meth)acrylate, such as 4-hydroxyhexyl (meth)acrylate, 4-hydroxyheptyl (meth)acrylate, 4-hydroxyoctyl (meth)acrylate; 2-Chloro-2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and the like. Among these, from the viewpoint of durability, it is preferable that n is 2 in terms of 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. Hydroxy (meth) acrylate; 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 3-hydroxypentyl (meth) acrylate, etc. n is 3 containing a hydroxyl group ( Methyl) acrylate. Particularly preferred is a hydroxyl group-containing (meth) acrylate wherein n is 2, and among these, 2-hydroxyethyl (meth)acrylate is preferred.

Specific examples of the hydroxyl group-containing (meth) acrylate (a2) include 5-hydroxypentyl (meth)acrylate, 5-hydroxyhexyl (meth)acrylate, and 5-hydroxyglycol (meth)acrylate. a 5-hydroxy C _5-12 alkyl (meth)acrylate such as an ester, 5-hydroxyoctyl (meth)acrylate or 5-hydroxydecyl (meth)acrylate; 6-hydroxyhexyl (meth)acrylate, (meth)acrylic acid 6-hydroxyheptyl (meth)acrylate, 6-hydroxyoctyl (meth)acrylate, 6-hydroxydecyl (meth)acrylate, 6-hydroxydecyl (meth)acrylate, etc. - Hydroxy C _6-13 alkyl ester; 7-hydroxyheptyl (meth)acrylate, 7-hydroxyoctyl (meth)acrylate, 7-hydroxydecyl (meth)acrylate, 7-hydroxyl (meth)acrylate 7-hydroxy C _7-14 alkyl (meth)acrylate such as decyl ester, 7-hydroxyundecyl (meth)acrylate; 8-hydroxyoctyl (meth)acrylate, 8-hydroxyindole (meth)acrylate Ester, 8-hydroxydecyl (meth)acrylate, 8-hydroxyundecyl (meth)acrylate, 8-hydroxydodecylate (meth)acrylate, etc. 8-hydroxy C _8-15 alkyl (meth)acrylate Ester; 9-hydroxydecyl (meth)acrylate, 9-hydroxydecyl (meth)acrylate, 9-hydroxyundecyl (meth)acrylate, 9-hydroxydodecyl (meth)acrylate, (A) Acetyl 9-hydroxyl Triesters (meth) acrylate, 9-hydroxyrisperidone C _9-16 alkyl acrylate; (meth) acrylate, 10-hydroxydecyl (meth) acrylate, hydroxybutyl eleven 10- (meth) acrylate, hydroxybutyl ten 10- Diester, 10-hydroxyl-tridecyl acrylate, 10-hydroxycyl (meth) acrylate, etc. 10-hydroxy C _10-17 alkyl (meth) acrylate; 11-hydroxyundecyl (meth) acrylate, 11-hydroxydodecanyl (meth)acrylate, 11-hydroxytridecyl (meth)acrylate, 11-hydroxytetradecyl (meth)acrylate, 11-hydroxypentadecyl (meth)acrylate, etc. (meth)acrylic acid 10-hydroxy C _11-18 alkyl ester; (meth)acrylic acid 12-hydroxydodecyl ester, (meth)acrylic acid 12-hydroxytridecyl ester, (meth)acrylic acid 12-hydroxytetradecyl ester, etc. 12-hydroxy C _12-19 alkyl methacrylate; 13-hydroxy pentadecyl (meth) acrylate, 13-hydroxytetradecyl (meth) acrylate, 13-hydroxy pentadecyl (meth) acrylate, etc. 13-hydroxy C _13-20 alkyl (meth)acrylate; 14-hydroxytetradecyl (meth)acrylate, 14-hydroxypentadecyl (meth)acrylate, etc. (meth)acrylic acid 14-hydroxy C _{14- 21} alkyl acrylate; (meth) acrylate, hydroxybutyl fifteen 15- ester, (meth) acrylic acid esters 15 seventeen hydroxyethyl (meth) acrylate, hydroxyalkyl 15- C _15-22 alkyl acrylate. Among these, from the viewpoint of durability, 5-hydroxypentyl (meth)acrylate, 5-hydroxyhexyl (meth)acrylate, and 5-hydroxyheptyl (meth)acrylate are preferred. A (meth) acrylate having a hydroxyl group of n such as 5-hydroxyoctyl (meth)acrylate or 5-hydroxydecyl (meth)acrylate, and particularly preferably 5-hydroxypentyl (meth)acrylate.

The ratio of the constituent unit derived from the hydroxyl group-containing (meth) acrylate represented by the formula (a1) is preferably 1.5 to 4.5 by weight based on 100 parts by weight of all the constituent units constituting the (meth)acrylic resin. The proportion of the constituent unit derived from the hydroxyl group-containing (meth) acrylate represented by the formula (a2) is preferably 0.25 to 1.0 part by weight. Further, the ratio of the constituent unit derived from the hydroxyl group-containing (meth) acrylate represented by the formula (a1) to the constituent unit derived from the hydroxyl group-containing (meth) acrylate represented by the formula (a2) (weight) The ratio is not particularly limited as long as it is within the above range, and is preferably (a1)/(a2)=13/1 to 3/1 (for example, 11/1 to 3/1), more preferably 9/1 to 4/. 1, especially good for 7/1~5/1. If it is in the above range, it is advantageous in forming an optimum crosslinked structure, and further, characteristics such as durability can be improved.

The (meth)acrylic resin (A) may further comprise a constituent unit derived from an alkyl acrylate (a3) and an alkyl acrylate derived from a substituent. The constituent unit of the ester (a4).

Among the alkyl acrylates (a3), the alkyl acrylate (a3-1) having a glass transition temperature (Tg) of the homopolymer of less than 0 ° C may, for example, be ethyl acrylate, acrylic acid and isopropyl ester, or acrylic acid. And isobutyl ester, n-amyl acrylate, n-isohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-isodecyl acrylate, n- and decyl acrylate, A linear or branched chain alkyl acrylate having an alkyl group such as n-dodecyl acrylate having a carbon number of about 2 to 12. The alkyl acrylate (a3) may also be an alkyl acrylate (cycloalkyl acrylate) having an alicyclic structure, and is preferably from the viewpoint of the followability (or softness or adhesion) to the optical film. The alkyl ester having 2 to 10 carbon atoms is preferably an alkyl ester having 3 to 8 carbon atoms, more preferably an alkyl ester having 4 to 6 carbon atoms, and particularly preferably n-butyl acrylate. When n-butyl acrylate is used, the followability can be improved, and for example, peeling resistance and the like can be favored. These alkyl acrylates (a3-1) may be used alone or in combination of two or more.

Examples of the alkyl acrylate (a3-2) having a Tg of 0 ° C or higher as a homopolymer include methyl acrylate, cycloalkyl acrylate (for example, cyclohexyl acrylate, isodecyl acrylate), stearyl acrylate, acrylic acid. The third butyl ester or the like is particularly preferably methyl acrylate. If methyl acrylate is used, the strength can be increased, which is advantageous for, for example, agglutination failure. These alkyl acrylates (a3-2) may be used alone or in combination of two or more. Further, the Tg of the homopolymer of the alkyl acrylate can be referred to, for example, the literature value of POLYMER HANDBOOK (Wiley-Interscience) or the like.

(meth)acrylic resin (A) derived from acrylic acid The ratio of the constituent unit of the alkyl ester is 100 parts by weight based on all the constituent units constituting the (meth)acrylic resin (A) from the viewpoint of durability and reworkability of the optical film to which the adhesive layer is attached. For example, it is 40 parts by weight or more (for example, 50 to 98 parts by weight), preferably 60 parts by weight or more (for example, 70 to 95 parts by weight), more preferably 70 parts by weight or more (for example, 80 to 90 parts by weight).

