JP6511580B2 - LAMINATED OPTICAL FILM, METHOD FOR MANUFACTURING THE SAME, AND IMAGE DISPLAY DEVICE - Google Patents

Description

  The present invention relates to a laminated optical film in which a transparent protective film is laminated on at least one surface of an optical film via an adhesive layer formed by curing an adhesive composition, and a method for producing the same. The laminated optical film can form an image display device such as a liquid crystal display (LCD), an organic EL display, a CRT, or a PDP.

  Liquid crystal display devices are rapidly developing in the market for watches, mobile phones, PDAs, laptop computers, monitors for personal computers, DVD players, TVs and the like. The liquid crystal display device visualizes the polarization state by switching of the liquid crystal, and a polarizer is used from the display principle. In particular, in applications such as TVs, increasingly higher brightness, higher contrast, and wider viewing angle are required, and even for polarizing films, increasingly higher transmittance, higher degree of polarization, higher color reproducibility, and the like are required.

  As a polarizer, for example, iodine-based polarizers having a structure in which iodine is adsorbed to polyvinyl alcohol (hereinafter, also simply referred to as “PVA”) and stretched and having a high transmittance and a high polarization degree are most generally widely used. It is used. In general, as the polarizing film, one in which a transparent protective film is attached to both sides of a polarizer by a so-called water-based adhesive in which a polyvinyl alcohol-based material is dissolved in water is used (Patent Document 1 below). As the transparent protective film, triacetyl cellulose having high moisture permeability is used. When the water-based adhesive is used (so-called wet lamination), a drying step is required after laminating the polarizer and the transparent protective film.

  On the other hand, an active energy ray-curable adhesive composition has been proposed instead of the water-based adhesive. In the case of producing a polarizing film using the active energy ray-curable adhesive composition, the productivity of the polarizing film can be improved because a drying step is not required. For example, the present inventors have proposed a radical polymerization type active energy ray-curable adhesive composition using an N-substituted amide-based monomer as a curable component (Patent Document 2 below).

JP 2001-296427 A JP, 2012-052000, A

  An adhesive layer formed using the active energy ray-curable adhesive composition described in Patent Document 2 is excellent in adhesion, but in the market, under an environment inferior to the optical film, for example, under severe humidification conditions And so on may require to have excellent adhesion. For example, although the active energy ray-curable adhesive composition is superior to the water-based adhesive with respect to the humidification optical durability, the conventionally known active energy ray-curable adhesive composition has a room for further improvement. The current situation was.

  This invention is developed in view of the said situation, and it aims at providing the lamination optical film excellent in adhesiveness between an optical film and a transparent protective film.

  MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors paid attention to the interface between the transparent protective film with which a laminated optical film is equipped, and an adhesive bond layer, and conducted earnestly examination. As a result, the inventors have found that the problem can be solved by forming a compatible layer in which the composition of the transparent protective film and the composition of the adhesive layer continuously change at such an interface.

That is, the present invention is a laminated optical film in which a transparent protective film is laminated on at least one surface of an optical film via an adhesive layer formed by curing an adhesive composition, and the transparent protection described above The present invention relates to a laminated optical film characterized in that a compatible layer in which the composition continuously changes is formed between a film and the adhesive layer.

  In the above laminated optical film, the SP value distance between the SP value of the transparent protective film and the SP value of the adhesive composition is preferably 12 or less.

  In the laminated optical film, the compatible layer is formed by applying the adhesive composition after bringing the organic solvent into contact with the surface of the transparent protective film on which the adhesive layer is to be formed. It is preferred that

  In the laminated optical film, the compatible layer is brought into contact with an organic solvent on the surface of the transparent protective film on which the adhesive layer is to be formed, and then the optical film coated with the adhesive composition is obtained. It is preferable that it is formed by bonding to the contact surface with the said organic solvent of the said transparent protective film from the coating surface side of the said adhesive composition.

  In the laminated optical film, after the organic solvent is brought into contact with the surface of the transparent protective film on which the compatible layer is to form the adhesive layer, the contact surface of the transparent protective film with the organic solvent and The adhesive composition is applied to both surfaces of the optical film on the side of the transparent protective film, and the transparent protective film and the optical film are laminated from both coated sides. Is preferred.

  In the above laminated optical film, the SP value distance between the SP value of the transparent protective film and the SP value of the organic solvent is preferably 12 or less.

  In the laminated optical film, the adhesive composition is preferably an active energy ray-curable adhesive composition containing a monomer having a polymerizable group.

  In the laminated optical film, the optical film is preferably a polyvinyl alcohol-based polarizer.

  In the laminated optical film, the transparent protective film is preferably at least one thermoplastic resin selected from the group consisting of polyarylates, polycarbonates, acrylic polymers and triacetylcelluloses.

  The present invention is also a method for producing a laminated optical film in which a transparent protective film is laminated on at least one surface of an optical film via an adhesive layer formed by curing an adhesive composition, A pretreatment step of bringing an organic solvent having an SP value distance of 12 or less with the transparent protective film into contact with the surface of the transparent protective film on which the adhesive layer is to be formed, and the organic solvent of the transparent protective film A coating step of directly coating the adhesive composition on at least one surface of the contact surface and the surface on the transparent protective film side of the optical film, the transparent protective film, and the optical film, the adhesive composition A laminating step of forming a compatible layer in which the composition continuously changes between the transparent protective film and the adhesive layer by laminating them through an object; The optical film and the transparent protective film are adhered via an adhesive layer formed by irradiating the active energy ray from the film side or the transparent protective film side to cure the adhesive composition. The present invention relates to a method for producing a laminated optical film including a bonding step.

  In the method for producing a laminated optical film, it is preferable that an SP value distance between the SP value of the transparent protective film and the SP value of the adhesive composition is 12 or less.

  Furthermore, the present invention relates to an image display apparatus characterized in that the laminated optical film described in any of the above is used.

  In the laminated optical film according to the present invention, a compatible layer in which the composition changes continuously is formed between the transparent protective film and the adhesive layer. Thereby, the adhesion of the laminated optical film is improved due to the improvement of the adhesion between the transparent protective film and the adhesive layer. In particular, when the SP value distance between the SP value of the transparent protective film and the SP value of the adhesive composition is 12 or less, the compatible layer is more reliably formed, and finally the laminated optical film Adhesion is further improved.

  In the present invention, the SP value refers to the solubility parameter proposed by Hansen et al., And such SP value is represented by one point in a three-dimensional space. The affinity between two substances (eg, transparent protective film and adhesive composition) can be evaluated by the distance between two SP values (SP value distance), and the SP value distance between the two substances is small. And affinity is great.

In the present invention, after the organic solvent is brought into contact with the surface of the transparent protective film on which the adhesive layer is to be formed, (1) the adhesive composition is applied to the contact surface of the transparent protective film with the organic solvent. ,
(2) The adhesive composition is applied to an optical film, and the optical film is coated with the adhesive composition of the optical film from the coated side to the contact surface of the transparent protective film with the organic solvent, or (3) the adhesive composition By applying the transparent protective film to the contact surface with the organic solvent and further applying the adhesive composition to the optical film, and then bonding the transparent protective film and the optical film through the adhesive composition. And compatible layers can be formed. When the compatible layer is thus formed, the adhesiveness of the laminated optical film is further improved. The following can be considered as the reason why such an effect can be obtained.

  The transparent protective film which is a constituent material of the laminated optical film has a skin layer (area with a small free volume) on the surface, and such a skin layer has a drawback that the adhesive composition is difficult to penetrate. However, particularly in the laminated optical film provided with the compatible layer formed by the method (1) to (3) above, the skin layer on the surface of the transparent protective film is eliminated, and the adhesive composition easily penetrates. As a result, between the transparent protective film and the adhesive layer, a compatible layer whose composition continuously changes is stably and reliably formed, and the adhesion of the laminated optical film is further improved.

  When the surface of the transparent protective film on which the adhesive layer is to be formed is pretreated with an organic solvent having an SP value distance to the transparent protective film of 12 or less, between the transparent protective film and the adhesive layer, A compatible layer in which the composition changes continuously is formed more stably and reliably, and the optical properties and adhesion of the laminated optical film are particularly improved.

  In the laminated optical film according to the present invention, a transparent protective film is laminated on at least one surface of the optical film via an adhesive layer formed by curing an adhesive composition, and a transparent protective film is formed. It is characterized in that a compatible layer in which the composition of the transparent protective film and the adhesive layer continuously changes is formed between the film and the adhesive layer.

  “A compatible layer in which the composition of the transparent protective film and the adhesive layer changes continuously” is, for example, (1) a cross-sectional image by a Transmission Electron Microscope (TEM), (2) a time-of-flight secondary ion Compositional analysis in the depth direction by time-of-flight secondary ion mass spectrometry (TOF-SIMS), or (3) three-wavelength tube inspection, laser interference, optical interference presence analysis by reflection spectrum, etc. can do.

In the present invention, such a compatible layer can be exemplified as one formed as follows.
(1) A compatible layer formed by applying an adhesive composition after bringing an organic solvent into contact with the surface of the transparent protective film on which the adhesive layer is to be formed;
(2) After bringing the organic solvent into contact with the surface of the transparent protective film on which the adhesive layer is to be formed, the optical film to which the adhesive composition is applied is a transparent protective film from the coated surface side of the adhesive composition The organic solvent is brought into contact with the compatible layer formed by laminating on the contact surface with the organic solvent of (3), or (3) the side of the transparent protective film on which the adhesive layer is to be formed. The adhesive composition was applied to both the surface in contact with the solvent and the surface on the transparent protective film side of the optical film, and it was formed by laminating the transparent protective film and the optical film from both coated surface sides Compatible layer.
Even in any of the above (1) to (3), the skin layer existing on the surface of the transparent protective film is eliminated by treating with an organic solvent, and the adhesive composition becomes a transparent protective film. It becomes easy to penetrate and then the adhesive composition cures to form a compatible layer between the transparent protective film and the adhesive layer, the composition of which changes continuously. In the above (3), an adhesive composition of the same composition may be used as the adhesive composition applied to the transparent protective film and the adhesive composition applied to the optical film, and adhesion of different compositions may be used. Agent compositions may be used. However, even when using adhesive compositions having different compositions, as described later, use adhesive compositions having an SP value distance of 12 or less to the SP value of the transparent protective film constituting the laminated optical film. Is preferred.

  The adhesive composition used as the raw material of the adhesive bond layer with which a lamination | stacking optical film is equipped is demonstrated below. In the present invention, the adhesive composition is preferably cured by irradiation with an active energy ray, and an active energy ray-curable adhesive composition capable of forming an adhesive layer can be used.

<Active energy ray-curable adhesive composition>
The active energy ray-curable adhesive composition which can be used in the present invention can be roughly classified into electron beam-curable, ultraviolet-curable and visible light-curable. Moreover, as a form of hardening, it can be divided into a radical polymerization curing type adhesive composition and a cationically polymerizable adhesive composition. In the present invention, active energy rays in the wavelength range of 10 nm to less than 380 nm are represented as ultraviolet light, and active energy rays in the wavelength range of 380 nm to 800 nm are represented as visible light. In particular, the active energy ray-curable adhesive composition which can be used in the present invention is particularly preferably visible light-curable using visible light of 380 nm to 450 nm.

<1: Radical polymerization curable compound>
Examples of the radically polymerizable compound include compounds having a radically polymerizable functional group of carbon-carbon double bond such as (meth) acryloyl group and vinyl group. As these curable components, either a monofunctional radically polymerizable compound or a bifunctional or higher polyfunctional radically polymerizable compound can be used. Moreover, these radically polymerizable compounds can be used individually by 1 type or in combination of 2 or more types. As these radically polymerizable compounds, for example, compounds having a (meth) acryloyl group are suitable. In the present invention, (meth) acryloyl means an acryloyl group and / or a methacryloyl group, and “(meth)” has the same meaning as follows. Examples of the compound having a (meth) acryloyl group include (meth) acrylamide derivatives having a (meth) acrylamide group, and (meth) acrylates having a (meth) acryloyloxy group. The compounds having a (meth) acryloyl group are exemplified below, but can be selected variously and are not particularly limited. In the active energy ray-curable adhesive composition of the present invention, the content of the radically polymerizable compound is preferably 10% by weight or more.

で表される化合物（ただし、Ｒ^１は水素原子またはメチル基であり、Ｒ^２およびＲ^３はそれぞれ独立に、水素原子、アルキル基、ヒドロキシアルキル基、アルコキシアルキル基または環状エーテル基であって、Ｒ^２およびＲ^３は環状複素環を形成してもよい）が挙げられる。アルキル基、ヒドロキシアルキル基、および／またはアルコキシアルキル基のアルキル部分の炭素数は特に限定されないが、例えば１〜４個のものが例示される。また、Ｒ^２およびＲ^３が形成してもよい環状複素環は、例えばＮ−アクリロイルモルフォリンが挙げられる。 «Monofunctional radically polymerizable compound»
As a monofunctional radically polymerizable compound, for example, the following general formula (1)

Wherein R ¹ is a hydrogen atom or a methyl group, and R ² and R ³ are each independently a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group or a cyclic ether group, R ² and R ³ may form a cyclic heterocyclic ring). The carbon number of the alkyl part of the alkyl group, the hydroxyalkyl group and / or the alkoxyalkyl group is not particularly limited, but is, for example, 1 to 4. Moreover, the cyclic heterocyclic ring which R ² and R ³ may form includes, for example, N-acryloyl morpholine.

  Specific examples of the compound represented by the general formula (1) include, for example, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl ( N-alkyl group-containing (meth) acrylamide derivatives such as meth) acrylamide, N-butyl (meth) acrylamide and N-hexyl (meth) acrylamide; N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N N-hydroxyalkyl group-containing (meth) acrylamide derivatives such as methylol-N-propane (meth) acrylamide; N-alkoxy group-containing (meth) acrylamide derivatives such as N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide etc Be In addition, as the cyclic ether group-containing (meth) acrylamide derivative, a heterocycle-containing (meth) acrylamide derivative in which the nitrogen atom of the (meth) acrylamide group forms a heterocycle is mentioned, for example, N-acryloyl morpholine, N -Acryloyl piperidine, N-methacryloyl piperidine, N-acryloyl pyrrolidine etc. are mention | raise | lifted. Among these, N-hydroxyethyl acrylamide and N-acryloyl morpholine can be suitably used from the point of being excellent in reactivity, being able to obtain a cured product of high elastic modulus, and being excellent in adhesion to a polarizer. it can.

  For example, from the viewpoint of improvement of adhesion and water resistance when bonding a polarizer and a transparent protective film via an adhesive layer, and further improvement of productivity due to high polymerization speed, in an adhesive composition, generally The content of the compound described in Formula (1) is preferably 1 to 50% by weight, and more preferably 3 to 20% by weight. In particular, when the content of the compound described in the general formula (1) is too large, the water absorption of the cured product may be high, and the water resistance may be deteriorated.