When the Tg of the homopolymer is used in combination with an alkyl acrylate of less than 0 ° C and an alkyl acrylate of a homopolymer having a Tg of 0 ° C or higher, both agglomeration resistance and followability (foam resistance and resistance) can be achieved. Exfoliation) improves the durability of dimensional changes to optical films such as polarizers.

The glass transition temperature derived from the homopolymer is a constituent unit of the alkyl acrylate (a3-1) which is less than 0 ° C, and a constituent unit derived from the alkyl acrylate (a3-2) having a glass transition temperature of 0 ° C or higher. The ratio (weight ratio) is (a3-1) / (a3-2) = 20/80 to 95/5 (for example, 30/70 to 90/10), preferably 40/60 to 85/15, more preferably 55/45~75/25. If it is in the above range, the durability can be further improved. The larger the proportion of the constituent units derived from the alkyl acrylate (a3-1) whose glass transition temperature is less than 0 ° C, the higher the followability. The larger the proportion of constituent units derived from the alkyl acrylate (a3-2) having a glass transition temperature of 0 ° C or higher, the more the agglomeration resistance is improved.

The alkyl acrylate (a4) having a substituent is, for example, an alkyl acrylate obtained by introducing a substituent (the hydrogen atom of the alkyl group is substituted with a substituent) to the alkyl group in the alkyl acrylate (a3-1). The substituent may, for example, be an aryl group (phenyl group or the like), an aryloxy group (phenoxy group), an alkoxy group (e.g., a methoxy group, an ethoxy group, etc.) or the like. The alkyl acrylate (a3-3) having a substituent may, for example, be an alkoxyalkyl acrylate (for example, 2-methoxyethyl acrylate or ethoxymethyl acrylate) or an aryloxyalkyl acrylate ( For example, phenoxyethyl acrylate or the like), aryloxy polyalkylene glycol monoacrylate, polyalkylene glycol monoacrylate, and the like. These alkyl acrylates (a3-3) can be used individually or in combination of 2 or more types. By including an alkyl acrylate containing an aromatic ring such as an aryl group or an aryloxy group, the whitening of the polarizing plate during the endurance test can be improved. Further, the alkylene group of the aryloxy polyalkylene glycol monoacrylate and the polyalkylene glycol monoacrylate may be, for example, a C _1-6 alkylene group such as a methylene group, an exoethyl group or a propyl group (preferably The repeating unit of the oxyalkylene group may be, for example, 2 to 7, preferably 2 to 5 (particularly 2) from the viewpoint of durability of the adhesive layer. In the present invention, the (meth)acrylic resin (A) and the crosslinking agent (B) described later are contained in the adhesive composition, and an optimum crosslinked structure (or crosslinking density) can be formed, so that even oxygen is contained. The number of repeating units of alkylene groups is relatively small, and also shows good reworkability. Specifically, examples thereof include phenoxy diethylene glycol acrylate, phenoxy two to seven C _1-3 alkylene glycol acrylate, diethylene glycol monoacrylate two to seven C _1-3, etc. Alkyl monoacrylate and the like.

The ratio of the constituent unit derived from the alkyl acrylate having a substituent is, for example, 0 to 30 parts by weight (for example, 1 to 25) per 100 parts by weight of all the constituent units constituting the (meth)acrylic resin (A). The parts by weight are preferably 3 to 20 parts by weight, more preferably 5 to 15 parts by weight.

The (meth)acrylic resin (A) may contain (meth)acrylates (a1) and (a2) derived from a hydroxyl group, and an alkyl acrylate (a3). And a constituent unit of the monomer (a5) other than the alkyl acrylate (a4) having a substituent. Other monomers may be used alone or in combination of two or more. Examples of the other monomer (a5) include a monomer (a5-1) having a polar functional group other than a hydroxyl group, a acrylamide monomer (a5-2), and a methacrylate (ester of methacrylic acid) ( A5-3), a methacrylamide amine monomer (a5-4), a styrene monomer (a5-5), a vinyl monomer (a5-6), and a plurality of (methyl) groups in the molecule A monomer of acrylonitrile (a5-7), and the like.

The monomer (a5-1) having a polar functional group other than a hydroxyl group may, for example, be a (meth) acrylate having a substituent such as a carboxyl group, a substituted or unsubstituted amino group or a heterocyclic group such as an epoxy group. Specific examples thereof include acryloyl morpholine, vinyl caprolactam, N-vinyl-2-pyrrolidone, vinyl pyridine, (meth)acrylic acid tetrahydrofuran methyl ester, and caprolactone-modified acrylic acid tetrahydrofuran. a monomer having a heterocyclic group such as a methyl ester, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate or 2,5-dihydrofuran; (methyl) a monomer having a substituted or unsubstituted amino group such as aminoethyl acrylate, N,N-dimethylaminoethyl (meth)acrylate, or dimethylaminopropyl (meth)acrylate; (Meth)acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, carboxyalkyl (meth)acrylate (for example, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate), etc. A monomer having a carboxyl group. These monomers may be used alone or in combination of two or more. Moreover, from the viewpoint of preventing the peeling property of the separator which can be laminated on the pressure-sensitive adhesive layer from being lowered, it is preferable that the constituent unit derived from the monomer having an amine group is substantially not contained. In addition, the substantially free means is not related to 100 parts by weight of all the constituent units constituting the (meth)acrylic resin (A). Up to 1.0 part by weight.

In the present invention, even if it does not contain a constituent unit derived from a monomer having a carboxyl group (a constituent unit derived from a carboxyl group-containing (meth) acrylate) which is considered to increase corrosiveness of ITO, it is also high. Durability, both durability and ITO corrosion resistance.

On the other hand, when a constituent unit derived from a monomer having a carboxyl group (a constituent unit derived from a carboxyl group-containing (meth) acrylate) is contained, durability can be further improved. In the present invention, even if the proportion of the constituent unit derived from the carboxyl group-containing (meth) acrylate is small, the durability can be effectively improved, so that corrosion of ITO can be suppressed and durability can be improved.

The ratio of the constituent unit derived from the carboxyl group-containing (meth) acrylate is, for example, 5.0 parts by weight or less (for example, 0 to 3 parts by weight) based on 100 parts by weight of the constituent unit derived from the (meth) acrylate. Preferably, it is 1.0 part by weight or less (for example, 0 to 0.8 part by weight), more preferably 0.5 part by weight or less (for example, 0.001 to 0.5 part by weight), still more preferably 0.3 part by weight or less (for example, 0.005 to 0.3 part by weight), It is preferably 0.2 parts by weight or less (for example, 0.01 to 0.2 parts by weight), particularly preferably 0.15 parts by weight or less (for example, 0.05 to 0.15 parts by weight). When it is at most the upper limit value, ITO corrosion resistance can be suppressed, and if it is at least the lower limit value, durability can be improved.

Examples of the acrylamide-based monomer (a5-2) include N-methylol acrylamide, N-(2-hydroxyethyl) acrylamide, and N-(3-hydroxypropyl) acrylamide. , N-(4-hydroxybutyl) acrylamide, N-(5-hydroxypentyl) acrylamide, N-(6-hydroxyhexyl) acrylamide, N,N-dimethyl decylamine, N,N-diethyl acrylamide, N-isopropyl Acrylamide, N-(3-dimethylaminopropyl)propenylamine, N-(1,1-dimethyl-3-oxobutyl)propenylamine, N-[2- (2-Sideoxy-1-imidazolidinyl)ethyl]propenylamine, 2-propenylamino-2-methyl-1-propanesulfonic acid, N-(methoxymethyl)propene oxime Amine, N-(ethoxymethyl)propenylamine, N-(propoxymethyl)propenylamine, N-(1-methylethoxymethyl)propenylamine, N-(1- Methylpropoxymethyl) acrylamide, N-(2-methylpropoxymethyl) acrylamide [alias: N-(isobutoxymethyl) acrylamide], N-(butyl) Oxymethyl) acrylamide, N-(1,1-dimethylethoxymethyl)propenylamine, N-(2-methoxyethyl)propenylamine, N-(2-B Oxyethyl) acrylamide, N-(2-propoxyethyl) acrylamide, N-[2-(1-methylethoxy)ethyl]propenylamine, N-[2- (1-methylpropoxy)ethyl]propenylamine, N-[2-(2-methylpropoxy)ethyl]propenylamine [alias: N-(2-isobutoxyethyl) Propylene amide, N-(2-butoxyethyl) acrylamide, N-[2-(1,1-dimethylethoxy)ethyl]propenylamine, and the like. Among these, N-(methoxymethyl)propenylamine, N-(ethoxymethyl)propenylamine, N-(propoxymethyl)propenylamine, N-( Butoxymethyl) acrylamide, N-(2-methylpropoxymethyl) acrylamide, and the like.