  Moreover, the adhesive composition used in this invention may contain another monofunctional radically polymerizable compound as a curable component other than the compound represented by General formula (1). As a monofunctional radically polymerizable compound, the various (meth) acrylic acid derivatives which have a (meth) acryloyloxy group are mentioned, for example. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-methyl-2-nitropropyl (meth) acrylate, n-butyl ( Meta) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 4-methyl-2-propylpentyl ( Meta) acrylate, n-o Tadeshiru (meth) (meth) acrylic acid (1-20 carbon atoms) such as acrylates alkyl esters.

  Moreover, as said (meth) acrylic acid derivative, For example, cycloalkyl (meth) acrylates, such as a cyclohexyl (meth) acrylate and a cyclopentyl (meth) acrylate; Aralkyl (meth) acrylates, such as a benzyl (meth) acrylate; 2-isobornyl (Meth) acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate, dicyclopentenyl (meth) ) Polycyclic (meth) acrylates such as acrylate, dicyclopentenyl oxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, etc .; 2-methoxyethyl (meth) acrylate, 2-ethoxy Ethyl (Meta) Aclay And alkoxy groups such as 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, alkyl phenoxy polyethylene glycol (meth) acrylate or phenoxy group Containing (meth) acrylates; and the like. When the resin composition of the present invention is used as an adhesive of a polarizing film, it contains an alkoxy group or phenoxy group such as phenoxyethyl (meth) acrylate or alkyl phenoxy polyethylene glycol (meth) acrylate from the viewpoint of adhesion to a protective film. It is preferable to contain (meth) acrylate. The content is preferably 1% by weight to 30% by weight with respect to the resin composition.

  Moreover, as said (meth) acrylic acid derivative, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- 4- Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxy lauryl (meth) acrylate And hydroxyl groups such as [4- (hydroxymethyl) cyclohexyl] methyl acrylate, cyclohexanedimethanol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate (Meth) acrylates; epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2, 2-trifluoroethylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, 3-chloro-2- Halogen-containing (meth) acrylates such as hydroxypropyl (meth) acrylate; alkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate; 3-oxetanylmethyl (meth) acrylate And oxetane groups such as 3-methyl-oxetanylmethyl (meth) acrylate, 3-ethyl-oxetanylmethyl (meth) acrylate, 3-butyl-oxetanylmethyl (meth) acrylate and 3-hexyl-oxetanylmethyl (meth) acrylate Containing (meth) acrylate; (meth) acrylate having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate or butyrolactone (meth) acrylate, neopentyl glycol hydroxypivalate (meth) acrylic acid adduct, p-phenylphenol (Meth) acrylate and the like. Among them, 2-hydroxy-3-phenoxypropyl acrylate is preferable because it is excellent in adhesion to various protective films.

  Examples of monofunctional radically polymerizable compounds include carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid and isocrotonic acid.

  In addition, as monofunctional radically polymerizable compounds, for example, lactam vinyl monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, methylvinylpyrrolidone and the like; vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, And vinyl monomers having a nitrogen-containing heterocycle such as vinylpyrrole, vinylimidazole, vinyloxazole and vinylmorpholine.

  Moreover, as a monofunctional radically polymerizable compound, a radically polymerizable compound having an active methylene group can be used. The radically polymerizable compound having an active methylene group is a compound having an active double bond group such as a (meth) acrylic group in the terminal or in the molecule and having an active methylene group. As an active methylene group, an acetoacetyl group, an alkoxy malonyl group, or a cyanoacetyl group etc. are mentioned, for example. It is preferable that the said active methylene group is an acetoacetyl group. Specific examples of the radically polymerizable compound having an active methylene group include, for example, 2-acetoacetoxyethyl (meth) acrylate, 2-acetoacetoxypropyl (meth) acrylate, 2-acetoacetoxy-1-methylethyl (meth) acrylate, etc. Acetoacetoxyalkyl (meth) acrylates; 2-ethoxymalonyloxyethyl (meth) acrylates, 2-cyanoacetoxyethyl (meth) acrylates, N- (2-cyanoacetoxyethyl) acrylamide, N- (2-propionylacetoxybutyl) Acrylamide, N- (4-acetoacetoxymethylbenzyl) acrylamide, N- (2-acetoacetylaminoethyl) acrylamide and the like can be mentioned. The radically polymerizable compound having an active methylene group is preferably acetoacetoxyalkyl (meth) acrylate.

«Multifunctional radically polymerizable compound»
Moreover, as the polyfunctional radically polymerizable compound having two or more functions, for example, N, N'-methylenebis (meth) acrylamide, tripropylene glycol di (meth) acrylate, tetraethylene glycol di, which is a polyfunctional (meth) acrylamide derivative (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di (meth) ) Acrylate, bisphenol A di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate Neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, dioxane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate (Meth) acrylics such as pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO modified diglycerin tetra (meth) acrylate Examples thereof include esterified products of acids and polyhydric alcohols, and 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene. Specific examples include ALONIX M-220 (manufactured by Toagosei Co., Ltd.), light acrylate 1, 9ND-A (manufactured by Kyoeisha Chemical Co., Ltd.), light acrylate DGE-4A (manufactured by Kyoeisha Chemical Co., Ltd.), light acrylate DCP-A (manufactured by Kyoeisha Chemical) , SR-531 (Sartomer), CD-536 (Sartomer) and the like are preferable. Moreover, various epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, various (meth) acrylate type monomers, etc. are mentioned as needed. The polyfunctional (meth) acrylamide derivative has high polymerization speed and excellent productivity, and is excellent in the crosslinkability when the resin composition is a cured product, and therefore, is preferably contained in the adhesive composition.

  A radically polymerizable compound is a combination of a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound from the viewpoint of achieving both the adhesiveness with a polarizer and various transparent protective films and the optical durability under severe environments. Is preferred. In addition, since a monofunctional radically polymerizable compound has comparatively low liquid viscosity, the liquid viscosity of a resin composition can be reduced by containing a resin composition. Moreover, a monofunctional radically polymerizable compound often has a functional group that expresses various functions, and when it is contained in a resin composition, it expresses various functions in the cured product of the resin composition and / or the resin composition. It can be done. The polyfunctional radically polymerizable compound is preferably contained in the resin composition because the cured product of the resin composition can be three-dimensionally crosslinked. The ratio of the monofunctional radically polymerizable compound to the polyfunctional radically polymerizable compound is to mix the polyfunctional radically polymerizable compound in the range of 10 parts by weight to 1,000 parts by weight with respect to 100 parts by weight of the monofunctional radically polymerizable compound Is preferred.

<2: Cationic Polymerizable Adhesive Composition>
The cationically polymerizable compound used in the cationically polymerizable adhesive composition includes a monofunctional cationically polymerizable compound having one cationically polymerizable functional group in the molecule, and two or more cationically polymerizable functional groups in the molecule. It is classified into having a multifunctional cationically polymerizable compound. Since the monofunctional cationically polymerizable compound has a relatively low liquid viscosity, the liquid viscosity of the resin composition can be reduced by containing the monofunctional cationic polymerizable compound in the resin composition. Moreover, a monofunctional cationically polymerizable compound often has a functional group that exhibits various functions, and when it is contained in the resin composition, it exhibits various functions in the cured product of the resin composition and / or the resin composition. It can be done. The polyfunctional cationically polymerizable compound is preferably contained in the resin composition because the cured product of the resin composition can be three-dimensionally crosslinked. The ratio of the monofunctional cationic polymerizable compound to the multifunctional cationic polymerizable compound is to mix the polyfunctional cationic polymerizable compound in a range of 10 parts by weight to 1000 parts by weight with respect to 100 parts by weight of the monofunctional cationic polymerizable compound. Is preferred. As a cationically polymerizable functional group, an epoxy group, an oxetanyl group, and a vinyl ether group are mentioned. As a compound which has an epoxy group, an aliphatic epoxy compound, an alicyclic epoxy compound, and an aromatic epoxy compound are mentioned, As a cationically polymerizable adhesive composition of this invention, since it is excellent in curability and adhesiveness, It is particularly preferred to contain a cycloaliphatic epoxy compound. As the alicyclic epoxy compound, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, caprolactone-modified product of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and trimethylcaprolactone-modified product And valerolactone modified products, etc. Specifically, celoxide 2021, celoxide 2021A, celoxide 2021 P, celoxide 2081, celoxide 2083, celoxide 2085 (manufactured by Daicel Chemical Industries, Ltd.), Cyracure UVR-6105, Cyracure UVR -6107, Cyracure 30, R-6110 (all manufactured by Dow Chemical Japan Ltd.), etc. The compound having an oxetanyl group is cationically polymerizable according to the present invention. It is preferable that the adhesive composition has an effect of improving the curability of the adhesive composition or reducing the liquid viscosity of the composition, and the compound having an oxetanyl group is 3-ethyl-3-hydroxymethyl oxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, di [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl -3- (2-ethylhexyloxymethyl) oxetane, phenol novolac oxetane, etc., and aron oxetane OXT-101, aron oxetane OXT-121, aron oxetane OXT-211, aron oxetane OXT-221, aron oxetane OXT-212 (The above, manufactured by Toagosei Co., Ltd.) and the like are commercially available. It is preferable to incorporate a compound having a vinyl ether group, since it has the effect of improving the curability of the cationically polymerizable adhesive composition of the present invention or reducing the liquid viscosity of the composition. As 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, cyclohexane dimethanol monovinyl ether, tricyclodecane vinyl ether, cyclohexyl vinyl ether, methoxy Ethyl vinyl ether, ethoxyethyl vinyl ether, pentaerythritol type tetravinyl ether and the like can be mentioned.

  The cell inhibitor is a compound capable of reducing the surface tension by being incorporated into the adhesive composition, and thereby has an effect of reducing the air bubbles between the adherend to be bonded. Examples of the bubble suppressor include silicone-based bubble suppressors having a polysiloxane skeleton such as polydimethylsiloxane, (meth) acrylic bubble suppressors having a (meth) acrylic skeleton obtained by polymerizing (meth) acrylic acid ester, etc. When added to an adhesive composition, such as a polyether foam inhibitor obtained by polymerizing a vinyl ether or cyclic ether, or a fluorofoam inhibitor composed of a fluorine compound having a perfluoroalkyl group, the surface tension is reduced Can be used with the following effects.

  Examples of the reactive group possessed by the cell inhibitor include polymerizable functional groups, and specific examples thereof include radically polymerizable functional groups having an ethylenic double bond such as (meth) acryloyl group, vinyl group and allyl group, and glycidyl. Examples thereof include epoxy groups such as groups, oxetane groups, vinyl ether groups, cyclic ether groups, cyclic thioether groups, and cationically polymerizable functional groups such as lactone groups. From the viewpoint of reactivity in the adhesive composition, a cell inhibitor having a double bond as a reactive group is preferable, and more preferably a cell inhibitor having a (meth) acryloyl group.

  Among the above-mentioned air bubble suppressors, silicone air bubble suppressors are preferable in consideration of the laminate air bubble suppressing effect and the adhesive property improving effect. Further, among the air bubble suppressors, in consideration of the adhesion of the adhesive layer, those containing a urethane bond or an isocyanurate ring structure in the main chain skeleton or side chain are preferable. A commercial item can also be used conveniently as a silicone type foam control agent, for example, "BYK-UV3505" (made by BIC-Chemie Japan company) which is an acryl group modified polydimethylsiloxane is mentioned.

  In order to achieve both the adhesive strength of the obtained adhesive layer and the reduction effect of the laminated air bubbles, when the total amount of the adhesive composition is 100% by weight, the content of the air bubble suppressor is 0.01 to 0. It is preferably 6% by weight.

<Aspect of Radically Polymerizable Adhesive Composition>
When using an electron beam or the like for the active energy ray, the adhesive composition does not need to contain a photopolymerization initiator, but when ultraviolet or visible light is used for the active energy ray, the adhesive composition The substance preferably contains a photopolymerization initiator.

«Photoinitiator»
The photoinitiator in the case of using a radically polymerizable compound is suitably selected by the active energy ray. In the case of curing with ultraviolet light or visible light, ultraviolet or visible light cleaving photoinitiators are used. Examples of the photopolymerization initiator include benzophenone compounds such as benzyl, benzophenone, benzoylbenzoic acid and 3,3'-dimethyl-4-methoxybenzophenone; 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2) Aromatic ketone compounds such as -propyl) ketone, α-hydroxy-α, α'-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, α-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy- Acetophenone compounds such as 2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropane-1, etc .; Benzoin methyl ether, Benzoin ethyl ether, benzoin Benzoin alkyl ether compounds such as isopropyl ether, benzoin butyl ether and anisoin methyl ether; aromatic ketal compounds such as benzyl dimethyl ketal; aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; 1-phenone Photoactive oxime compounds such as 1,1-propanedione-2- (o-ethoxycarbonyl) oxime; thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4- Thioxanthone compounds such as dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone; camphor quinone; halogenated ketones; Le phosphino sulfoxide; an acyl phosphonium diisocyanate and the like.

  The compounding quantity of the said photoinitiator is 20 weight% or less with respect to whole quantity of adhesive composition. The blending amount of the photopolymerization initiator is preferably 0.01 to 20% by weight, more preferably 0.05 to 10% by weight, and further preferably 0.1 to 5% by weight.

  When the adhesive composition used in the present invention is used for visible light curing containing a radically polymerizable compound as a curing component, a photopolymerization initiator highly sensitive to light of 380 nm or more is used in particular. Is preferred. The highly sensitive photopolymerization initiator for light of 380 nm or more will be described later.

（式中、Ｒ^４およびＲ^５は−Ｈ、−ＣＨ_２ＣＨ_３、−ｉＰｒまたはＣｌを示し、Ｒ^４およびＲ^５は同一または異なっても良い）を単独で使用するか、あるいは一般式（２）で表される化合物と後述する３８０ｎｍ以上の光に対して高感度な光重合開始剤とを併用することが好ましい。一般式（２）で表される化合物を使用した場合、３８０ｎｍ以上の光に対して高感度な光重合開始剤を単独で使用した場合に比べて接着性に優れる。一般式（２）で表される化合物の中でも、Ｒ^４およびＲ^５が−ＣＨ_２ＣＨ_３であるジエチルチオキサントンが特に好ましい。接着剤組成物中の一般式（４）で表される化合物の組成比率は、接着剤組成物の全量に対して、０．１〜５重量％であることが好ましく、０．５〜４重量％であることがより好ましく、０．９〜３重量％であることがさらに好ましい。 As the photopolymerization initiator, a compound represented by the following general formula (2):

(Wherein R ⁴ and R ^{5 each} represent —H, —CH ₂ CH ₃ , —iPr or Cl, and R ⁴ and R ⁵ may be the same or different) or used alone or as It is preferable to use together the compound represented by 2) and a highly sensitive photoinitiator for light of 380 nm or more described later. When the compound represented by General formula (2) is used, it is excellent in adhesiveness compared with the case where a highly sensitive photoinitiator is used alone with respect to the light 380 nm or more. Among the compounds represented by the general formula (2), diethylthioxanthone in which R ⁴ and R ⁵ are —CH ₂ CH ₃ is particularly preferable. The composition ratio of the compound represented by the general formula (4) in the adhesive composition is preferably 0.1 to 5% by weight with respect to the total amount of the adhesive composition, and 0.5 to 4%. %, More preferably 0.9 to 3% by weight.

  Moreover, it is preferable to add a polymerization start auxiliary as needed. As a polymerization initiation aid, triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, etc. And ethyl 4-dimethylaminobenzoate is particularly preferred. When using a polymerization start auxiliary, the addition amount thereof is usually 0 to 5% by weight, preferably 0 to 4% by weight, and most preferably 0 to 3% by weight, with respect to the total amount of the adhesive composition.

  Moreover, a well-known photoinitiator can be used together as needed. Since the transparent protective film having UV absorbing ability does not transmit light of 380 nm or less, it is preferable to use a photopolymerization initiator highly sensitive to light of 380 nm or more as the photopolymerization initiator. Specifically, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 , 2- (Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine Oxide, bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) 1-yl) -phenyl) titanium and the like.

（式中、Ｒ^６、Ｒ^７およびＲ^８は−Ｈ、−ＣＨ_３、−ＣＨ_２ＣＨ_３、−ｉＰｒまたはＣｌを示し、Ｒ^６、Ｒ^７およびＲ^８は同一または異なっても良い）を使用することが好ましい。一般式（３）で表される化合物としては、市販品でもある２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン（商品名：ＩＲＧＡＣＵＲＥ９０７ メーカー：ＢＡＳＦ）が好適に使用可能である。その他、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１（商品名：ＩＲＧＡＣＵＲＥ３６９ メーカー：ＢＡＳＦ）、２−（ジメチルアミノ）−２−［（４−メチルフェニル）メチル］−１−［４−（４−モルホリニル）フェニル］−１−ブタノン（商品名：ＩＲＧＡＣＵＲＥ３７９ メーカー：ＢＡＳＦ）が感度が高いため好ましい。 In particular, a compound represented by the following general formula (3) in addition to the photopolymerization initiator of the general formula (2) as a photopolymerization initiator;

(Wherein, R ⁶ , R ⁷ and R ^{8 each} represent —H, —CH ₃ , —CH ₂ CH ₃ , —iPr or Cl, and R ⁶ , R ⁷ and R ⁸ may be the same or different) It is preferred to use. As the compound represented by the general formula (3), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE 907 manufacturer: BASF) which is also a commercial product is preferable It can be used for In addition, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE 369 manufacturer: BASF), 2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE 379 manufacturer: BASF) is preferred because of its high sensitivity.

<Radical Polymerizable Compound Having Active Methylene Group and Radical Polymerization Initiator Having a Hydrogen-Extracting Action>
When a radically polymerizable compound having an active methylene group is used as the radically polymerizable compound in the adhesive composition, it is preferable to use it in combination with a radical polymerization initiator having a hydrogen abstraction function. According to such a configuration, the adhesiveness of the adhesive layer of the polarizing film is remarkably improved, even in a high humidity environment or immediately after being taken out of water (in a non-dried state). Although this reason is not clear, the following causes can be considered. That is, the radically polymerizable compound having an active methylene group is incorporated into the main chain and / or side chain of the base polymer in the adhesive layer while polymerizing with other radically polymerizable compounds constituting the adhesive layer, and adhesion Form an agent layer. In the polymerization process, when a radical polymerization initiator having a hydrogen abstraction function is present, hydrogen is abstracted from the radically polymerizable compound having an active methylene group while forming a base polymer constituting the adhesive layer, to form a methylene group. Radicals are generated. And the methylene group which radical generate | occur | produced and the hydroxyl group of polarizers, such as PVA, react, and a covalent bond is formed between an adhesive bond layer and a polarizer. As a result, it is presumed that the adhesion of the adhesive layer of the polarizing film is significantly improved even in the non-dried state.

In the present invention, examples of the radical polymerization initiator having a hydrogen abstraction action include thioxanthone radical polymerization initiators and benzophenone radical polymerization initiators. The radical polymerization initiator is preferably a thioxanthone radical polymerization initiator. As a thioxanthone type radical polymerization initiator, the compound represented, for example by the said General formula (2) is mentioned. As a specific example of a compound represented by General formula (2), a thioxanthone, a dimethyl thioxanthone, a diethyl thioxanthone, isopropyl thioxanthone, a chloro thioxanthone etc. are mentioned, for example. Among the compounds represented by the general formula (2), diethylthioxanthone in which R ⁴ and R ⁵ are —CH ₂ CH ₃ is particularly preferable.

  When the adhesive composition contains a radically polymerizable compound having an active methylene group and a radical polymerization initiator having a hydrogen abstraction function, the active methylene when the total amount of the curable component is 100% by weight. It is preferable to contain 1 to 50% by weight of a radically polymerizable compound having a group, and 0.1 to 10% by weight of a radical polymerization initiator based on the total amount of the curable resin composition.

  As described above, in the present invention, a radical is generated in the methylene group of a radically polymerizable compound having an active methylene group in the presence of a radical polymerization initiator having a hydrogen abstraction function, and such a methylene group and a polarizer such as PVA React with the hydroxyl group of to form a covalent bond. Therefore, in order to generate radicals in the methylene group of the radically polymerizable compound having an active methylene group and sufficiently form such covalent bond, the radical having an active methylene group when the total amount of the curable component is 100% by weight. The polymerizable compound is preferably contained in an amount of 1 to 50% by weight, and more preferably 3 to 30% by weight. In order to sufficiently improve the water resistance and improve the adhesion in the non-dried state, the content of the radically polymerizable compound having an active methylene group is preferably 1% by weight or more. On the other hand, if it exceeds 50% by weight, curing failure of the adhesive layer may occur. The content of the radical polymerization initiator having a hydrogen abstracting action is preferably 0.1 to 10% by weight, more preferably 0.3 to 9% by weight, based on the total weight of the adhesive composition. . In order for the hydrogen abstraction reaction to proceed sufficiently, it is preferable to use a radical polymerization initiator at 0.1% by weight or more. On the other hand, if it exceeds 10% by weight, it may not be completely dissolved in the composition.

<Photo cationic polymerization initiator>
The cationically polymerizable adhesive composition contains at least one compound selected from the compound having an epoxy group, the compound having an oxetanyl group, and the compound having a vinyl ether group described above as a curable component, and all of them are cationically polymerized. The photo cationic polymerization initiator is blended because it is cured by the The photocationic polymerization initiator generates a cationic species or a Lewis acid by irradiation of active energy rays such as visible light, ultraviolet rays, X-rays and electron beams, and starts polymerization reaction of an epoxy group or oxetanyl group. As the photocationic polymerization initiator, a photoacid generator and a photobase generator can be used, and a photoacid generator described later is suitably used. When the adhesive composition used in the present invention is used with visible light curing, it is preferable to use a photocationic polymerization initiator which is highly sensitive to light of 380 nm or more, but it is preferable to use a photocationic polymerization initiator. In general, since the compound exhibits maximum absorption in a wavelength range around 300 nm or shorter, it is possible to incorporate a photosensitizer exhibiting maximum absorption in light of a longer wavelength range, specifically, a wavelength longer than 380 nm. It can be sensitive to light of a wavelength near this, and can promote the generation of cationic species or acid from the photocationic polymerization initiator. Examples of photosensitizers include anthracene compounds, pyrene compounds, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, photoreducible dyes and the like. Two or more types may be mixed and used. In particular, anthracene compounds are preferable because they are excellent in photosensitizing effect, and specific examples thereof include Anthracure UVS-1331 and Anthracure UVS-1221 (manufactured by Kawasaki Kasei Co., Ltd.). The content of the photosensitizer is preferably 0.1% by weight to 5% by weight, and more preferably 0.5% by weight to 3% by weight.

<Other ingredients>
The adhesive composition used in the present invention preferably contains the following components.

<Acrylic oligomer>
The adhesive composition used in the present invention may contain an acrylic oligomer obtained by polymerizing a (meth) acrylic monomer, in addition to the curable component of the radically polymerizable compound. By containing the components in the adhesive composition, the cure shrinkage when the composition is irradiated and cured with active energy rays is reduced, and the adhesive and the adherend such as a polarizer and a transparent protective film Interface stress can be reduced. As a result, it is possible to suppress the decrease in the adhesion between the adhesive layer and the adherend. In order to sufficiently suppress the cure shrinkage of the cured product layer (adhesive layer), the content of the acrylic oligomer is preferably 20% by weight or less with respect to the total amount of the adhesive composition, and is preferably 15% It is more preferable that the content is less than%. When the content of the acrylic oligomer in the adhesive composition is too large, the reaction rate at the time of irradiating the composition with active energy rays is extremely reduced, which may result in curing failure. On the other hand, the acrylic oligomer is preferably contained in an amount of 3% by weight or more, more preferably 5% by weight or more, based on the total amount of the adhesive composition.

The adhesive composition preferably has a low viscosity when considering the workability and uniformity at the time of coating, and therefore it is preferable that the acrylic oligomer formed by polymerizing a (meth) acrylic monomer also have a low viscosity. . As an acrylic oligomer having a low viscosity and capable of preventing cure shrinkage of the adhesive layer, one having a weight average molecular weight (Mw) of 15000 or less is preferable, one having a weight average of 10000 or less is more preferable, and one having a weight of 5000 or less preferable. On the other hand, in order to sufficiently suppress the cure shrinkage of the cured product layer (adhesive layer), the weight average molecular weight (Mw) of the acrylic oligomer is preferably 500 or more, and more preferably 1,000 or more. It is particularly preferable that it is 1500 or more. Specific examples of the (meth) acrylic monomer constituting the acrylic oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate and 2-methyl- 2-nitropropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, S-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (Meth) acrylate, 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, cetyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl ( Meta) acrylate (Meth) acrylic acid (1 to 20 carbon atoms) alkyl esters such as 4-methyl-2-propylpentyl (meth) acrylate and N-octadecyl (meth) acrylate; further, for example, cycloalkyl (meth) acrylate (eg , Cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate etc., aralkyl (meth) acrylates (eg benzyl (meth) acrylate etc.), polycyclic (meth) acrylates (eg 2-isobornyl (meth) acrylate, 2 -Norbornylmethyl (meth) acrylate, 5-norbornen-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (meth) acrylate etc., hydroxyl group-containing (meth) acrylic acid ester Class (eg, hydro 2-ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropylmethyl-butyl (meth) methacrylate etc., alkoxy group or phenoxy group-containing (meth) acrylic acid esters (2-methoxyethyl Meta) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate etc., epoxy Group-containing (meth) acrylic acid esters (eg, glycidyl (meth) acrylate etc.), halogen-containing (meth) acrylic acid esters (eg, 2,2,2-trifluoroethyl (meth) acrylate, 2,2, 2- Trifluoroethylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, etc., alkylaminoalkyl (meth) Acrylate (for example, dimethylaminoethyl (meth) acrylate etc.) etc. are mentioned. These (meth) acrylates can be used alone or in combination of two or more. Specific examples of the acrylic oligomer include “ARUFON” manufactured by Toagosei Co., Ltd., “Actflow” manufactured by Soken Chemical Co., Ltd., “JONCRYL” manufactured by BASF Japan, and the like.

<Photo acid generator>
The adhesive composition may contain a photoacid generator. When a photoacid generator is contained in the adhesive composition, the water resistance and durability of the adhesive layer can be dramatically improved as compared to the case where the photoacid generator is not contained. The photoacid generator can be represented by the following general formula (4).

（ただし、Ｌ^＋は、任意のオニウムカチオンを表す。また、Ｘ⁻は、ＰＦ_６ ⁻、ＳｂＦ_６ ⁻、ＡｓＦ_６ ⁻、ＳｂＣｌ_６ ⁻、ＢｉＣｌ_５ ⁻、ＳｎＣｌ_６ ⁻、ＣｌＯ_４ ⁻、ジチオカルバメートアニオン、ＳＣＮ⁻よりからなる群より選択されるカウンターアニオンを表す。） General formula (4)

(However, L ⁺ represents any onium cation.) X ⁻ represents PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, SCN ^- represents a counter anion selected from the group more consisting).

Next, the counter anion X ⁻ in the general formula (4) will be described.

Formula (4) counter anion X in ^- are but are not theoretically limited to, non-nucleophilic anion is preferred. In the case where the counter anion X ^- is a non-nucleophilic anion, the photoacid generator represented by the general formula (4) as a result itself is less likely to cause a nucleophilic reaction in the cation coexisting in the molecule and various materials used in combination. And it is possible to improve the temporal stability of the composition using it. The non-nucleophilic anion as used herein refers to an anion having a low ability to cause a nucleophilic reaction. Such anions include PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, SCN ^{− and the} like.

  Specifically, “Cyracure UVI-6992”, “Cyracure UVI-6974” (above, made by Dow Chemical Japan Ltd.), “Adeka Optomer SP150”, “Adeka Optomer SP 152”, “Adeka Optomer SP170 "," ADEKA OPTOMER SP172 "(above, made by ADEKA Corporation)," IRGACURE 250 "(made by Ciba Specialty Chemicals)," CI-5102 "," CI-2855 "(above, made by Nippon Soda Co., Ltd.), “San Aid SI-60L”, “San Aid SI-80 L”, “San Aid SI-100 L”, “San Aid SI-110 L”, “San Aid SI-180 L” (all manufactured by Sanshin Chemical Co., Ltd.), “CPI-100 P”, “CPI-100A” (above, manufactured by San-Apro Co., Ltd.), “WPI-069 "WPI-113", "WPI-116", "WPI-041", "WPI-044", "WPI-054", "WPI-055", "WPAG-281", "WPAG-567", " WPAG-596 "(all manufactured by Wako Pure Chemical Industries, Ltd.) can be mentioned as a preferred specific example of the photoacid generator of the present invention.

  The content of the photoacid generator is 10% by weight or less, preferably 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the adhesive composition. More preferably, 0.1 to 3% by weight is particularly preferable.

<Photo base generator>
The photobase generator can function as a catalyst for the polymerization reaction of a radically polymerizable compound or an epoxy resin, when the molecular structure is changed by light irradiation such as ultraviolet light or visible light, or the molecule is cleaved. It is a compound that produces one or more basic substances. The basic substance is, for example, a secondary amine or a tertiary amine. As the photo base generator, for example, the above α-aminoacetophenone compound, the above oxime ester compound, an acyloxyimino group, N-formylated aromatic amino group, N-acylated aromatic amino group, nitrobenzyl carbamate group, alco The compound which has substituents, such as an oxy benzyl carbamate group, is mentioned. Among them, oxime ester compounds are preferable.

  Examples of the compound having an acyloxyimino group include O, O'-succinic acid diacetophenone oxime, O, O'-succinic acid dinaphthophenone oxime, and benzophenone oxime acrylate-styrene copolymer.