Examples of the methacrylate (ester of methacrylic acid) (a5-3) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, and methacrylic acid. A linear alkyl methacrylate such as octyl ester or lauryl methacrylate; isobutyl methacrylate, 2-ethylhexyl methacrylate, isooctyl methacrylate, etc. Branched chain alkyl methacrylate; isodecyl methacrylate, cyclohexyl methacrylate, dicyclopentyl methacrylate, cyclododecan methacrylate, methylcyclohexyl methacrylate, A Mono or dicycloalkyl methacrylate such as trimethylcyclohexyl acrylate, t-butylcyclohexyl methacrylate or cyclohexyl phenyl methacrylate; 2-methoxyethyl methacrylate, A An alkoxyalkyl methacrylate such as ethoxymethyl acrylate; an aryl methacrylate such as benzyl methacrylate.

The methacrylamide-based monomer (a5-4) may, for example, be a methacrylamide-based monomer corresponding to the acrylamide-based monomer described in (a5-2).

Examples of the styrene-based monomer (a5-5) include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, and triethylbenzene. Alkyl styrene such as ethylene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene; fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, iodobenzene Halogenated styrene such as ethylene; nitrostyrene; ethoxylated styrene; methoxystyrene; divinylbenzene.

Examples of the vinyl monomer (a5-6) include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl laurate; vinyl chloride and vinyl bromide. Ethylene halide; vinylidene halide such as vinylidene chloride; nitrogen-containing aromatic vinyl such as vinylpyridine, vinylpyrrolidone or vinylcarbazole; butadiene, isoprene, chloroprene, etc. Conjugated diene monomer; unsaturated nitrile such as acrylonitrile or methacrylonitrile.

Examples of the monomer (a5-7) having a plurality of (meth) acrylonitrile groups in the molecule include, for example, 1,4-butanediol di(meth)acrylate and 1,6-hexanediol II ( Methyl) acrylate, 1,9-nonanediol di(meth) acrylate, ethylene glycol di(meth) acrylate, diethylene glycol di(meth) acrylate, tetraethylene glycol bis ( a monomer having two (meth) acrylonitrile groups in a molecule such as a methyl acrylate or a tripropylene glycol di(meth) acrylate; and a trimethylolpropane tri(meth) acrylate or the like has a molecule Three (meth)acrylonitrile groups and the like.

Further, from the viewpoint of reworkability of the optical film 1 with an adhesive layer, the (meth)acrylic resin (A) is preferably derived from methacrylate (ester of methacrylic acid) (a5-3) The ratio (or content) of the constituent units of the methacrylic monomer such as the methacrylamide monomer (a5-4) is small. In other words, the ratio of the constituent unit is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of all the constituent units constituting the (meth)acrylic resin (A). It is 1 part by weight or less.

In addition, the ratio of the constituent units derived from the other monomer (a5) may be, for example, 0 to 20 parts by weight, preferably 100 parts by weight, based on 100 parts by weight of all the constituent units constituting the (meth)acrylic resin (A). It is 0 to 10 parts by weight (for example, 0.001 to 10 parts by weight), more preferably 0 to 5 parts by weight (for example, 0.01 to 3 parts by weight).

The weight average molecular weight (Mw) of the (meth)acrylic resin (A) in terms of standard polystyrene by gel permeation chromatography GPC is, for example, 6.0 × 10 ⁵ to 2.5 × 10 ⁶ (for example, 8.0 × 10 ⁵ to 2.5). ×10 ⁶ ), preferably 1.0 × 10 ⁶ to 2.0 × 10 ⁶ , more preferably 1.2 × 10 ⁶ to 1.8 × 10 ⁶ (for example, 1.3 × 10 ⁶ to 1.6 × 10 ⁶ ). When the Mw is at most the upper limit, it is advantageous from the viewpoint of coatability when the adhesive composition is applied to the substrate, and if the Mw is at least the lower limit, it is advantageous to raise the adhesive layer to the optical film. The follow-up of dimensional changes. The molecular weight distribution expressed by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw/Mn) is usually 2 to 10, preferably 3 to 8, more preferably 4 to 6.

Further, the (meth)acrylic resin (A) preferably has a single peak in the range of 1.0 × 10 ³ to 2.5 × 10 ⁶ in the discharge curve of the GPC. When the (meth)acrylic resin (A) having the number of spikes is used, it is advantageous to improve the durability of the optical film with the adhesive layer and the laminate including the layers.

In the range of the discharge curve obtained in the "having a single peak" in a range means based ^{Mw 1.0 × 10 3 ~ 2.5 ×} 10 6 in holding only one of the maximum value. In the present specification, in the GPC discharge curve, a S/N ratio of 30 or more is defined as a peak. Further, the number of peaks of the GPC discharge curve and the Mw and Mn of the (meth)acrylic resin (A) can be determined by the GPC measurement conditions described in the paragraphs of the examples.

When the (meth)acrylic resin (A) is dissolved in ethyl acetate to form a solution having a concentration of 20% by weight, the viscosity at 25 ° C is preferably 20 Pa‧s or less, more preferably 0.1 to 7 Pa‧s. If it is the viscosity of this range, it is advantageous from the viewpoint of the coatability at the time of apply|coating an adhesive composition to a base material. Alternatively, the viscosity can be determined by a Brookfield viscometer.

The glass transition temperature (Tg) of the (meth)acrylic resin (A) may be, for example, -60 to 0 ° C (for example, -50 to -10 ° C), preferably -50 to -20 ° C, more preferably -40. ~-20 ° C (for example -40 ~ -25 ° C). If it is in this range, it is advantageous in improving durability. In addition, the glass transition temperature can be measured by a differential scanning calorimeter (DSC).

The (meth)acrylic resin (A) can be produced by a known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, or an emulsion polymerization method, and particularly preferably a solution polymerization method. Examples of the solution polymerization method include mixing a monomer and an organic solvent, and adding a thermal polymerization initiator in a nitrogen atmosphere, and stirring at a temperature of about 40 to 90 ° C (preferably 50 to 80 ° C). 3~15 hours or so. For the reaction control, a monomer or a thermal polymerization initiator may be added continuously or intermittently in the polymerization. The monomer or hot starter may also be in a state of being added to an organic solvent.

As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, or the like is used. The photopolymerization initiator may, for example, be 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl) ketone or the like. Examples of the thermal polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 1,1'-azobis (cyclohexane). Alkan-1--1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxy An azo compound such as valeronitrile), dimethyl-2,2'-azobis(2-methylpropionate) or 2,2'-azobis(2-hydroxymethylpropionitrile); Oxidized lauryl, tert-butyl hydroperoxide, benzammonium peroxide, tert-butyl peroxybenzylate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, Peroxidic neodecanoic acid third Organic peroxides such as esters, tert-butyl peroxypivalate, peroxidized (3,5,5-trimethylhexyl), inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide Wait. Further, a redox initiator such as a peroxide and a reducing agent may be used in combination.