  Examples of the compound having an N-formylated aromatic amino group and an N-acylated aromatic amino group include di-N- (p-formylamino) diphenylmethane, di-N (p-aceethylamino) diphenyl melan, Di-N- (p-benzoamido) diphenylmethane, 4-formylamino toluylene, 4-acetylamino toluylene, 2,4-diformylamino toluylene, 1-formylaminonaphthalene, 1-acetylaminonaphthalene, 1,5 -Diformylaminonaphthalene, 1-formylaminoanthracene, 1,4-diformylaminoanthracene, 1-acetylaminoanthracene, 1,4-diformylaminoanthraquinone, 1,5-diformylaminoanthraquinone, 3,3'- Dimethyl-4,4'-diformylaminobiphenyl 4, '- di formylamino benzophenones.

  Examples of the compound having a nitrobenzyl carbamate group and an alkooxy benzyl carbamate group include, for example, bis {{(2-nitrobenzyl) oxy} carbonyl} diaminodiphenylmethane, 2,4-di {{(2-nitrobenzyl) oxy} toluylene And bis {{(2-nitrobenzyloxy) carbonyl} hexane-1,6-diamine, m-xylidine {{(2-nitro-4-chlorobenzyl) oxy} amide}.

  The photobase generator is preferably at least one of an oxime ester compound and an α-aminoacetophenone compound, and more preferably an oxime ester compound. As the α-aminoacetophenone compound, one having two or more nitrogen atoms is particularly preferable.

  As other photobase generators, WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate), WPBG-027 (trade name: (E) -1- [3- (2-hydroxyphenyl) -2- (trade name) Photobase generator such as propenoyl] piperidine, WPBG-082 (trade name: guanidinium 2- (3-benzoylphenyl) propionate), WPBG-140 (trade name: 1- (anthraquinon-2-yl) ethyl imidazole carboxylate) is used It can also be done.

Compounds containing either an alkoxy group or an epoxy group
In the above-mentioned adhesive composition, a compound containing a photoacid generator and either an alkoxy group or an epoxy group can be used in combination in the adhesive composition.

(Compounds and Polymers Having an Epoxy Group)
When a compound having one or more epoxy groups in the molecule or a polymer having two or more epoxy groups in the molecule (epoxy resin) is used, a functional group having reactivity with the epoxy group is contained in the molecule. You may use together the compound which has two or more. Here, examples of the functional group having reactivity with an epoxy group include a carboxyl group, a phenolic hydroxyl group, a mercapto group, and a primary or secondary aromatic amino group. It is particularly preferable to have two or more of these functional groups in one molecule in consideration of three-dimensional curability.

  Examples of polymers having one or more epoxy groups in the molecule include epoxy resins, bisphenol A epoxy resins derived from bisphenol A and epichlorohydrin, and bisphenol F epoxy derived from bisphenol F and epichlorohydrin Resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, Multifunctional epoxy resin such as naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, trifunctional epoxy resin and tetrafunctional epoxy resin There are glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, aliphatic chain epoxy resin etc. These epoxy resins may be halogenated and are hydrogenated. May be As epoxy resin products marketed, for example, JER coats made by Japan Epoxy Resins Co., Ltd., JER coat 828, 1001, 801 N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000, Epiclon manufactured by DIC Corporation. 830, EXA835LV, HP4032D, HP820, EP4100 series manufactured by ADEKA Corporation, EP4000 series, EPU series, Celoxide series manufactured by Daicel Chemical Industries, Ltd. (2021, 2021P, 2083, 2085, 3000, etc.), Epolide series, EHPE Series, YD series manufactured by Nippon Steel Chemical Co., Ltd., YDF series, YDCN series, YDB series, phenoxy resins (poly compounds synthesized from bisphenols and epichlorohydrin Mud carboxymethyl at both ends with polyether having an epoxy group; and YP series), Nagase ChemteX Corporation of Denacol series manufactured by Kyoeisha although chemical Co. Epo light series are exemplified but not limited thereto. Two or more of these epoxy resins may be used in combination.

(Compounds and Polymers Having an Alkoxyl Group)
Any compound having an alkoxyl group in the molecule may be used without particular limitation as long as it has one or more alkoxyl groups in the molecule. As such a compound, a melamine compound, an amino resin, a silane coupling agent etc. are mentioned as a representative.

  The compounding amount of the compound containing either an alkoxy group or an epoxy group is usually 30% by weight or less based on the total amount of the adhesive composition, and when the content of the compound in the composition is too large, the adhesiveness is It may decrease and the impact resistance to the drop test may deteriorate. The content of the compound in the composition is more preferably 20% by weight or less. On the other hand, from the viewpoint of water resistance, the composition preferably contains 2% by weight or more, and more preferably 5% by weight or more.

<Silane coupling agent>
When the adhesive composition used in the present invention is curable by active energy ray curing, the silane coupling agent is preferably a compound which is curable by active energy ray, but it is not curable by active energy ray. Similar water resistance can be provided.

  Specific examples of the silane coupling agent include, as active energy ray-curable compounds, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycide Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane and the like can be mentioned.

  Preferred are 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane.

  As a specific example of a silane coupling agent which is not active energy ray curable, a silane coupling agent (D1) having an amino group is preferable. Specific examples of the silane coupling agent (D1) having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane , Γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane , Γ- (6-aminohexyl) Minopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyl Amino group-containing silanes such as trimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine; N- (1,3-dimethylbutyl) Riden) 3 may be mentioned ketimines type silanes such as (triethoxysilyl) -1-propanamine.

  Only one type of silane coupling agent (D1) having an amino group may be used, or a plurality of types may be used in combination. Among these, in order to ensure good adhesion, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane , Γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl)- 1-Propanamine is preferred.

  The compounding amount of the silane coupling agent is preferably in the range of 0.01 to 20% by weight, preferably 0.05 to 15% by weight, and 0.1 to 10% by weight based on the total amount of the adhesive composition. More preferably, it is%. When the amount is more than 20% by weight, the storage stability of the adhesive composition is deteriorated, and when it is less than 0.1% by weight, the effect of adhesion water resistance is not sufficiently exhibited.

  Specific examples of silane coupling agents which are not active energy ray curable other than the above are 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxy Silane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, imidazole silane and the like can be mentioned.

<Compound Having a Vinyl Ether Group>
When the adhesive composition used by this invention contains the compound which has a vinyl ether group, since the adhesive water resistance of a polarizer and an adhesive layer improves, it is preferable. Although the reason why such an effect is obtained is not clear, it is speculated that it is one of the reasons that the adhesion between the polarizer and the adhesive layer is enhanced by the interaction of the vinyl ether group possessed by the compound with the polarizer. Ru. In order to further improve the adhesion water resistance between the polarizer and the adhesive layer, the compound is preferably a radically polymerizable compound having a vinyl ether group. In addition, the content of the compound is preferably 0.1 to 19% by weight based on the total amount of the adhesive composition.

<A compound which produces keto-enol tautomerism>
The adhesive composition used in the present invention can contain a compound that produces keto-enol tautomerism. For example, in an adhesive composition that can be used by blending an adhesive composition containing a crosslinking agent or a crosslinking agent, an embodiment including a compound that produces the above-mentioned keto-enol tautomerism can be preferably adopted. Thus, the effect of prolonging the pot life of the composition can be realized by suppressing excessive viscosity increase and gelation of the adhesive composition after compounding the organometallic compound, and formation of a microgel product.

  As a compound which produces the said keto- enol tautomerism, various (beta) -dicarbonyl compounds can be used. Specific examples thereof include acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2,4-dione, 2,6-dimethylheptane-. Β-diketones such as 3,5-dione; acetoacetic acid esters such as methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate; ethyl propionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, propionyl acetate Propionyl acetate esters such as tert-butyl; isobutyryl acetate esters such as ethyl isobutyryl acetate, ethyl isobutyryl acetate, isopropyl isobutyryl acetate, tert-butyl isobutyryl acetate; malonic acid esters such as methyl malonate and ethyl malonate Le acids; and the like. Among them, preferred compounds include acetylacetone and acetoacetic acid esters. The compounds that produce such keto-enol tautomerism may be used alone or in combination of two or more.

  The amount of the compound that produces keto-enol tautomerism is, for example, 0.05 parts by weight to 10 parts by weight, preferably 0.2 parts by weight to 3 parts by weight (eg, 0.3 parts by weight) with respect to 1 part by weight of the organometallic compound. Parts by weight to 2 parts by weight). When the amount of the compound used is less than 0.05 parts by weight with respect to 1 part by weight of the organic metal compound, it may be difficult to exhibit a sufficient use effect. On the other hand, if the amount of the compound used is more than 10 parts by weight with respect to 1 part by weight of the organometallic compound, the organometallic compound may excessively interact and it may be difficult to express the target water resistance.

<Polyrotaxane>
The adhesive composition of the present invention can contain a polyrotaxane. The above polyrotaxane is a cyclic molecule, a linear molecule penetrating the opening of the cyclic molecule, and a block arranged at both ends of the linear molecule so that the cyclic molecule is not separated from the linear molecule. And a group. The cyclic molecule preferably has an active energy ray-curable functional group.

  The cyclic molecule is not particularly limited as long as it is a molecule that can be skewedly embedded in a linear molecule at the opening thereof and can move on the linear molecule and has an active energy ray polymerizable group. In the present specification, "cyclic" of "cyclic molecule" means substantially "cyclic". That is, cyclic molecules may not be completely closed as long as they can move on linear molecules.

  Specific examples of cyclic molecules are preferably cyclic polymers such as cyclic polyethers, cyclic polyesters, cyclic polyether amines, cyclic polyamines, and cyclodextrins such as α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin and the like. Be Among them, cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin are preferable because they are relatively easily available and that many kinds of blocking groups can be selected. Two or more types of cyclic molecules may be mixed in the polyrotaxane or in the adhesive.

  In the polyrotaxane used in the present invention, the cyclic molecule has an active energy ray polymerizable group. As a result, the polyrotaxane and the active energy ray curable component react with each other to obtain an adhesive having a movable crosslinking point even after curing. The active energy ray polymerizable group possessed by the cyclic molecule may be any group capable of polymerizing with the above-mentioned active energy ray curable compound, and for example, radical polymerizable groups such as (meth) acryloyl group, (meth) acryloyloxy group etc. It can be mentioned.

  When cyclodextrin is used as the cyclic molecule, the active energy ray-polymerizable group is preferably introduced to the hydroxyl group of cyclodextrin via any appropriate linker. The number of active energy ray polymerizable groups contained in one molecule of polyrotaxane is preferably 2 to 1,280, more preferably 50 to 1,000, and still more preferably 90 to 900.

  It is preferable that a hydrophobic modifying group is introduced into the cyclic molecule. The introduction of the hydrophobic modifying group can improve the compatibility with the active energy ray curable component. Moreover, since hydrophobicity is provided, when it uses for a polarizing film, the penetration of the water to the interface of an adhesive bond layer and a polarizer can be prevented, and water resistance can be improved further. Examples of hydrophobic modifying groups include polyester chains, polyamide chains, alkyl chains, oxyalkylene chains, ether chains and the like. Specific examples thereof include groups described in [0027] to [0042] of WO2009 / 145073.

  A polarizing film using a resin composition containing polyrotaxane as an adhesive is excellent in water resistance. The reason why the water resistance of the polarizing film is improved is not clear, but is presumed as follows. That is, the ability of the crosslinking point to move due to the mobility of the cyclic molecules of the polyrotaxane (so-called, pulley effect) imparts flexibility to the cured adhesive, and the adhesion of the polarizer to the surface irregularities is increased. As a result, it is considered that the penetration of water to the interface between the polarizer and the adhesive layer is prevented. Furthermore, it is thought that the hydrophobicity was imparted to the adhesive by the polyrotaxane having the hydrophobic modifying group, which also contributed to the prevention of the penetration of water to the interface between the polarizer and the adhesive layer.

The content of polyrotaxane is preferably 2% by weight to 50% by weight with respect to the resin composition.

で表される化合物（ただし、Ｘはビニル基、（メタ）アクリル基、スチリル基、（メタ）アクリルアミド基、ビニルエーテル基、エポキシ基、オキセタン基およびメルカプト基からなる群より選択される少なくとも１種の反応性基を含む官能基であり、Ｒ^９およびＲ^１０はそれぞれ独立に、水素原子、置換基を有してもよい、脂肪族炭化水素基、アリール基、またはヘテロ環基を表す）を含有することができる。一般式（５）に記載の化合物は、ポリビニルアルコール系偏光子が有する水酸基と容易にエステル結合を形成する。また、前記一般式（５）に記載の化合物はさらに反応性基を含むＸを有し、Ｘが含む反応性基を介して接着剤組成物に含まれる他の硬化性成分と反応する。つまり、硬化性樹脂層が有するホウ酸基および／またはホウ酸エステル基が、偏光子が有する水酸基と共有結合を介して強固
に接着する。これにより、偏光子と硬化性樹脂層との界面に水分が存在しても、これらが水素結合および／またはイオン結合のみならず、共有結合を介して強固に相互作用しているため、偏光子と硬化性樹脂層との間の接着耐水性が飛躍的に向上する。偏光子と硬化物層との接着性および耐水性向上、特には偏光子と透明保護フィルムとを接着剤層を介して接着させる場合の接着性および耐水性向上の見地から、接着剤組成物中、一般式（５）に記載の化合物の含有量は、０．００１〜５０重量％であることが好ましく、０．１〜３０重量％であることがより好ましく、１〜１０重量％であることが最も好ましい。 The adhesive composition has the following general formula (5):

A compound represented by (wherein X is at least one selected from the group consisting of a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetane group and a mercapto group) R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aryl group or a heterocyclic group. can do. The compound described in the general formula (5) easily forms an ester bond with the hydroxyl group of the polyvinyl alcohol polarizer. Further, the compound described in the general formula (5) further has X containing a reactive group, and reacts with other curable components contained in the adhesive composition via the reactive group contained in X. That is, the boric acid group and / or boric acid ester group which a curable resin layer has adhere | attach firmly with the hydroxyl group which a polarizer has via a covalent bond. As a result, even if water is present at the interface between the polarizer and the curable resin layer, these are strongly interact not only with hydrogen bonds and / or ionic bonds but also with covalent bonds. Water resistance between the resin and the curable resin layer is dramatically improved. In the adhesive composition, from the standpoint of improving the adhesion and water resistance between the polarizer and the cured product layer, in particular, when the polarizer and the transparent protective film are adhered via the adhesive layer, the adhesion and water resistance are improved. The content of the compound described in the general formula (5) is preferably 0.001 to 50% by weight, more preferably 0.1 to 30% by weight, and 1 to 10% by weight. Is most preferred.