The ratio of the polymerization initiator is about 0.001 to 5 parts by weight based on 100 parts by weight of the total amount of the monomers constituting the (meth)acrylic resin. A polymerization method via an active energy ray (for example, ultraviolet ray) can also be used for the polymerization of the (meth)acrylic resin.

Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propanol and isopropanol; acetone, methyl ethyl ketone, and methyl group. Ketones such as isobutyl ketone.

[2-2] Crosslinking agent (B)

The adhesive composition contains a crosslinking agent (B). The crosslinking agent (B) is reacted with a hydroxyl group-containing polar functional group in the (meth)acrylic resin (A). In the present invention, the OH group (hydroxy group) having a hydroxyalkyl group having a different carbon chain (n and m) introduced into the side chain of the (meth)acrylic resin (A) is reacted with the crosslinking agent (B). A crosslinked structure which is advantageous for durability and reworkability is formed.

Examples of the crosslinking agent (B) include a conventional crosslinking agent (for example, an isocyanate compound, an epoxy compound, an aziridine compound, a metal chelate compound, a peroxide, etc.), and specifically, an adhesive composition. Applicability period and durability, crosslinking speed, etc. of the optical film with the adhesive layer From the viewpoint, an isocyanate compound is preferred.

The isocyanate-based compound is preferably a compound having at least two isocyanate groups (-NCO) in the molecule, and examples thereof include an aliphatic isocyanate compound (for example, hexamethylene diisocyanate) and an alicyclic isocyanate compound ( For example, isophorone diisocyanate), an aromatic isocyanate compound (for example, toluene diisocyanate, benzodimethyl diisocyanate, hydrogenated dimethyl diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene Diisocyanate, triphenylmethane triisocyanate, etc.). Further, the crosslinking agent (B) may be an adduct (adduct) of the above-mentioned isocyanate compound via a polyol compound (for example, an adduct via glycerin, trimethylolpropane or the like), isomeric cyanuric acid. An ester group, a biuret type compound, an amine group formed by addition reaction with a polyether polyol, a polyester polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol, or the like A derivative such as an acid ester prepolymer type isocyanate compound. The crosslinking agent (B) may be used alone or in combination of two or more. Among these, typical examples thereof include aromatic isocyanate compounds (for example, toluene diisocyanate and benzodimethyl diisocyanate), aliphatic isocyanate compounds (for example, hexamethylene diisocyanate), or the like. An adduct via a polyol compound (glycerol, trimethylolpropane). When the crosslinking agent (B) is an aromatic isocyanate compound and/or such an adduct via a polyol compound, it is advantageous in forming an optimum crosslinking density (or a crosslinked structure), so that adhesion can be improved. The durability of the optical film of the agent layer. Specifically, if it is a toluene diisocyanate-based compound and/or such an adduct via a polyol compound, durability can be further improved. (For example, durability in the case where an optical film with an adhesive layer is applied to an ITO substrate).

The ratio of the crosslinking agent (B) is, for example, 0.01 to 10 parts by weight (for example, 0.05 to 5 parts by weight), preferably 0.1 to 3 parts by weight based on 100 parts by weight of the (meth)acrylic resin (A). The parts by weight (e.g., 0.1 to 2 parts by weight) are more preferably 0.2 to 1 part by weight (e.g., 0.3 to 0.8 parts by weight). When it is less than the upper limit, it is advantageous for improving the followability (or peeling resistance), and if it is at least the lower limit, it is advantageous for improving the agglomeration resistance (or foaming resistance) or the reworkability.

[2-3] decane compound (C)

The adhesive composition contains a decane compound (C). By including the decane compound (C), the adhesion (or adhesion) of the adhesive layer, the metal layer, the transparent electrode, the glass substrate, and the like can be improved. The decane compound (C) may be a decane compound which can be bonded to a reactive group (for example, an OH group of a hydroxyl group) of the (meth)acrylic resin (A), and examples thereof include vinyl trimethoxy decane and ethylene. Triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, 3-glycidoxypropyl trimethoxy decane, 3-glycidoxypropyl triethoxy decane , 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylethoxydimethyl decane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxy Basear, 1,3-bis(3'-trimethoxypropyl)urea, and the like.

Further, the decane compound (C) may also be a compound of a polyoxyxene oligomer type, and if the polyoxyloxy oligomer is labeled with a combination of monomers, for example, 3-mercaptopropyldi or trisole may be mentioned. Oxydecane-tetramethoxynonane oligomer, 3-mercaptomethyldi or trimethoxydecane-tetraethoxydecane oligomer, 3-mercaptopropyldi or triethoxydecane-tetramethoxy a mercaptoalkyl group-containing oligomer such as a decyl oligo polymer, a 3-decylmethyl di or triethoxy decane-tetraethoxy decane oligomer; and a mercaptoalkyl group-containing oligomer An oligomer obtained by substituting a substituent with another substituent such as 3-glycidoxypropyl group, (meth)acryloxypropyl group, vinyl group, or an amine group.

The decane compound (C) is preferably a decane compound represented by the following formula (c1). When the adhesive composition contains the decane compound represented by the following formula (c1), the adhesion (or adhesion) can be further improved, so that an adhesive layer excellent in peeling resistance can be formed. Further, the adhesive layer is also excellent in reworkability. In particular, even in a high-temperature environment, when the adhesive layer is applied (or laminated) to a transparent electrode (for example, an ITO substrate or the like), the adhesion (or adhesion) can be maintained, and a high degree can be exhibited. Durability.

(wherein B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms; and -CH ₂ - constituting the alkanediyl group and the alicyclic hydrocarbon group may be substituted into -O - or -CO-, R ¹ represents an alkyl group having 1 to 5 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 5 carbon atoms or a carbon number of 1 to 5 Alkoxy)

In the formula (c1), B represents a methylene group, an exoethyl group, a trimethylene group, a tetramethylene group, a hexamethylene group, a hepethylene group, an octamethyl group, and the like, and an alkanediyl group having 1 to 20 carbon atoms. Cyclobutene butyl (e.g. 1,2-cyclopentene butyl), cyclopentyl (e.g. 1,2-cyclopentyl), cyclohexyl (e.g. 1,2-cyclohexyl), cycline a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms such as a group (e.g., 1,2-cyclooctyl); or -CH ₂ - constituting the alkanediyl group and the alicyclic hydrocarbon group, substituted with -O- or -CO-based base. Desirable B is an alkanediyl group having 1 to 10 carbon atoms. R ¹ represents an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a tert-butyl group or a pentyl group, and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 5 carbon atoms as exemplified in the above R ¹ ; or a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a second butoxy group. Alkoxy group having 1 to 5 carbon atoms such as a group and a third butoxy group. Desirable R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are alkoxy groups having 1 to 5 carbon atoms. These decane compounds (C) may be used alone or in combination of two or more.

Specific examples of the decane compound (c1) include (trimethoxyindenyl)methane, 1,2-bis(trimethoxyindenyl)ethane, and 1,2-bis(triethoxyindenyl)B. Alkane, 1,3-bis(trimethoxyindenyl)propane, 1,3-bis(triethoxyindenyl)propane, 1,4-bis(trimethoxydecyl)butane, 1,4- Bis(triethoxyindenyl)butane, 1,5-bis(trimethoxydecyl)pentane, 1,5-bis(triethoxydecyl)pentane, 1,6-bis (trimethyl) Oxyindenyl)hexane, 1,6-bis(triethoxyindenyl)hexane, 1,6-bis(tripropoxydecyl)hexane, 1,8-bis(trimethoxyanthracene) Bis(3C _1-5 alkoxyfluorenyl) such as octane, 1,8-bis(triethoxymethyl)octane, 1,8-bis(tripropoxydecyl)octane C _1-10 alkane; bis(dimethoxymethylindolyl)methane, 1,2-bis(dimethoxymethylindenyl)ethane, 1,2-bis(dimethoxyethylhydrazine) Ethylene, 1,4-bis(dimethoxymethylindenyl)butane, 1,4-bis(dimethoxyethylindenyl)butane, 1,6-bis(dimethoxy Methylmercapto)hexane, 1,6-bis(dimethoxyethylindenyl)hexane, 1,8-bis(dimethoxymethylindenyl)octane, 1,8-double (dimethoxyethylindenyl)octane, etc. Bis(diC _1-5 alkoxy C _1-5 alkyl fluorenyl) C _1-10 alkane; 1,6-bis(methoxydimethylmercapto)hexane, 1,8-bis (A) A bis(mono C _1-5 alkoxy-di C _1-5 alkyl fluorenyl) C _1-10 alkane or the like such as oxydimethylmercapto)octane. Among these, 1,2-bis(trimethoxyindenyl)ethane, 1,3-bis(trimethoxyindenyl)propane, and 1,4-bis(trimethoxyindenyl)butyl are preferred. Alkane, 1,5-bis(trimethoxydecyl)pentane, 1,6-bis(trimethoxydecyl)hexane, 1,8-bis(trimethoxyindenyl)octane, etc. C _1-3 alkoxyindenyl) C _1-10 alkane, particularly preferably 1,6-bis(trimethoxyindenyl)hexane, 1,8-bis(trimethoxyindenyl)octane.