<Organic metal compound>
When the adhesive composition of the present invention simultaneously contains at least one organometallic compound selected from the group consisting of metal alkoxides and metal chelates and a polymerizable compound having a polymerizable functional group and a carboxyl group, a polarizer It is preferable because adhesion water resistance between the resin and the adhesive layer is improved. The organometallic compound becomes an active metal species by the interposition of water, and as a result, the organometallic compound strongly interacts with both the polarizer and the active energy ray-curable component constituting the adhesive layer. As a result, even if water is present at the interface between the polarizer and the adhesive layer, these are strongly interact via the organometallic compound, so that the adhesion water resistance between the polarizer and the adhesive layer Improve dramatically. Although the organometallic compound greatly contributes to the improvement of the adhesion and water resistance of the adhesive layer, the composition containing this has a short pot life due to the instability of the liquid stability, and the productivity is It tends to get worse. This is because the organic metal compound is highly reactive, and contacts with water contained in a small amount in the composition to cause hydrolysis reaction and self condensation reaction, resulting in self aggregation and clouding of the composition liquid (aggregate Generation, phase separation, precipitation) is presumed to be one of the causes. However, when the composition contains a polymerizable compound having a polymerizable functional group and a carboxyl group together with the organic metal compound, the hydrolysis reaction and the self condensation reaction of the organic metal compound are suppressed, and the organic metal compound in the composition is Solution stability can be dramatically improved. The proportion of the organic metal compound is preferably 0.05 to 15% by weight of the total amount of the composition, and more preferably 0.1 to 10% by weight. If the amount is more than 15% by weight, the storage stability of the composition may be degraded, or the proportion of components for adhering to a polarizer or a protective film may be relatively short, resulting in a decrease in adhesion. On the other hand, if it is less than 0.05% by weight, the effect of adhesion water resistance is not sufficiently exhibited. When the total amount of the organic metal compound in the curable adhesive composition is α (mol), the content of the polymerizable compound having a functional group having a functional group and a carboxyl group is preferably 0.25 α (mol) or more It is more preferably 0.35 α (mol) or more, particularly preferably 0.5 α (mol) or more. When the content of the polymerizable compound having the affinity functional group and the carboxyl group is less than 0.25 α (mol), the stabilization of the organic metal compound becomes insufficient, and the hydrolysis reaction and the self condensation reaction proceed, and the pot life May be shortened. Although the upper limit of the content of the polymerizable compound to the total amount α (mol) of the organic metal compound is not particularly limited, for example, about 4 α (mol) can be exemplified.

<Chlorinated polyolefin>
Chlorinated polyolefin may be blended in the adhesive composition according to the present invention. In this case, the adhesive layer obtained has a remarkably reduced dyeability due to the iodine compound derived from the polyvinyl alcohol-based polarizer, and functions as a protective layer which suppresses the release and diffusion of the iodine compound from the polarizer. As a result, when the adhesive composition according to the present invention is used for a polarizing film application, the optical durability of the polarizing film is remarkably improved. The adhesive composition according to the present invention is required to be optically transparent, and as a polyolefin resin, a chlorinated polyolefin which is soluble in an active energy ray curable component and does not cause layer separation or precipitation is selected. It is preferable to do. Unchlorinated polyolefins are not preferable because they have extremely low solubility in curable components that are cured by irradiation with active energy rays.

  Examples of chlorinated polyolefins that can be used in the present invention include chlorinated polyethylene, chlorinated polypropylene, acrylic modified or urethane modified chlorinated polyolefin and the like.

  The chlorine content in the chlorinated polyolefin is preferably 25 to 50% by weight, and more preferably 30 to 45% by weight. If it is less than 25% by weight, the solubility to the active energy ray-curable component may be reduced, and it may be difficult to form an optically clear composition. If it exceeds 50% by weight, the change in optical properties under severe humid conditions when it is formed into a polarizing film may be large, and the effects of the present invention may not be obtained. The chlorine content in chlorinated polyolefin can be measured according to JIS-K7229. More specifically, for example, it can be measured using the “oxygen flask combustion method” in which a chlorine-containing resin is burned under an oxygen atmosphere, the generated gaseous chlorine is absorbed by water, and quantified by titration.

  In addition, the weight average molecular weight of the chlorinated polyolefin) is preferably 3,000 to 100,000, more preferably 5,000 to 80,000, and most preferably 10,000 to 20,000. Used. If the molecular weight of the chlorinated polyolefin is too low, the water resistance may not be sufficiently improved when made into a cured product. On the other hand, if the molecular weight is too high, the solubility in the active energy ray-curable component may be significantly reduced, and it may be difficult to form an optically clear composition.

  Examples of commercially available chlorinated polyolefins include, for example, Super Clon series (manufactured by Nippon Paper Chemicals Co., Ltd.), Harden series (manufactured by Toyobo Co., Ltd.), and Elastlen series (manufactured by Showa Denko Co., Ltd.). Can.

  Among commercially available products, Super Clon Series (manufactured by Nippon Paper Chemicals Co., Ltd.) “Super Clon 814 HS”, “Super Clon 390 S”, “Super Clon 803 MW”, “Super Clon 803 L”, “Super Clon B”, Harden series (made by Toyobo Co., Ltd.) "hardened 16-LP", "hardened 15-LP", eraslen series (made by Showa Denko) "elaslen 404B", "elaslen 402B", "elaslen 401A", etc. It can be used preferably, and in particular, it is preferable to use "Super Clon 814 HS" because it has excellent balance between solubility in active energy ray-curable components and stability of optical properties under severe humidified conditions when made into a polarizing film. Can.

<Additives other than the above>
Moreover, various additives can be mix | blended with the adhesive composition used by this invention in the range which does not impair the objective of this invention and an effect. Such additives include epoxy resin, polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, Polymers or oligomers such as silicone-based oligomers and polysulfide-based oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization start assistants; surfactants; plasticizers; UV absorbers Inorganic fillers; pigments; dyes and the like.

  The above-mentioned additive is usually 0 to 10% by weight, preferably 0 to 5% by weight, most preferably 0 to 3% by weight, based on the total amount of the adhesive composition.

<Characteristics of Adhesive Composition>
The SP value distance between the adhesive composition and the SP value of the transparent protective film constituting the laminated optical film is preferably 12 or less, and more preferably 10 or less. This is preferable because a compatible layer in which the composition continuously changes is formed more reliably between the transparent protective film and the adhesive layer. In the present invention, the SP value of the adhesive composition may be adjusted within a desired range by appropriately adjusting the mixing ratio and the like with reference to the SP values of monomers and the like constituting the adhesive composition. It is possible. In addition, the measuring method of SP value of adhesive composition is mentioned later.

  The adhesive composition used in the present invention preferably has a surface tension of 30 mN / m or less before curing in order to effectively suppress the generation of laminate bubbles. The method of measuring the surface tension of the adhesive composition before curing will be described later.

The adhesive composition used in the present invention preferably has a bulk water absorption of 10% by weight or less when the cured product obtained by curing the composition is immersed in pure water at 23 ° C. for 24 hours. Bulk water absorption is expressed by the following equation.
Formula: {(M2-M1) / M1} × 100 (%),
However, M1: the weight of the cured product before immersion, M2: the weight of the cured product after immersion By setting the bulk absorption coefficient to 10% by weight or less, polarization when the polarizing film is placed under a harsh high temperature and high humidity environment The movement of water to the child is suppressed, and the increase in the transmittance of the polarizer and the decrease in the degree of polarization can be suppressed. The bulk water absorption rate is preferably 5% by weight or less, and more preferably 3% by weight or less, from the viewpoint of making the optical durability better under a severe environment at high temperature for the adhesive layer of the polarizing film. Most preferably, it is 1% by weight or less. On the other hand, when laminating a polarizer and a transparent protective film, the polarizer holds a certain amount of water, and when the curable adhesive and the water contained in the polarizer come in contact with each other, such as repelling or air bubbles. Poor appearance may occur. In order to suppress appearance defects, the curable adhesive is preferably capable of absorbing a certain amount of water. More specifically, the bulk water absorption is preferably 0.01% by weight or more, and more preferably 0.05% by weight or more.

  The viscosity of the adhesive composition used in the present invention is preferably 3 to 100 mPa · s, more preferably 5 to 50 mPa · s, and most preferably 10 to 30 mPa · s. When the viscosity of the adhesive composition is high, the surface smoothness after application is poor and appearance defects occur, which is not preferable. The adhesive composition used in the present invention can be applied by heating or cooling the composition to adjust the viscosity to a preferred range.

The adhesive composition used in the present invention preferably has a high octanol / water distribution coefficient (hereinafter referred to as log Pow value). The log Pow value is an index that represents the lipophilicity of a substance, and means the logarithmic value of the octanol / water partition coefficient. A high logPow means that it is lipophilic, that is, it has a low water absorption. The log Pow value can also be measured (flask dipping method according to JIS-Z-7260), but it is calculated based on the structure of each compound that is a component (curable component etc.) of the curable adhesive for polarizing film It can also be calculated by In the present specification, the logPow value calculated by ChemDraw Ultra made by Cambridge Software Co., Ltd. is used.
Based on the above calculated value, the log Pow value of the curable adhesive for polarizing film in the present invention can be calculated by the following equation.
Curing adhesive logPow = 型 (logPowi × Wi)
log Powi: log Pow value of each component of the curable adhesive Wi: (mole number of component i) / (total number of moles of each component of the curable adhesive)
In the above calculation, among the components of the curable adhesive, components which do not form a skeleton of a cured product (adhesive layer) such as a polymerization initiator or a photoacid generator are removed from the components in the above calculation. The log Pow value of the curable adhesive for polarizing film of the present invention is preferably 1 or more, more preferably 1.5 or more, and most preferably 2 or more. Thereby, adhesion water resistance and humidification durability can be improved. On the other hand, the log Pow value of the curable adhesive for polarizing film of the present invention is usually about 8 or less, preferably 5 or less, more preferably 4 or less. If the logPow value is too high, it is not preferable because appearance defects such as repelling and air bubbles are likely to occur as described above.

  Furthermore, it is preferable that the adhesive composition used in the present invention be substantially free of water or volatile solvent. Since the heat treatment becomes unnecessary and it is not only excellent in productivity but it can suppress the optical characteristic fall of the polarizer by heat by containing substantially no volatile solvent, it is preferable. "Substantially free" means containing less than 5% by weight, for example, when the total amount of adhesive composition is 100% by weight or less, and in particular, means containing less than 2% by weight I assume.

  In addition, since the adhesive composition used in the present invention has a curable component, when the adhesive composition is cured, curing shrinkage usually occurs. The cure shrinkage rate is an index indicating the rate of cure shrinkage when forming an adhesive layer from a resin composition. When the cure shrinkage rate of the adhesive layer is increased, interface distortion is caused when the adhesive composition is cured to form an adhesive layer, which is preferable in order to suppress the occurrence of adhesion failure. From the above viewpoint, the cure shrinkage of the cured product obtained by curing the resin composition having the effects of the present invention is preferably 10% or less. The curing shrinkage is preferably small, and the curing shrinkage is preferably 8% or less, more preferably 5% or less. The said cure shrinkage rate is measured by the method of Unexamined-Japanese-Patent No. 2013-104869, and is specifically measured by the method by the cure shrinkage sensor by Sentec Co., Ltd. which is described in an Example.

  Moreover, as for the adhesive composition used by this invention, it is preferable to use the material with a low skin irritation as said curable component from a safety viewpoint. Skin irritation is P.I. I. It can be judged by the index I. P. I. I is widely used as an indicator of the degree of skin damage and is measured by the drape method. The measured value is displayed in the range of 0 to 8, and the smaller the value is, the lower the stimulability is judged to be. However, since the error of the measured value is large, it is preferable to be regarded as a reference value. P. I. I is preferably 4 or less, more preferably 3 or less, and most preferably 2 or less.

  The present invention is characterized in that a compatible layer in which the composition changes continuously is formed between the transparent protective film constituting the laminated optical film and the adhesive layer. Below, a transparent protective film is demonstrated.

<Transparent Protective Film>
In order to form a compatible layer with the adhesive layer, it is preferable to use a transparent protective film that has been subjected to a pretreatment step of bringing an organic solvent into contact with the surface on which the adhesive layer is to be formed. Is preferred. In the pre-treatment step, for example, the transparent protective film may be dipped in an organic solvent, but it is preferable to apply the organic solvent to the transparent protective film in consideration of productivity.

  The method for applying the organic solvent to the transparent protective film is appropriately selected depending on the intended coating thickness, and for example, a reverse coater, a gravure coater (direct, reverse or offset), a bar reverse coater, a roll coater, a die coater, A bar coater, a rod coater and the like can be mentioned.

  As the organic solvent, those having an SP value distance to the transparent protective film of 12 or less can be suitably used. For example, esters such as ethyl acetate, butyl acetate and 2-hydroxyethyl acetate; methyl ethyl ketone, acetone, cyclohexanone, Methyl isobutyl ketone, diethyl ketone, methyl-n-propyl ketone, ketones such as acetylacetone; cyclic ethers such as tetrahydrofuran (THF), dioxane etc .; aliphatic or alicyclic hydrocarbons such as n-hexane, cyclohexane etc .; toluene And aromatic hydrocarbons such as xylene; aliphatic or alicyclic alcohols such as methanol, ethanol, n-propanol, isopropanol and cyclohexanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethyl Glycol ethers such as glycol monoethyl ether; diethylene glycol monomethyl ether acetate, and the like diethylene glycol ether acetates, such as monoethyl ether acetate and mixtures thereof. As the organic solvent, it is more preferable to use one having an SP value distance of 10 or less to the transparent protective film. The organic solvent to be used preferably contains substantially no solute, more specifically, the solute content of the organic solvent is preferably less than 5% by weight, and more preferably less than 1% by weight. It is further preferred to use an organic solvent free of solutes. The method of measuring the SP value of the organic solvent will be described later.

  As the transparent protective film, a film having an SP value distance of 10 or less to the adhesive composition as a raw material for forming the adhesive layer can be suitably used. The measuring method of SP value of a transparent protective film is mentioned later.

  As the transparent protective film, those excellent in transparency, mechanical strength, thermal stability, water blocking property, isotropy and the like are preferable. For example, polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, and styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) Examples include system polymers and polycarbonate polymers. In addition, polyethylene, polypropylene, polyolefin having a cyclo-based or norbornene structure, polyolefin-based polymer such as ethylene-propylene copolymer, vinyl chloride-based polymer, amide-based polymer such as nylon and aromatic polyamide, imide-based polymer, sulfone-based polymer , Polyether sulfone polymers, polyetheretherketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers, or the above Blends of polymers and the like are also mentioned as examples of the polymer forming the above-mentioned transparent protective film. Among these, in the present invention, polyarylate, polycarbonate, acrylic polymer and triacetyl cellulose are preferable. The transparent protective film may contain one or more types of any appropriate additive. As an additive, an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, a coloring agent etc. are mentioned, for example. The content of the above-mentioned thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, particularly preferably 70 to 97% by weight . When content of the said thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has can not fully be expressed.

  The laminated optical film according to the present invention, in particular the polarizing film, is preferably a polarizer and a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm, laminated via an adhesive layer. The adhesive composition used in the present invention cures the adhesive layer by irradiating the ultraviolet light through the transparent protective film having UV absorbing ability by containing the photopolymerization initiator of the general formula (2) described above. It can be formed. Therefore, an adhesive bond layer can be hardened also in a polarizing film which laminated a transparent protective film which has UV absorption power on both sides of a light polarizer. However, as a matter of course, the adhesive layer can be cured also in a polarizing film in which a transparent protective film having no UV absorbing ability is laminated. In addition, the transparent protective film which has UV absorption ability means the transparent protective film whose transmittance | permeability with respect to 380 nm light is less than 10%.

  As a method for imparting the UV absorbing ability to the transparent protective film, there is a method in which an ultraviolet light absorber is contained in the transparent protective film, and a method in which a surface treatment layer containing an ultraviolet light absorber is laminated on the surface of the transparent protective film.

  Specific examples of the UV absorber include, for example, conventionally known oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like. .

  In UV curing or visible light curing, it is preferable to heat the adhesive composition for polarizing film before irradiation with ultraviolet light or visible light (heating before irradiation), in which case heating to 40 ° C. or higher Is preferable, and heating to 50 ° C. or more is more preferable. It is also preferable to heat the adhesive composition for polarizing film after irradiation with ultraviolet light or visible light (heating after irradiation), in which case heating to 40 ° C. or higher is preferable, and heating to 50 ° C. or higher Is more preferred.

  Moreover, as a transparent protective film, the polymer film as described in Unexamined-Japanese-Patent No. 2001-343529 (WO01 / 37007), for example, the thermoplastic resin which has a substituted and / or non-substituted imide group in (A) side chain, Examples include resin compositions containing thermoplastic resins having substituted and / or unsubstituted phenyl and nitrile groups in the chain. As a specific example, a film of a resin composition containing an alternating copolymer of isobutylene and N-methyl maleimide and an acrylonitrile / styrene copolymer can be mentioned. As the film, a film formed of a mixed extruded product of a resin composition can be used. These films have small retardation and small photoelastic coefficient, so that problems such as unevenness due to distortion of the polarizing film can be eliminated, and since the moisture permeability is small, the humidity resistance is excellent.

  As a transparent protective film, Tg (glass transition temperature) becomes like this. Preferably it is 115 degreeC or more, More preferably, it is 120 degreeC or more, More preferably, it is 125 degreeC or more, Especially preferably, it is 130 degreeC or more. When the Tg is 115 ° C. or more, the durability of the polarizing film can be excellent. The upper limit of the Tg of the transparent protective film is not particularly limited, but is preferably 170 ° C. or less from the viewpoint of formability and the like.

As the transparent protective film provided on one side or both sides of the above-mentioned polarizer, those excellent in transparency, mechanical strength, heat stability, water blocking property, isotropy and the like are preferable, and in particular, the moisture permeability is 150 g / m ² / more preferably not more 24h or less, particularly preferably those following 140 g ^/ m 2 / 24h, more preferably the following 120g ^/ m 2 ^/ 24h. The moisture permeability is determined by the method described in the examples.

  Examples of materials for forming the transparent protective film satisfying the low moisture permeability include polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate resins; arylate resins; amide resins such as nylon and aromatic polyamide; polyethylene and polypropylene A polyolefin polymer such as ethylene / propylene copolymer, a cyclic olefin resin having a cyclo or norbornene structure, a (meth) acrylic resin, or a mixture thereof can be used. Among the above resins, polycarbonate resins, cyclic polyolefin resins and (meth) acrylic resins are preferable, and cyclic polyolefin resins and (meth) acrylic resins are particularly preferable.

  The thickness of the transparent protective film can be appropriately determined, but in general, 5 to 100 μm is preferable in terms of strength, workability such as handleability, thin layer property, and the like. In particular, 10 to 60 μm is preferable, and 20 to 40 μm is more preferable.

  As the transparent protective film, one having an in-plane retardation of less than 40 nm and a thickness direction retardation of less than 80 nm is usually used. The front phase difference Re is represented by Re = (nx−ny) × d. The thickness direction retardation Rth is represented by Rth = (nx−nz) × d. Further, the Nz coefficient is represented by Nz = (nx−nz) / (nx−ny). [However, the refractive indices in the slow axis direction, fast axis direction and thickness direction of the film are nx, ny and nz, respectively, and d (nm) is the film thickness. The slow axis direction is the direction in which the refractive index in the film plane is maximum. ]. The transparent protective film is preferably as colorless as possible. A protective film having a thickness direction retardation value of -90 nm to +75 nm is preferably used. By using one having a thickness direction retardation value (Rth) of −90 nm to +75 nm, it is possible to substantially eliminate the coloring (optical coloring) of the polarizing film caused by the transparent protective film. The thickness direction retardation value (Rth) is more preferably -80 nm to +60 nm, particularly preferably -70 nm to +45 nm.

  On the other hand, a retardation plate having a front retardation of 40 nm or more and / or a thickness direction retardation of 80 nm or more can be used as the transparent protective film. The in-plane retardation is usually controlled in the range of 40 to 200 nm, and the thickness direction retardation is usually controlled in the range of 80 to 300 nm. When using a retardation plate as a transparent protective film, since the said retardation plate functions also as a transparent protective film, thickness reduction can be achieved.

  Examples of the retardation plate include a birefringent film formed by uniaxially or biaxially stretching a polymer material, an alignment film of liquid crystal polymer, and a film supporting an alignment layer of liquid crystal polymer. The thickness of the retardation plate is not particularly limited, but is generally about 20 to 150 μm. As the polymer material, for example, polyvinyl alcohol, polyvinyl butyral, polymethyl vinyl ether, polyhydroxyethyl acrylate, hydroxyethyl cellulose, hydroxypropyl cellulose, methylcellulose, polycarbonate, polyarylate, polysulfone, polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, Polyphenylene sulfide, polyphenylene oxide, polyallyl sulfone, polyamide, polyimide, polyolefin, polyvinyl chloride, cellulose resin, cyclic polyolefin resin (norbornene resin), or these binary and ternary copolymers, graft copolymer Polymers, blends and the like can be mentioned. These polymer materials become oriented products (stretched films) by stretching or the like.

  Examples of the liquid crystal polymer include various types of main chain type and side chain types in which a conjugated linear atomic group (mesogen) imparting liquid crystal orientation is introduced into the main chain or side chain of the polymer, and the like. . Specific examples of the main chain type liquid crystal polymer include a polyester-based liquid crystalline polymer, a discotic polymer, a cholesteric polymer, and the like having a structure in which a mesogenic group is bonded by a spacer portion which imparts flexibility. Specific examples of the side chain type liquid crystal polymer include a polysiloxane, a polyacrylate, a polymethacrylate, or a polymalonate as a main chain skeleton, and a para-substituted nematic alignment imparting agent through a spacer portion composed of a conjugated atomic group as a side chain. What has a mesogenic part which consists of a cyclic compound unit etc. are mentioned. These liquid crystal polymers are prepared, for example, by rubbing a surface of a thin film of polyimide, polyvinyl alcohol or the like formed on a glass plate, a solution of a liquid crystalline polymer on an alignment treated surface such as one having oblique deposition of silicon oxide. It is carried out by developing and heat treating.

  The retardation plate may have an appropriate phase difference according to the purpose of use, for example, for the purpose of compensating for coloration due to birefringence of various wavelength plates and liquid crystal layers or viewing angle etc. What laminated | stacked the retardation plate and controlled optical characteristics, such as a phase difference, etc. may be used.

  The retardation plate has the following relationship: nx = ny> nz, nx> ny> nz, nx> ny = nz, nx> nz> ny, nz = nx> ny, nz> nx> ny, nz> nx = ny What is satisfied is selected and used according to various applications. Note that ny = nz includes not only cases in which ny and nz are completely identical but also cases in which ny and nz are substantially the same.

  For example, in a retardation plate satisfying nx> ny> nz, the front retardation is 40 to 100 nm, the thickness direction retardation is 100 to 320 nm, and the Nz coefficient is 1.8 to 4.5. Is preferred. For example, with a retardation plate (positive A plate) satisfying nx> ny = nz, it is preferable to use one having an in-plane retardation of 100 to 200 nm. For example, with a retardation plate (negative A plate) satisfying nz = nx> ny, it is preferable to use one having an in-plane retardation of 100 to 200 nm. For example, in a retardation plate satisfying nx> nz> ny, it is preferable to use one having an in-plane retardation of 150 to 300 nm and an Nz coefficient of more than 0 and not more than 0.7. Further, as described above, for example, those satisfying nx = ny> nz, nz> nx> ny, or nz> nx = ny can be used.

  A transparent protective film can be suitably selected according to the liquid crystal display device applied. For example, in the case of VA (including Vertical Alignment, MVA and PVA), it is preferable that at least one (cell side) transparent protective film of the polarizing film have a retardation. As a concrete phase difference, it is desirable that it is the range of Re = 0-240 nm and Rth = 0-500 nm. In terms of three-dimensional refractive index, it is preferable that nx> ny = nz, nx> ny> nz, nx> nz> ny, and nx = ny> nz (positive A plate, biaxial, negative C plate). In the VA type, it is preferable to use a combination of a positive A plate and a negative C plate, or one biaxial film. When using a polarizing film in the upper and lower sides of a liquid crystal cell, both the upper and lower sides of a liquid crystal cell may have a phase difference, or the transparent protective film in any one of the upper and lower sides may have a phase difference.

  For example, in the case of IPS (In-Plane Switching, including FFS), either one of the transparent protective films of the polarizing film may or may not have retardation. For example, in the case where the liquid crystal cell does not have a phase difference, it is desirable that the liquid crystal cell has no phase difference on both sides (cell side). In the case of having a phase difference, in the case where both of the upper and lower portions of the liquid crystal cell have a phase difference, it is preferable that either upper or lower portion have a phase difference (for example, nx> nz> ny on the upper side) A biaxial film satisfying the relationship, no phase difference on the lower side, or a positive A plate on the upper side, and a positive C plate on the lower side). When it has a phase difference, the range of Re = −500 to 500 nm and Rth = −500 to 500 nm is desirable. In terms of three-dimensional refractive index, nx> ny = nz, nx> nz> ny, nz> nx = ny, nz> nx> ny (positive A plate, biaxial, positive C plate) is desirable.

  The transparent protective film may further be laminated with a peelable substrate in order to compensate for its mechanical strength and handleability. Before or after the transparent protective film and the polarizer are bonded to each other, the peelable substrate can be peeled off from the laminate including the transparent protective film and the polarizer during or in a separate step.

<Optical film>
In the laminated optical film according to the present invention, the optical film is preferably a polarizer, and particularly in the present invention, the laminated optical film is formed by curing an adhesive composition on at least one surface of the polarizer. It is preferable that it is a polarizing film by which the transparent protective film was laminated | stacked through the adhesive layer.

<Polarizer>
The polarizer is not particularly limited, and various ones can be used. As a polarizer, for example, hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, ethylene / vinyl acetate copolymer-based partially saponified films, etc., dichromatic dyes such as iodine and dichroic dyes, etc. Materials which have been made to adsorb and uniaxially be stretched, and a polyene-based oriented film such as a dehydrated product of polyvinyl alcohol and a dehydrochlorinated product of polyvinyl chloride. Among these, a polarizer made of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is preferably 2 to 30 μm, more preferably 4 to 20 μm, and most preferably 5 to 15 μm. When the thickness of the polarizer is thin, the optical durability is unfavorably reduced. When the thickness of the polarizer is large, the dimensional change under high temperature and high humidity becomes large, and a problem of display unevenness occurs, which is not preferable.

  The polarizer which dye | stained the polyvinyl alcohol-type film with iodine, and uniaxially stretched it can be produced by, for example, dyeing | staining by immersing polyvinyl alcohol in the aqueous solution of iodine, and extending | stretching 3 to 7 times of original length. It can also be immersed in an aqueous solution such as boric acid or potassium iodide, if necessary. If necessary, the polyvinyl alcohol-based film may be dipped in water and rinsed before dyeing. In addition to being able to wash the stains and antiblocking agents on the surface of the polyvinyl alcohol film by washing the polyvinyl alcohol film with water, the polyvinyl alcohol film is also effective in preventing nonuniformity such as unevenness in dyeing by swelling the film. is there. The stretching may be performed after staining with iodine, may be stretching while staining, or may be stretched and then stained with iodine. It can also be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.

  In the adhesive composition used in the present invention, when a thin polarizer having a thickness of 10 μm or less is used as a polarizer, the effect (satisfying the optical durability in a severe environment under high temperature and high humidity) is obtained. It can be prominently expressed. A polarizer with a thickness of 10 μm or less is relatively affected by moisture relatively to a polarizer with a thickness of more than 10 μm, and the optical durability is not sufficient in an environment under high temperature and high humidity, and the transmittance increases and the degree of polarization Deterioration is likely to occur. That is, when the polarizer of 10 μm or less is laminated with the adhesive layer having a bulk water absorption rate of 10% by weight or less according to the present invention, the movement of water to the polarizer is suppressed in an environment under severe high temperature and high humidity. As a result, it is possible to significantly suppress the deterioration of the optical durability such as the increase in the transmittance of the polarizing film and the decrease in the degree of polarization. The thickness of the polarizer is preferably 1 to 7 μm from the viewpoint of thinning. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, and furthermore, the thickness as the polarizing film can be reduced.

  As a thin polarizer, typically, the specification of Japanese Patent Application Laid-Open Nos. 51-069644, 2000-338329, WO 2010/100917, PCT / JP2010 / 001460, or Japanese Patent Application No. 2010- Examples thereof include thin polarizing films described in Japanese Patent Application Laid-Open No. 269002 and Japanese Patent Application No. 2010-263692. These thin polarizing films can be obtained by a manufacturing method including the steps of stretching a polyvinyl alcohol resin (hereinafter, also referred to as a PVA resin) layer and a stretching resin base material in the state of a laminate and dyeing. With this manufacturing method, even if the PVA-based resin layer is thin, it is possible to stretch without any trouble such as breakage due to stretching by being supported by the stretching resin base material.

  Among the thin polarizing films described above, among the processes of stretching in the state of a laminate and the process of dyeing, WO2010 / 100917 pamphlet, in that it can be stretched at high magnification to improve polarization performance. Preferred are those obtained by the process comprising drawing in an aqueous solution of boric acid as described in the specification of JP2010 / 001460, or Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692, particularly What is obtained by the manufacturing method which includes the process of air-drawing auxiliary | assistant before extending | stretching in the boric-acid aqueous solution which is described in Japanese Patent Application No. 2010-269002 specification and Japanese Patent Application No. 2010-263692 specification is preferable.