The ratio of the decane compound (C) is, for example, 0.01 to 10 parts by weight (for example, 0.03 to 5 parts by weight), preferably 0.05 to 3 parts by weight, per 100 parts by weight of the (meth)acrylic resin (A). More preferably, it is 0.1 to 1 part by weight (for example, 0.2 to 0.5 part by weight). When it is less than the upper limit, it is advantageous in suppressing the decane compound (C) from oozing out from the adhesive layer, and if it is at least the lower limit value, it is easy to improve the adhesion of the adhesive layer to the metal layer or the glass substrate ( Or adhesion), which is beneficial to improve the peeling resistance and the like.

[2-4] Antistatic agent

The adhesive composition may further comprise an antistatic agent. By including an antistatic agent, the antistatic property of the optical film to which the adhesive layer is attached can be improved (for example, a problem caused by static electricity generated when the release film or the protective film is peeled off) can be suppressed. The antistatic agent may, for example, be a conventional one, and is preferably an ionic antistatic agent. Examples of the cationic component constituting the ionic antistatic agent include an organic cation, an inorganic cation, and the like. Examples of the organic cation include a pyridinium cation, an imidazolium cation, an ammonium cation, a phosphonium cation, and a phosphonium cation. Examples of the inorganic cation include an alkali metal cation such as a lithium cation, a potassium cation, a sodium cation or a phosphonium cation, and an alkaline earth metal cation such as a magnesium cation or a calcium cation. The anion component constituting the ionic antistatic agent may be an inorganic anion or an organic anion, and is preferably an anion component of a fluorine atom in terms of excellent antistatic property. Examples of the anion component of the fluorine-containing atom include a hexafluorophosphate anion (PF ₆ -), a bis(trifluoromethanesulfonyl)imide anion [(CF ₃ SO ₂ ) ₂ N-], and a bis (fluorosulfonate). Indenyl) an imide anion [(FSO ₂ ) ₂ N-], tetrakis(pentafluorophenyl) borate anion [(C ₆ F ₅ ) ₄ B-], and the like. These antistatic agents may be used alone or in combination of two or more. In particular, bis(trifluoromethanesulfonyl)imide anion [(CF ₃ SO ₂ ) ₂ N-], bis(fluorosulfonyl)imide anion [(FSO ₂ ) ₂ N-] is preferred. , tetrakis(pentafluorophenyl)borate anion [(C ₆ F ₅ ) ₄ B-].

The ionic antistatic agent which is solid at room temperature is preferred in terms of excellent stability against time of the antistatic property of the adhesive composition.

The ratio of the antistatic agent is, for example, 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 1 to 3 parts by weight per 100 parts by weight of the (meth)acrylic resin (A).

[2-5] Other ingredients

The adhesive composition may include one or more solvents, cross-linking catalysts, ultraviolet absorbers, weathering stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, light-scattering fine particles, and the like. . Further, it is also useful to blend an ultraviolet curable compound into an adhesive composition, and to form a harder adhesive layer by irradiating ultraviolet rays and hardening them after forming an adhesive layer. Examples of the crosslinking catalyst include hexamethylenediamine, ethylenediamine, polyethylenimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, and isophoronediamine. An amine compound such as trimethylenediamine, a polyamine resin, or a melamine resin.

The adhesive composition may contain a rust preventive agent from the viewpoint of improving the optical film of the adhesive layer and the metal corrosion resistance of the optical laminate. Examples of the rust inhibitor include a triazole compound such as a benzotriazole compound; a thiazole compound such as a benzothiazole compound; an imidazole compound such as a benzyl imidazole compound; an imidazoline compound; and a quinoline compound; Pyridine compound; pyrimidine compound; anthraquinone compound; amine compound; urea compound; sodium benzylate; benzyl fluorenyl compound;

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

As shown in Fig. 1, the optical film 1 with an adhesive layer includes an optical film 10 and an adhesive layer 20 laminated on at least one surface thereof. The adhesive layer 20 is laminated on one or both sides of the optical film 10. When the adhesive layer 20 is laminated on the surface of the optical film 10, it is preferable to form an undercoat layer on the bonding surface of the optical film 10 and/or the bonding surface of the adhesive layer 20, or to perform surface activation treatment (for example, electricity). Pulp treatment, corona treatment, etc.), especially for corona treatment.

In the case where the optical film 10 is a single-sided protective polarizing plate as shown in FIG. 2, the adhesive layer 20 is usually laminated (preferably directly laminated) on the polarizing plate surface, that is, in the polarizing plate 2 and the first resin film. 3 opposite sides. In the case where the optical film 10 is a double-sided protective polarizing plate as shown in FIG. 3, the adhesive layer 20 may be laminated on the outer surface of any of the first and second resin films 3 and 4, or may be laminated on both. Outside.

An antistatic layer may be additionally provided between the optical film 10 and the adhesive layer 20. As the antistatic layer, a lanthanoid material such as polyoxyalkylene oxide, an inorganic metal material such as tin-doped indium oxide or tin-doped cerium oxide, or an organic polymer material such as polythiophene, polystyrene sulfonic acid or polyaniline can be used. .

The optical film 1 with an adhesive layer may also include a separator (release film) laminated on the outer surface of the adhesive layer 20. This separator is usually peeled off when the adhesive layer 20 is used (for example, when laminated to a transparent conductive electrode or a glass substrate). The separator may be, for example, a surface on which the adhesive layer 20 including a film of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, or polyarylate is formed. Oxygen treatment of the isolator.

The optical film 1 with an adhesive layer can constitute the above-mentioned adhesive Each component of the composition of the agent is dissolved or dispersed in a solvent to prepare a solvent-containing adhesive composition, which is then coated/dried on the surface of the optical film 10 to form an adhesive layer 20. Further, the optical film 1 with the adhesive layer may be formed by forming the adhesive layer 20 in the same manner as described above on the release-treated surface of the separator, and laminating (transferring) the adhesive layer 20 to the optical film 10. Obtained from the surface.

The thickness of the adhesive layer is usually 2 to 40 μm, from the viewpoints of the optical film with the adhesive layer and the durability of the optical laminate including the optical laminate, or the reworkability of the optical film with the adhesive layer. Preferably, it is 5 to 30 μm, more preferably 10 to 25 μm. When it is less than the upper limit, the adhesive layer has a good followability (or followability) to the dimensional change of the optical film, and when it is at least the lower limit value, the reworkability becomes good.