で表される化合物（ただし、Ｘは反応性基を含む官能基であり、Ｒ^１０およびＲ^１１はそれぞれ独立に、水素原子、置換基を有してもよい、脂肪族炭化水素基、アリール基、またはヘテロ環基を表す）を備えてもよい。前記脂肪族炭化水素基としては、炭素数１〜２０の置換基を有してもよい直鎖または分岐のアルキル基、炭素数３〜２０の置換基を有してもよい環状アルキル基、炭素数２〜２０のアルケニル基が挙げられ、アリール基としては、炭素数６〜２０の置換基を有してもよいフェニル基、炭素数１０〜２０の置換基を有してもよいナフチル基等が挙げられ、ヘテロ環基としては例えば、少なくとも一つのヘテロ原子を含む、置換基を有してもよい５員環または６員環の基が挙げられる。これらは互いに連結して環を形成してもよい。一般式（６）中、Ｒ^１０およびＲ^１１として好ましくは、水素原子、炭素数１〜３の直鎖または分岐のアルキル基であり、最も好ましくは、水素原子である。なお、一般式（６）で表される化合物は積層光学フィルム中で、未反応の状態で偏光子と接着剤層との間および／または透明保護フィルムと接着剤層との間に介在しても良く、各官能基が反応した状態で介在しても良い。また、「偏光子の貼合面に、一般式（６）で表される化合物を備える」とは、例えば一般式（６）で表される化合物が、該貼合面に少なくとも１分子存在することを意味する。ただし、偏光子と接着剤層との間の接着耐水性を十分に向上させるためには、一般・BR>ョ（６）で表される化合物を含む易接着組成物を用いて、易接着層を該貼合面の少なくとも一部に形成することが好ましく、該貼合面の全面に易接着層を形成することがより好ましい。 In the present invention, on the bonding surface of the polarizer constituting the laminated optical film, the following general formula (6):

A compound represented by (wherein X is a functional group containing a reactive group, and R ¹⁰ and R ¹¹ are each independently a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aryl group Or a heterocyclic group) may be provided. As said aliphatic hydrocarbon group, the linear or branched alkyl group which may have a C1-C20 substituent, the cyclic alkyl group which may have a C3-C20 substituent, carbon Alkenyl groups of 2 to 20 may be mentioned, and examples of the aryl group include a phenyl group which may have a substituent of 6 to 20 carbon atoms, a naphthyl group which may have a substituent of 10 to 20 carbon atoms, etc. The heterocyclic group includes, for example, an optionally substituted 5- or 6-membered ring group containing at least one hetero atom. They may be linked to each other to form a ring. In the general formula (6), preferred as R ¹⁰ and R ¹¹ are a hydrogen atom and a linear or branched alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom. In the laminate optical film, the compound represented by the general formula (6) is interposed between the polarizer and the adhesive layer and / or between the transparent protective film and the adhesive layer in an unreacted state. The functional groups may be in a reacted state. In addition, “having the compound represented by the general formula (6) on the bonding surface of the polarizer” means, for example, that at least one molecule of the compound represented by the general formula (6) exists on the bonding surface. It means that. However, in order to sufficiently improve the adhesion water resistance between the polarizer and the adhesive layer, an easy-adhesion layer is formed using an easy-adhesion composition containing a compound represented by General (BR) ョ (6) It is preferable to form in at least one part of this bonding surface, and it is more preferable to form an easily bonding layer in the whole surface of this bonding surface.

  X contained in the compound represented by the general formula (6) is a functional group containing a reactive group, which is a functional group capable of reacting with the curable component constituting the adhesive layer, and as the reactive group contained in X Is, for example, a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, an epoxy group, an oxetane group, an α, β-unsaturated carbonyl Groups, mercapto groups, halogen groups and the like. When the curable resin composition constituting the adhesive layer is active energy ray curable, the reactive group contained in X is a vinyl group, a (meth) acrylic group, a styryl group, a (meth) acrylamide group, a vinyl ether group, It is preferable that it is at least one reactive group selected from the group consisting of an epoxy group, an oxetane group and a mercapto group, and particularly when the curable resin composition constituting the adhesive layer is radical polymerizable, X is The reactive group contained is preferably at least one reactive group selected from the group consisting of (meth) acrylic group, styryl group and (meth) acrylamide group, and the compound represented by the general formula (6) When it has a (meth) acrylamide group, it is more preferable because the reactivity is high and the copolymerization rate with the active energy ray curable resin composition is increased. Moreover, since the polarity of a (meth) acrylamide group is high and it is excellent in adhesiveness, it is preferable also from the point that the effect of this invention is acquired efficiently. When the curable resin composition constituting the adhesive layer is cationically polymerizable, the reactive group contained in X is selected from a hydroxyl group, an amino group, an aldehyde, a carboxyl group, a vinyl ether group, an epoxy group, an oxetane group and a mercapto group It is preferable to have at least one functional group to be selected, and in the case of having an epoxy group, it is preferable because the adhesion between the resulting curable resin layer and the adherend is excellent, and in the case of having a vinyl ether group, a curable resin composition It is preferable because of its excellent curability.

で表される化合物（ただし、Ｙは有機基であり、Ｘ、Ｒ^１０およびＲ^１１は前記と同じ）が挙げられる。さらに好適には、以下の化合物（６ａ）〜（６ｄ）が挙げられる。

Preferred specific examples of the compound represented by the general formula (6) include the following general formula (6 ′)

And a compound represented by the above (wherein Y is an organic group, and X, R ¹⁰ and R ¹¹ are as defined above) can be mentioned. More preferably, the following compounds (6a) to (6d) can be mentioned.

  In the present invention, the compound represented by the general formula (6) may be a compound in which a reactive group and a boron atom are directly bonded, but as shown in the specific example, the compound represented by the general formula (6) It is preferable that the compound represented by these is what the reactive group and the boron atom couple | bonded through the organic group, ie, it is a compound represented by General formula (6 '). If the compound represented by the general formula (6) is bonded to a reactive group via, for example, an oxygen atom bonded to a boron atom, the adhesion water resistance of the polarizing film tends to be deteriorated. On the other hand, the compound represented by the general formula (1) does not have a boron-oxygen bond, but contains a reactive group while having a boron-carbon bond by the bonding of a boron atom and an organic group. In the case of the general formula (6 '), it is preferable because the adhesion water resistance of the polarizing film is improved. Specifically, the organic group means an organic group having 1 to 20 carbon atoms which may have a substituent, and more specifically, for example, having a substituent having 1 to 20 carbon atoms A linear or branched alkylene group, a cyclic alkylene group which may have a substituent of 3 to 20 carbon atoms, a phenylene group which may have a substituent of 6 to 20 carbon atoms, a carbon number of 10 to 10 The naphthylene group etc. which may have 20 substituents are mentioned.

  As the compound represented by the general formula (6), in addition to the compounds exemplified above, an ester of hydroxyethyl acrylamide and boric acid, an ester of methylol acrylamide and boric acid, an ester of hydroxyethyl acrylate and boric acid, and hydroxybutyl Examples are esters of (meth) acrylates with boric acid, such as esters of acrylates with boric acid.

  As a method of forming an easily bonding layer using the easily bonding composition containing the compound represented by General formula (6) on the bonding surface of a polarizer, for example, the compound represented by General Formula (6) is included The easily adhesive composition (A) is manufactured and the method of forming this by apply | coating etc. on the bonding surface of a polarizer is mentioned. A solvent, an additive, etc. are mentioned as what may be contained in addition to the compound represented by General formula (6) in an easily bonding composition (A).

  When an easily bonding composition (A) contains a solvent, composition (A) may be apply | coated to the bonding surface of a polarizer, and a drying process and hardening treatment (heat processing etc.) may be performed as needed.

  As the solvent which may be contained in the easy adhesion composition (A), those which can stabilize and dissolve or disperse the compound represented by the general formula (6) are preferable. As the solvent, an organic solvent, water, or a mixed solvent thereof can be used. Examples of the solvent include esters such as ethyl acetate, butyl acetate and 2-hydroxyethyl acetate; ketones such as methyl ethyl ketone, acetone, cyclohexanone, methyl isobutyl ketone, diethyl ketone, methyl n-propyl ketone and acetylacetone; THF), cyclic ethers such as dioxane; aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; methanol, ethanol, n-propanol, isopropanol, cyclohexanol Aliphatic or alicyclic alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol ethers such as diethylene glycol monoethyl ether; diethylene glycol It is selected from the like; monomethyl ether acetate, diethylene glycol ether acetates, such as monoethyl ether acetate.

  Examples of additives which may be included in the adhesive composition (A) include surfactants, plasticizers, tackifiers, low molecular weight polymers, polymerizable monomers, surface lubricants, leveling agents, antioxidants, and corrosion inhibitors. Agents, light stabilizers, ultraviolet light absorbers, polymerization inhibitors, silane coupling agents, titanium coupling agents, inorganic or organic fillers, metal powders, particles, foils and the like.

  In addition, when an easily bonding composition (A) contains a polymerization initiator, the compound represented by General formula (6) may react in an easily bonding layer before laminating | stacking an adhesive bond layer, and In some cases, the adhesion water resistance improvement effect of the polarizing film, which is the purpose of the present invention, may not be sufficiently obtained. Accordingly, in the easily adhesive layer, the content of the polymerization initiator is preferably less than 2% by weight, preferably less than 0.5% by weight, and it is particularly preferable that the polymerization initiator is not contained.

  If the content of the compound represented by the general formula (6) in the easily adhesive layer is too small, the ratio of the compound represented by the general formula (6) present on the surface of the easily adhesive layer decreases and the adhesion effect is improved. It may be low. Therefore, the content of the compound represented by the general formula (1) in the easily adhesive layer is preferably 1% by weight or more, more preferably 20% by weight or more, and 40% by weight or more. Is more preferred.

  As a method of forming an easily bonding layer on a polarizer using the easily bonding composition (A), a method of directly immersing a polarizer in a treatment bath of the composition (A) or a known coating method may be appropriately used. . Specific examples of the coating method include, but are not limited to, roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating and curtain coating methods.

  In the present invention, when the thickness of the easy adhesion layer included in the polarizer is too thick, the cohesion of the easy adhesion layer may be reduced, and the easy adhesion effect may be lowered. Therefore, the thickness of the easy adhesion layer is preferably 2000 nm or less, more preferably 1000 nm or less, and still more preferably 500 nm or less. On the other hand, as the lower limit of the thickness for the easily bonding layer to sufficiently exhibit the effect, the thickness of the monomolecular film of the compound represented by at least the general formula (1) is mentioned, preferably 1 nm or more. Preferably it is 2 nm or more, More preferably, it is 3 nm or more.

  When an easily bonding layer is formed on the bonding surface of the polarizer, in the easily bonding layer formed on the bonding surface of the polarizer, in addition to the compound described in the general formula (6), M- It may contain a compound having an O bond (M is silicon, titanium, aluminum or zirconium, and O is an oxygen atom). In the present invention, in particular, as the compound having an M-O bond, an organosilicon compound and at least one organometallic compound selected from the group consisting of a metal alkoxide and a metal chelate are preferable.

  As the organosilicon compound, one having a Si-O bond can be used without particular limitation, and as a specific example, an active energy ray curable organic silicon compound or an organosilicon compound which is not active energy ray curable can be used. It can be mentioned. In particular, the carbon number of the organic group contained in the organosilicon compound is preferably 3 or more. Vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidide as active energy ray-curable compounds Xypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, etc. are mentioned.

  Preferred are 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane.

  As a specific example of the compound which is not active energy ray curable, a compound having an amino group is preferable. Specific examples of the compound having an amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyldi Ethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2- Aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, γ- (6- Aminohexyl) aminopropyl trimeth Sisilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl -Γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, Amino group-containing silanes such as (2-aminoethyl) aminomethyltrimethoxysilane, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine; N- (1,3-dimethylbutylidene) -3 -(Triethoxy May be mentioned ketimines type silanes such as Le) -1-propanamine.

  The compound having an amino group may be used alone or in combination of two or more. Among these, in order to ensure good adhesion, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane , Γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl)- 1-Propanamine is preferred.

  Specific examples of compounds which are not active energy ray curable other than the above are 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis Examples include (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, and imidazolesilane.

  The metal alkoxide is a compound in which at least one alkoxy group which is an organic group is bonded to a metal, and the metal chelate is a compound in which an organic group is bonded or coordinated to a metal via an oxygen atom. The metal is preferably titanium, aluminum or zirconium. Among these, aluminum and zirconium have quicker reactivity than titanium, and the pot life of the composition (A) forming the easily adhesive layer may be shortened, and the effect of improving adhesion water resistance may be lowered. Therefore, titanium is more preferable as the metal of the organometallic compound from the viewpoint of improving the adhesion water resistance of the easy adhesion layer.

  When the easily bonding composition (A) for forming the easily bonding layer contains a metal alkoxide as the organic metal compound, it is preferable to use one having 3 or more carbon atoms of the organic group contained in the metal alkoxide, It is more preferable to contain the above. When the carbon number is 2 or less, the pot life of the composition (A) may be shortened, and the effect of improving the adhesion water resistance may be lowered. Examples of the organic group having 6 or more carbon atoms include, for example, an octoxy group, which can be suitably used. Examples of suitable metal alkoxides include, for example, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetraoctyl titanate, tertiary amyl titanate, tetra tert-butyl titanate, tetrastearyl titanate, zirconium tetraisopropoxide, zirconium Tetranormal butoxide, Zirconium tetraoctoxide, Zirconium tetratertiary butoxide, Zirconium tetrapropoxide, Aluminum sec butyrate, Aluminum ethylate, Aluminum isoproperate, Aluminum butyrate, Aluminum diisopropylate mono secondary butyrate, Mono sec butoxy aluminum Diisopropylate, etc. may be mentioned. Among these, tetraoctyl titanate is preferable.

  When the easily bonding composition (A) for forming the easily bonding layer contains a metal chelate as an organic metal compound, it is preferable that the carbon number of the organic group of the metal chelate is 3 or more. While the pot life of an easily bonding composition (A) becomes short that carbon number is two or less, the improvement effect of adhesion water resistance may become low. Examples of the organic group having 3 or more carbon atoms include acetylacetonate group, ethylacetoacetate group, isostearate group, octylene glycolate group and the like. Among these, an acetylacetonato group or an ethylacetoacetate group is preferable as the organic group from the viewpoint of improving the adhesion water resistance of the easily adhesive layer. Examples of suitable metal chelates include, for example, titanium acetylacetonate, titanium octylene glycolate, titanium tetraacetylacetonate, titanium ethyl acetoacetate, polyhydroxy titanium stearate, dipropoxy-bis (acetylacetonato) titanium, di- Butoxytitanium-bis (octylene glycolate), dipropoxytitanium-bis (ethylacetoacetate), titanium lactate, titanium diethanolaminate, titanium triethanolaminate, dipropoxytitanium bis (lactate), dipropoxytitanium bis ( Triethanolaminato), di-n-butoxytitanium-bis (triethanolaminate), tri-n-butoxytitanium monostearate, diisopropoxy bis (ethylacetoacetate) Titanium, diisopropoxy bis (acetyl acetate) titanium, diisopropoxy bis (acetyl acetone) titanium, titanium phosphate compound, titanium lactate ammonium salt, titanium 1,3-propanedioxy bis (ethyl acetoacetate), dodecyl Benzene sulfonic acid titanium compounds, titanium aminoethylaminoethanolate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate, zirconium acetylacetonate bisethylacetoacetate, zirconium acetate, tri-n-butoxyethylacetoate Acetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoa) Tate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, aluminum ethylacetoacetate, aluminum acetylacetonate, aluminum acetylacetonate bisethylacetoacetate, Isopropoxyethylacetoacetate aluminum, diisopropoxyacetylacetonatoaluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonato) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum , Monoacetylacetonato bis (ethylacetoacetate) H) Aluminum is mentioned. Among them, titanium acetylacetonate and titanium ethylacetoacetate are preferable.