The adhesive layer is preferably one having a storage elastic modulus of 0.1 to 5 MPa in a temperature range of 23 to 80 °C. Thereby, the optical film with an adhesive layer and the durability of the optical laminated body containing these can be improved more effectively. "The storage elastic modulus of 0.1 to 5 MPa is exhibited in the temperature range of 23 to 80 ° C" means that the storage elastic modulus is any value within the above range at any temperature in this range. Since the storage elastic modulus generally decreases as the temperature rises, as long as the storage elastic modulus at 23 ° C and 80 ° C is within the above range, it can be assumed that the storage elasticity in the above range is exhibited at the temperature in this range. Modulus. The storage elastic modulus of the adhesive layer can be measured using a commercially available viscoelasticity measuring device such as a viscoelasticity measuring device "DYNAMIC ANALYZER RDA II" manufactured by REOMETRIC.

The gel fraction can be used as an indicator of the crosslink density. this The adhesive layer of the invention has a predetermined crosslink density and thus exhibits a predetermined gel fraction. That is, the gel fraction of the adhesive layer of the present invention may be, for example, 50 to 95% by weight (for example, 55 to 93% by weight), preferably 60 to 90% by weight (for example, 65 to 90% by weight), more preferably 70 to 85% by weight (for example, 80 to 85% by weight). When the gel fraction is at least the lower limit value, it is advantageous in the foaming resistance (agglomerative destructive property) or reworkability of the adhesive layer, and if the gel fraction is equal to or less than the upper limit, it is advantageous in peeling resistance. . Further, the gel fraction can be measured by the method described in the paragraph of the examples.

The adhesive layer of the present invention has a predetermined adhesive force. That is, the adhesive layer is bonded to the glass substrate, and the adhesive force of the adhesive layer after 24 hours at a temperature of 23 ° C and a relative humidity of 50% can be, for example, 0.5 at a peeling speed of 300 mm/min. 25N (for example, 0.5 to 20N), preferably 0.5 to 10N (for example, 1 to 10N), more preferably 1 to 8N. When the adhesive force is at least the lower limit value, the adhesiveness (or adhesion) is improved, and the peeling resistance is favored. When the adhesive force is at most the upper limit value, the reworkability is facilitated. Further, the adhesion can be measured by the method described in the paragraph of the examples.

<Optical laminate>

4 to 8 are schematic cross-sectional views showing an example of an optical layered body according to the present invention.

The optical layered body 5 shown in Fig. 4 is an optical film 1a (or a polarizing plate with an adhesive layer) laminated on the metal layer 30 (or the metal wiring layer 30) laminated on the substrate 40 to the above-mentioned adhesive layer. An optical laminate of the side of the adhesive layer side of 1a). The optical film 1a with the aforementioned adhesive layer is an adhesive layer 20 is laminated on the side of the polarizing plate 2 of the polarizing plate 10a.

The optical layered body 6 shown in Fig. 5 is an adhesive layer side on which the metal layer 30 laminated on the substrate 40 is laminated on the optical film 1b (or the polarizing plate 1b with the adhesive layer) to which the adhesive layer is attached. The optical laminate of the surface. The optical film 1b with the adhesive layer is an optical film in which the adhesive layer 20 is laminated on the surface of the polarizing plate 10b on the second resin film 4 side.

The optical laminates 5 and 6 can be obtained by bonding the optical film (1a, 1b) with the adhesive layer to the metal layer 30 laminated on the substrate 40 via the adhesive layer 20.

As a method of forming the metal layer 30 on the substrate 40, for example, a sputtering method or the like can be mentioned. The substrate 40 may be a transparent substrate constituting a liquid crystal cell included in the touch input element, and is preferably a glass substrate. As a material of the glass substrate, soda lime glass, low alkali glass, alkali-free glass, or the like can be used. The metal layer 30 may be formed on the entire surface of the substrate 40 or may be formed in a part thereof.

The metal layer 30 may be, for example, a layer containing at least one metal element selected from the group consisting of aluminum, copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and an alloy containing two or more of these metals. Among these, from the viewpoint of conductivity, it is preferably a layer containing at least one 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 the aluminum element may preferably be a layer containing an aluminum element as a main component (constituting 50% by weight or more of all metal components of the metal layer 30).

The metal layer 30 may be, for example, a transparent electrode layer of ITO (tin-doped indium oxide) or the like, or may have a transparent electrode layer containing a metal oxide such as ITO together with the metal layer 30. In addition, metal wiring for thin wires can also be used. The layer is placed on a metal mesh on the substrate or a layer in which metal nanoparticles or metal nanowires are added to the binder.

The method of preparing the metal layer 30 is not particularly limited, and may be a metal foil, or may be formed by a vacuum deposition method, a sputtering method, an ion plating method, an inkjet printing method, or a gravure printing method, and is preferably borrowed. The metal layer formed by the sputtering method, the inkjet printing method, or the gravure printing method is more preferably a metal layer formed by sputtering. The thickness of the metal layer 30 is not particularly limited, but is usually 3 μm or less, preferably 1 μm or less, more preferably 0.8 μm or less, and usually 0.01 μm or more. In the case where the metal layer 30 is a metal wiring layer (for example, a metal mesh), the line width of the metal wiring is usually 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less, and usually 0.5 μm or more.

The optical layered body 7 shown in Fig. 6 is an optical layered body in which the adhesive layer 20 of the optical film 1 with the adhesive layer is laminated on the substrate 40.

The optical layered body 8 shown in Fig. 7 is a resin layer 50 which is laminated on the surface of the metal layer 30 laminated on the substrate 40 (on the side opposite to the substrate 40), and laminated thereon. An optical layered body on the side of the adhesive layer 20 of the optical film 1 with an adhesive layer. The resin constituting the resin layer 50 may, for example, be a resin constituting the first or second resin film exemplified above.

In the optical layered body 9 shown in FIG. 8, a plurality of metal layers 30 are laminated on the substrate 40 at intervals in the longitudinal and lateral directions, and a resin layer 50 is formed (or laminated) between the plurality of metal layers 30 (or a gap). The surface of the metal layer 30 (the surface on the opposite side to the substrate 40) is the same as that of the optical layered body 7. In the case of the optical layered body 8 (the metal layer 30 is patterned into a predetermined shape), the metal layer 30 may be, for example, a metal wiring layer (ie, an electrode) having a touch input element of a touch input type liquid crystal display device. Floor).

In the optical laminate 8, a plurality of metal layers 30 may be in contact with the adhesive layer 20 in whole or in part, or may not be in contact. Further, the metal layer 30 may be a continuous film containing the above metal or alloy. Further, the resin layer 50 may be omitted.

After the optical film (1, 1a, 1b) with the adhesive layer is adhered to the substrate 40 (glass substrate, transparent substrate, etc.) or the metal layer 30 (transparent electrode layer) to form an optical layered body, there is any defect. In the case of the case, there is a need to peel off the optical film with the adhesive layer from the substrate 40 or the metal layer 30, and attach the optical film 1 with the other adhesive layer to the substrate 40 or the metal layer 30. The situation of processing operations. The optical film 1 with an adhesive layer according to the present invention is less likely to be illegible or residual on the surface of the glass substrate or the transparent electrode after peeling, and is excellent in reworkability.

<Liquid crystal display device>

The liquid crystal display device according to the present invention is the optical film 1 including the above-described adhesive layer according to the present invention, and more preferably includes the optical laminate. Therefore, the liquid crystal display device according to the present invention has excellent durability.

The liquid crystal display device according to the present invention may have touch Panel function touch input type liquid crystal display device. The touch input type liquid crystal display device includes a touch input element including a liquid crystal cell, and a backlight. The configuration of the touch panel may be a well-known method (for example, an extracellular type, a cell type, an intracellular type, etc.), and the touch panel may be operated in a known manner (for example, a resistive film method or an electrostatic capacitance method). Surface type electrostatic capacitance method, projection type electrostatic capacitance method, etc.). The optical film 1 with an adhesive layer according to the present invention may be disposed on the visual recognition side of the touch input element (liquid crystal cell), may be disposed on the backlight side, or may be disposed on both sides. The driving method of the liquid crystal cell may be any conventionally known method such as a TN method, a VA method, an IPS method, a multi-region method, or an OCB method. Further, in the liquid crystal display device according to the present invention, the substrate 40 having the optical layered body may be a substrate (typically a glass substrate) included in the liquid crystal cell.

[Examples]

Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited by these examples. Hereinafter, the amount of use, the amount of the content, and the % are indicated, and are taken up before being determined in particular, and are based on the weight.

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

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirrer, a solution obtained by mixing a monomer having a composition shown in Table 1 (the numerical value in Table 1 is part by weight) with 81.8 parts of ethyl acetate was charged. After the air in the reaction vessel was replaced with nitrogen, the internal temperature was made 60 °C. Then, add 0.12 parts of azobisisobutyronitrile was dissolved in a solution of 10 parts of ethyl acetate. After maintaining at the same temperature for 1 hour, the internal temperature was maintained at 54 to 56 ° C, and ethyl acetate was continuously added to the reaction vessel at a rate of addition of 17.3 parts/Hr at a polymer concentration of about 35%. After the addition of the ethyl acetate, the internal temperature was maintained at 54 to 56 ° C, and then ethyl acetate was further added and the concentration of the polymer was adjusted to 20% to obtain a (meth)acrylic acid system. An ethyl acetate solution of the resin (A-1). The weight average molecular weight Mw of the obtained (meth)acrylic resin (A-1) was 1.39 million, and the ratio (Mw/Mn) of the weight average molecular weight Mw to the number average molecular weight Mn was 5.32.

<Production Example 2-12: Production of (meth)acrylic resin (A-2 to 12) for an adhesive layer>

An ethyl acetate solution of a (meth)acrylic resin (A-2 to 12) was obtained in the same manner as in Production Example 1 except that the composition of the monomer was changed to the composition shown in Table 1. (Resin concentration: 20 %). The weight average molecular weight Mw of the obtained (meth)acrylic resin (A-2 to 12) is in the range of 1.3 to 1.5 million, and Mw/Mn is in the range of 4 to 6.

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

The glass transition temperature Tg is determined by using a differential scanning calorimeter (DSC) "EXSTAR DSC6000" manufactured by SII NanoTechnology Co., Ltd. under a nitrogen atmosphere at a temperature range of -80 to 50 ° C and a temperature rising rate of 10 ° C / min. Determination.

The composition of the monomers in each of the production examples (the values in Table 1 are parts by weight) are shown in Table 1.

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

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

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

HEA: 2-hydroxyethyl acrylate

4HBA: 4-hydroxybutyl acrylate

5HPA: 5-hydroxypentyl acrylate

PEA: phenoxyethyl acrylate

PEA2: phenoxy diethylene glycol acrylate

BMAA: Butoxymethyl propylene amide

AA: Acrylic

<Examples 1 to 13 and Comparative Examples 1 to 8>

(1) Modulation of adhesive composition

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

In Table 2, the details of the respective blended components indicated by the abbreviation are as follows.

(crosslinking agent)

B-1: Ethyl acetate solution of trimethylolpropane adduct of toluene diisocyanate (solid content: 75%), trade name "Coronate L" obtained from Tosoh Corporation.

B-2: trimethylolpropane adduct of benzenedimethyl diisocyanate Ethyl acetate solution (solids concentration: 75%), trade name "Takenate D-110N" obtained from Mitsui Chemicals Co., Ltd.

(decane compound)

C-1:1,6-bis(trimethoxyindenyl)hexane, C-2:1,8-bis(trimethoxydecyl)hexane, C-3: containing methyl/methoxy Polyoxyl oligo, confidently traded under the trade name "X-40-9250", C-4: 1,3-bis(3'-trimethoxypropyl)urea.

(ionic compound)

D-1: bis(fluorosulfonyl) quinone imine N-mercaptopyridinium, D-2: potassium bis(fluorosulfonyl) phthalimide, D-3: bis(trifluoromethylsulfonyl) Lithium quinone iodide, D-4: N-decylpyridinium tetrakis(pentafluorophenyl)borate.

(2) Production of adhesive layer

The adhesive composition prepared in the above (1) was applied to the polyethylene terephthalate-containing film subjected to release treatment by using an applicator to a thickness of 20 μm after drying. The release treatment surface of the film (trade name "PLR-382051" obtained from LINTEC Co., Ltd.) was dried at 100 ° C for 1 minute to prepare an adhesive layer (adhesive sheet).

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

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

A transparent protective film (KONICA MINOLTA OPTO, trade name "KC2UA", manufactured by KONICA MINOLTA OPTO Co., Ltd.) having a thickness of 25 μm was bonded to the obtained product via an adhesive containing an aqueous solution of a polyvinyl alcohol-based resin. One side of the polarizer. Then, a zero-phase retardation film (trade name "ZEONOR" manufactured by Nippon Zeon Co., Ltd.) containing a cyclic polyolefin resin having a thickness of 23 μm is bonded to the polarized light via an adhesive containing an aqueous solution of a polyvinyl alcohol resin. A polarizing plate was produced on the opposite side of the sheet from the triacetyl cellulose film. Next, after the corona discharge treatment for improving the adhesion is performed on the surface of the zero retardation film opposite to the surface on which the polarizer is in contact with each other, the adhesive prepared in the above (2) is bonded by a laminator. After the surface of the layer opposite to the separator (adhesive layer), it was aged at a temperature of 23 ° C and a relative humidity of 65% for 7 days to obtain an optical film (P-1) with an adhesive layer.

(4) Durability evaluation of optical film with adhesive layer

The optical film (P-1) with the adhesive layer prepared in the above (3) is cut into a size of 300 mm × 220 mm so that the direction of the extension axis of the polarizing plate becomes a long side, and the separator is peeled off, and the exposed film is exposed. The adhesive layer is attached to a glass substrate with a glass substrate or ITO (tin-doped indium oxide). The obtained test piece to which the glass substrate was attached (the optical film with the adhesive layer attached to the glass substrate) was pressurized in an autoclave at a temperature of 50 ° C and a pressure of 5 kg/cm ² (490.3 kPa) for 20 minutes. . An alkali-free glass (trade name "Eagle XG") manufactured by CORNING Co., Ltd. was used as a glass substrate. In addition, as the ITO-attached glass substrate, an ITO layer of 30 nm was formed by ITO vapor deposition on an alkali-free glass (trade name "Eagle XG" manufactured by CORNING Co., Ltd.).

The following three durability tests were carried out for the obtained optical laminate.

[durability test]

‧ Heat resistance test (glass substrate) maintained at a temperature of 95 ° C for 1000 hours, ‧ Heat resistance test (glass with ITO) maintained at a temperature of 95 ° C for 1000 hours, ‧Resistance test (glass substrate) maintained at 1000 °C for 60 hours at a temperature of 60 ° C and a relative humidity of 90% ‧ Maintaining for 30 minutes under dry conditions at a temperature of 85 ° C, followed by drying at a temperature of -40 ° C for 30 minutes as a cycle, repeating 1000 cycles of heat shock (HS) test (glass) Substrate).

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

5: No change in appearance such as floating, peeling, foaming, etc., 4: almost no appearance change such as floating, peeling, foaming, etc. 3: appearance change such as floating, peeling, foaming, etc. is slightly obvious, 2 : Appearance changes such as floating, peeling, and foaming are obvious, and 1: Appearance changes such as floating, peeling, and foaming are remarkably confirmed.

(5) Evaluation of adhesion of optical film with adhesive layer

The optical film (P-1) with the adhesive layer prepared in the above (3) was cut into a test piece having a size of 25 mm × 150 mm. The separator was peeled off from the test piece, and the adhesive surface was attached to the glass substrate. The obtained test piece to which the glass substrate was attached (the optical film with the adhesive layer attached to the glass substrate) was pressurized in an autoclave at a temperature of 50 ° C and a pressure of 5 kg/cm ² (490.3 kPa) for 20 minutes. . After storage for 24 hours in an environment of a temperature of 23 ° C and a relative humidity of 50%, the optical film was peeled off from the test piece together with the adhesive layer at a speed of 300 mm/min toward the 180° direction. The average peel force at the time of peeling was defined as the adhesive force and is shown in Table 3. When the adhesive force is 10 N or less, the reworkability is excellent, and when it is 0.5 N or more, peeling is hard to occur even when the impact is received by the end portion of the polarizing plate.

[Evaluation of ITO Corrosion of Optical Laminates]

The ITO layer of the glass substrate with the ITO layer was measured by a low resistivity meter (trade name "Loresta-AX" manufactured by Mitsubishi Chemical Corporation ANALYTECH Co., Ltd.). Surface resistance of the surface (surface resistance value before the test). Next, the polarizing plate on which the adhesive layer formed in the above (3) was formed was cut into a test piece having a size of 20 mm × 40 mm, and adhered to the ITO layer side of the glass substrate via an adhesive layer. The obtained optical layered body was stored in an oven at a temperature of 60 ° C and a relative humidity of 90% for 500 hours, and then peeled off between the ITO layer and the pressure-sensitive adhesive layer in an environment of a temperature of 23 ° C and a relative humidity of 50%. The surface resistance (surface resistance value after the test) of the ITO layer after peeling was measured. The rate of change in resistance before and after the test was calculated by the following formula and evaluated according to the following criteria. The smaller the rate of change in resistance, the lower the corrosion of ITO. The results are shown in Table 3.

Resistance change rate (%) = [(surface resistance value after test) - (surface resistance value before test)] / [surface resistance value before test] × 100

<Evaluation Criteria for ITO Corrosion>

○: An optical layered body having a resistance change rate of less than 50% and excellent ITO corrosion.

X: The rate of change in electric resistance was 50% or more, and the ITO corrosion resistance of the optical layered product was poor.

(6) Evaluation of antistatic property of optical film with adhesive layer

After peeling off the separator of the obtained polarizing film of the adhesive layer, the surface of the adhesive was measured by a surface specific resistance measuring device [Hiresta-up MCP-HT450 (trade name) manufactured by Mitsubishi Chemical Corporation). resistance. The measurement conditions were carried out under the application of a voltage of 250 V and an application time of 10 seconds. As long as the surface resistance value is 1.0 × 10 ¹² Ω / □ or less, good antistatic properties can be obtained.

[Gel fraction of adhesive sheet]

A method for evaluating the gel fraction of the adhesive sheet of the present invention is shown. The greater the gel fraction, the more crosslinking reaction proceeds in the adhesive and can be used as a benchmark for crosslink density. The gel fraction is a value measured in accordance with the following (1) to (4).

(1) An adhesive sheet having an area of about 8 cm × about 8 cm was bonded to a metal mesh containing SUS304 of about 10 cm × 10 cm (the weight was set to Wm).

(2) The composition obtained in the above (1) was weighed and set to Ws, and secondly, folded four times in a manner of wrapping the adhesive sheet and fixed by a stapler (binding machine). Weigh and weigh the weight as Wb.

(3) The sieve fixed by the stapler in the above (2) was placed in a glass container, and 60 mL of ethyl acetate was added thereto and immersed, and the glass container was stored at room temperature for 3 days.

(4) The screen was taken out from the glass container, dried at 120 ° C for 24 hours, weighed, and the weight was determined as Wa, and the gel fraction was calculated based on the following formula.

Gel fraction (% by weight) = [{Wa-(Wb-Ws)-Wm}/(Ws-Wm)] × 100

1‧‧‧Optical film with adhesive layer

10‧‧‧Optical film

20‧‧‧Adhesive layer

Claims (13)

An optical film with an adhesive layer comprising an optical film and an adhesive layer laminated on at least one side of the optical film, wherein the adhesive layer comprises a (meth)acrylic resin (A) and a crosslinking agent. (B) and a reaction product of the adhesive composition of the decane compound (C), wherein the (meth)acrylic resin (A) contains a hydroxyl group derived from the following formula (a1) ( a constituent unit of a methyl acrylate and a constituent unit derived from a hydroxyl group-containing (meth) acrylate represented by the following formula (a2), In the formula, n represents an integer of 1 to 4, A ¹ represents a hydrogen atom or an alkyl group, X ¹ represents a methylene group which may have a substituent, and when n is 2 or more, the substituents may be the same or different; In the formula, m represents an integer of 5 or more, A ² represents a hydrogen atom or an alkyl group, and X ² represents a methylene group which may have a substituent, and the above substituents may be the same or different. The optical film with an adhesive layer according to claim 1, wherein all the constituent units constituting the (meth)acrylic resin are The ratio of the constituent unit derived from the hydroxyl group-containing (meth) acrylate represented by the formula (a1) is from 1.5 to 4.5 parts by weight, based on 100 parts by weight, derived from the hydroxyl group represented by the formula (a2). The ratio of the constituent units of the acrylate is 0.25 to 1.0 part by weight. The optical film with an adhesive layer according to claim 1 or 2, wherein the (meth)acrylic resin comprises a constituent unit derived from an alkyl acrylate (a3) derived from an alkyl acrylate ( The constituent unit of a3) is a constituent unit containing an alkyl acrylate (a3-1) having a glass transition temperature of less than 0 ° C derived from a homopolymer, and an acrylic acid having a glass transition temperature of 0 ° C or higher derived from a homopolymer. The constituent unit of the alkyl ester (a3-2). The optical film with an adhesive layer according to claim 3, wherein the glass transition temperature derived from the homopolymer is a constituent unit of the alkyl acrylate (a3-1) which is less than 0 ° C, and is derived from The ratio (weight ratio) of the constituent units of the alkyl acrylate (a3-2) having a glass transition temperature of 0 ° C or higher of the homopolymer is (a3-1) / (a3-2) = 20/80 to 95/5. The optical film with an adhesive layer according to any one of claims 1 to 4, wherein the weight average molecular weight of the (meth)acrylic resin is 6.0×10 ⁵ to 2.5× in terms of polystyrene. 10 ⁶ . The optical film with an adhesive layer according to any one of claims 1 to 5, wherein the crosslinking agent (B) is an aromatic isocyanate compound and/or the aromatic isocyanate compound via a polyol compound Additives. The optical film with an adhesive layer according to any one of claims 1 to 6, wherein the ratio of the crosslinking agent (B) is 100 parts by weight relative to the (meth)acrylic resin (A). It is 0.01 to 10 parts by weight. The optical film with an adhesive layer according to any one of claims 1 to 7, wherein the decane compound (C) is a decane compound represented by the following formula (c1), In the formula, B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and -CH ₂ - constituting the alkanediyl group and the alicyclic hydrocarbon group may be substituted into -O- Or -CO-, R ¹ represents an alkyl group having 1 to 5 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 5 carbon atoms or a carbon number of 1 to 5; Alkoxy. The optical film with an adhesive layer according to claim 8, wherein B of the formula (c1) is an alkanediyl group having 1 to 10 carbon atoms, and R ¹ is an alkyl group having 1 to 5 carbon atoms, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkoxy group having 1 to 5 carbon atoms. The optical film with an adhesive layer according to any one of claims 1 to 9, wherein the ratio of the decane compound (C) is 100 parts by weight based on the (meth)acrylic resin (A). It is 0.01 to 10 parts by weight. The optical film with an adhesive layer according to any one of claims 1 to 10, wherein the adhesive layer has a gel fraction of 50 to 95%. The optical film with an adhesive layer according to any one of claims 1 to 11, wherein the adhesive layer is bonded to a glass substrate at a temperature of 23 ° C and a relative humidity of 50%. The adhesive force of the aforementioned adhesive layer after 24 hours was 0.5 to 10 N/25 mm at a peeling speed of 300 mm/min. An optical laminate comprising an optical film with an adhesive layer according to any one of claims 1 to 12.