  As organic metal compounds usable in the present invention, organic acid carboxylate metal salts such as zinc octylate, zinc laurate, zinc stearate, tin octylate and the like other than the above, zinc acetate acetylacetonate, zinc chelate benzoylacetone, zinc zinc dibenzoylmethane And chelates and zinc chelate compounds such as ethyl acetoacetate zinc chelate.

  The content of the compound having an M-O bond in the easily adhesive layer is preferably 0 to 90% by weight, more preferably 1 to 70% by weight, and particularly preferably 10 to 50% by weight preferable.

  The polarizer and the transparent protective film may be subjected to surface modification treatment before laminating the above adhesive composition. In particular, the polarizer is preferably subjected to surface modification treatment on the surface of the polarizer before applying or bonding the adhesive composition. Examples of the surface modification treatment include treatments such as corona treatment, plasma treatment, itro treatment, excimer treatment, and low pressure UV treatment, and corona treatment is particularly preferable. By performing the corona treatment, a polar functional group such as a carbonyl group or an amino group is generated on the surface of the polarizer, and the adhesion to the curable resin layer is improved. In addition, foreign matter on the surface is removed by the ashing effect, and unevenness on the surface is reduced, so that a polarizing film having excellent appearance characteristics can be formed.

  When the polarizer is subjected to a surface modification treatment, it is preferable that the surface roughness of the surface of the polarizer be 0.6 nm or more. The surface roughness is preferably 0.8 nm or more, more preferably 1 nm or more. By setting the surface roughness to 0.6 nm or more, the polarizer can be favorably transported even when the surface of the polarizer is brought into contact with the guide roll in the manufacturing process of the polarizing film. The surface roughness is preferably 10 nm or less, more preferably 5 nm or less, because the hot water resistance is deteriorated if the surface roughness is too large.

  The measurement of the surface roughness is a parameter representing the surface roughness by the calculated average roughness (average value of surface irregularities). The measurement of the surface roughness is a value measured in Tapping mode using a Bico atomic force microscope (AFM) Nanoscope IV. As a cantilever, for example, a metrology probe: Tap300 (RTESP type) was used. The measurement range is 1 μm square.

<Polarizing film>
The thickness of the polyvinyl alcohol-based polarizer, the adhesive layer, the transparent protective film, and the polarizing film obtained by laminating the pressure-sensitive adhesive layer as necessary is preferably 150 μm or less, more preferably 100 μm or less. When the thickness of the polarizing film is too thick, dimensional change under high temperature and high humidity becomes large, and a problem of display unevenness occurs, which is not preferable.

  It is preferable that the thickness of the hardened | cured material layer formed by the said adhesive composition, especially the adhesive layer is 0.2-3 micrometers. When the thickness of the cured material layer is too thin, the cohesion of the cured material layer is insufficient and the peeling force is reduced, which is not preferable. If the thickness of the cured product layer is too large, peeling is likely to occur when a stress is applied to the cross section of the polarizing film, and peeling defects due to impact occur, which is not preferable. The thickness of the adhesive layer is more preferably 0.3 to 2 μm, and most preferably 0.4 to 1.5 μm.

When the thickness of the adhesive layer is d μm and the content of the air bubble suppressor contained in the adhesive layer is y wt%, when the following formula (1) is satisfied, the effect of suppressing laminate air bubbles and the effect of improving adhesiveness are It is preferable because
0.1-0.02 d ≦ y ≦ 0.6-0.08 d (1)

The laminated optical film according to the present invention, in particular the polarizing film, is produced by the following method:
A method for producing a laminated optical film in which a transparent protective film is laminated on at least one surface of an optical film via an adhesive layer formed by curing an adhesive composition, which is an adhesive for a transparent protective film A pretreatment step of bringing an organic solvent having an SP value distance with the transparent protective film of 10 or less into contact with the surface forming the layer, a contact surface of the transparent protective film with the organic solvent and the transparent protective film side of the optical film The transparent protective film and the adhesive layer are formed by laminating the transparent protective film and the optical film via the adhesive composition, and a coating step of directly coating the adhesive composition on at least one of the surfaces of And a bonding step of forming a compatible layer in which the composition changes continuously, and irradiating active energy rays from the optical film side or the transparent protective film side. Through an adhesive layer formed by curing the adhesive composition, a method of manufacturing a laminated optical film comprising a bonding step for bonding the optical film and the transparent protective film can be manufactured by. Here, the SP value distance between the SP value of the transparent protective film and the SP value of the adhesive composition is preferably 10 or less.

  The method for applying the adhesive composition is appropriately selected according to the viscosity of the composition and the intended thickness, and for example, a reverse coater, a gravure coater (direct, reverse or offset), a bar reverse coater, a roll coater, a die coater , Bar coaters, rod coaters and the like.

  Usually, when laminating two films, it is customary to apply and laminate an adhesive composition on the bonding surface of one film, for example, the contact surface of the transparent protective film with the organic solvent, The adhesive layer is coated and then laminated on both the contact surface of the transparent protective film with the organic solvent and the surface of the optical film on the transparent protective film side, so that the appearance quality is excellent. A laminated film can be obtained. As a method of coating, a post-weighing coating method is preferable. In the present invention, the “post-metering coating method” refers to a method in which an external force is applied to the liquid film to remove excess liquid, thereby obtaining a predetermined coated film thickness. In the method for producing a polarizing film according to the present invention, when an external force applied to a liquid film made of an adhesive composition is applied, foreign substances such as dust and dirt present on the bonding surface are scraped off. Although a gravure roll coating method, a forward roll coating method, an air knife coating method, a rod / bar coating method etc. are mentioned as a specific example of a post-weighing coating method, the removal precision of a foreign material and the coating film thickness are uniform. From the viewpoint of properties and the like, in the present invention, the coating method is preferably a gravure roll coating method using a gravure roll.

  A polarizer and a transparent protective film can be bonded together via the adhesive composition coated as mentioned above. The lamination of the polarizer and the transparent protective film can be performed by a roll laminator or the like. The method of laminating a protective film on both sides of a polarizer includes a method of laminating a polarizer and a sheet of protective film and then laminating another protective film and a polarizer and a sheet of protective film simultaneously It is selected from the matching method. The bite bubbles generated when bonding are significantly reduced by adopting the former method, that is, the method of bonding one more protective film after laminating the polarizer and one protective film. It is preferable because

  Active energy rays used in the curing step can be roughly classified into electron beam curing properties, ultraviolet curing properties, and visible light curing properties. In the present invention, active energy rays in the wavelength range of 10 nm to less than 380 nm are represented as ultraviolet light, and active energy rays in the wavelength range of 380 nm to 800 nm are represented as visible light. In the production of the polarizing film according to the present invention, it is particularly preferable to use visible light of 380 nm to 450 nm.

  In the laminated optical film according to the present invention, in particular, the polarizing film, after the polarizing film adhesive composition is directly coated on the polarizer and / or the transparent protective film and the polarizer and the transparent protective film are laminated, The adhesive composition is cured by irradiation with active energy rays (electron beam, ultraviolet light, visible light, etc.) to form an adhesive layer. The irradiation direction of the active energy ray (electron beam, ultraviolet light, visible light, etc.) can be irradiated from any appropriate direction. Preferably, it irradiates from the transparent protective film side. When irradiated from the polarizer side, the polarizer may be degraded by active energy rays (electron beam, ultraviolet light, visible light, etc.).

  With regard to the electron beam curing property, any appropriate condition can be adopted as long as the irradiation condition of the electron beam can cure the above adhesive composition for a polarizing film. For example, in the electron beam irradiation, the acceleration voltage is preferably 5 kV to 300 kV, and more preferably 10 kV to 250 kV. If the acceleration voltage is less than 5 kV, the electron beam may not reach the adhesive composition for polarizing film and curing may be insufficient. If the acceleration voltage exceeds 300 kV, the penetration through the sample is too strong and the transparent protective film And may damage the polarizer. The irradiation dose is 5 to 100 kGy, more preferably 10 to 75 kGy. When the irradiation dose is less than 5 kGy, the curing of the adhesive composition for polarizing film is insufficient, and when it exceeds 100 kGy, the transparent protective film and the polarizer are damaged, resulting in reduction of mechanical strength and yellowing. Optical properties can not be obtained.

  Electron beam irradiation is usually performed in an inert gas, but if necessary, it may be performed in the air or under a condition where a small amount of oxygen is introduced. Depending on the material of the transparent protective film, by appropriately introducing oxygen, it is possible to cause oxygen inhibition to occur on the transparent protective film surface that the electron beam first strikes, to prevent damage to the transparent protective film, and only to the adhesive Electron beams can be irradiated efficiently.

  In the method for producing a laminated optical film according to the present invention, in particular, a polarizing film, the active energy ray contains visible light in the wavelength range of 380 nm to 450 nm, particularly the irradiation amount of visible light in the wavelength range of 380 nm to 450 nm is the largest It is preferred to use active energy rays. In the case of using a transparent protective film provided with an ultraviolet absorbing ability (ultraviolet non-transparent transparent protective film) in ultraviolet curing and visible light curing, it absorbs light shorter than about 380 nm, so it has a wavelength shorter than 380 nm The light does not reach the adhesive composition and does not contribute to its polymerization reaction. Furthermore, light of a wavelength shorter than 380 nm absorbed by the transparent protective film is converted into heat, and the transparent protective film itself generates heat, which causes defects such as curls and wrinkles of the polarizing film. Therefore, in the present invention, in the case of adopting ultraviolet curability and visible light curability, it is preferable to use a device which does not emit light having a wavelength shorter than 380 nm as an active energy ray generator. More specifically, the wavelength range 380 It is preferable that ratio of the integral illumination intensity of -440 nm and the integral illumination intensity of a wavelength range 250-370 nm is 100: 0 to 100: 50, and it is more preferable that it is 100: 0 to 100: 40. As the active energy ray according to the present invention, a gallium-filled metal halide lamp and an LED light source emitting light in the wavelength range of 380 to 440 nm are preferable. Or UV light such as low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, super high pressure mercury lamp, incandescent lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser or sunlight A light source including visible light can be used, and a band pass filter can be used to block ultraviolet rays shorter than 380 nm. In order to prevent the curling of the polarizing film while enhancing the adhesion performance of the adhesive layer between the polarizer and the transparent protective film, a gallium-filled metal halide lamp can be used and light having a wavelength shorter than 380 nm can be blocked. It is preferable to use an active energy ray obtained through a band pass filter, or an active energy ray with a wavelength of 405 nm obtained using an LED light source.

  When the polarizing film according to the present invention is produced in a continuous line, the line speed depends on the curing time of the adhesive composition, preferably 5 to 100 m / min, more preferably 10 to 50 m / min, still more preferably 20 to 20 m / min. It is 30 m / min. If the line speed is too small, productivity is poor or damage to the transparent protective film is too large, and a polarizing film that can withstand durability tests and the like can not be produced. If the line speed is too high, the curing of the adhesive composition may be insufficient and the desired adhesion may not be obtained.

  The polarizing film of the present invention can be used as an optical film laminated with other optical layers in practical use. The optical layer is not particularly limited, but, for example, for the formation of a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including a wave plate such as 1/2 or 1/4), a viewing angle compensation film, etc. One or two or more optical layers may be used. In particular, a reflective polarizing film or a semitransparent polarizing film in which a reflecting plate or a semitransparent reflecting plate is further laminated to the polarizing film of the present invention, an elliptically polarizing film in which a retardation plate is further laminated to a polarizing film or circularly polarized light A film, a wide viewing angle polarizing film in which a viewing angle compensation film is further laminated on a polarizing film, or a polarizing film in which a brightness enhancement film is further laminated on a polarizing film is preferable.

  An optical film in which the above optical layer is laminated on a polarizing film can also be formed by a method of sequentially laminating separately in the production process of a liquid crystal display device or the like. It is excellent in stability, assembly work, etc., and there is an advantage which can improve manufacturing processes, such as a liquid crystal display. An appropriate adhesive means such as an adhesive layer may be used for lamination. When bonding the above-mentioned polarizing film and other optical films, their optical axes can be set at appropriate arrangement angles in accordance with the target retardation characteristics and the like.

  A pressure-sensitive adhesive layer for bonding to another member such as a liquid crystal cell can also be provided on the above-described polarizing film or an optical film in which at least one polarizing film is laminated. The pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer is not particularly limited, but, for example, one having an acrylic polymer, a silicone-based polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine-based or rubber-based polymer as a base polymer is appropriately selected. Can be used. In particular, those having excellent optical transparency such as acrylic pressure-sensitive adhesives, exhibiting appropriate wettability, cohesion, and adhesive properties such as adhesiveness, and being excellent in weather resistance, heat resistance and the like can be preferably used.

  The pressure-sensitive adhesive layer can also be provided on one side or both sides of a polarizing film or an optical film as an overlapping layer of different compositions or types. Moreover, when providing in both surfaces, it can also be set as adhesion layers, such as a different composition, a kind, and thickness, in the front and back of a polarizing film or an optical film. The thickness of the pressure-sensitive adhesive layer can be appropriately determined depending on the purpose of use, adhesive strength and the like, and is generally 1 to 100 μm, preferably 5 to 30 μm, and particularly preferably 10 to 20 μm.

  The exposed surface of the adhesive layer is temporarily attached and covered with a separator for the purpose of preventing contamination and the like until it is put to practical use. Thereby, it can prevent contacting an adhesion layer in the usual handling state. As the separator, except for the above thickness conditions, for example, suitable thin sheets such as plastic films, rubber sheets, paper, cloths, non-woven fabrics, nets, foamed sheets and metal foils, laminates thereof, silicone-based or long as required A suitable one according to the prior art may be used, such as one coated with a suitable release agent such as chain alkyl type, fluorine type or molybdenum sulfide.

  In the present invention, various laminated optical films can be produced by arbitrarily combining functional films such as the transparent protective film, the polarizer, and the brightness enhancement film described above. Below, an example of these is shown.

(Pattern 1)
A polarizing film comprising a transparent protective film laminated on one side of a polarizer via an adhesive layer formed by curing an adhesive composition, which is between a transparent protective film and an adhesive layer In addition, a polarizing film in which a compatible layer in which the composition changes continuously is formed. An easily adhesive layer containing at least the compound represented by the general formula (6) may be formed on the surface on the adhesive layer side of the polarizer.

(Pattern 2)
A polarizing film comprising a transparent protective film laminated on both sides of a polarizer via an adhesive layer formed by curing an adhesive composition, comprising at least one transparent protective film and an adhesive layer In the meantime, the polarizing film in which the compatible layer from which these compositions changed continuously was formed. An easily adhesive layer containing at least the compound represented by the general formula (6) may be formed on the surface on the adhesive layer side of the polarizer. Moreover, an adhesive layer may be laminated | stacked on the surface on the opposite side to the adhesive bond layer of a transparent protective film.

(Pattern 3)
A transparent protective film is laminated on one side of a polarizer via an adhesive layer formed by curing an adhesive composition, and polarized light is laminated on the other side of the polarizer. It is a film, Comprising: The polarizing film in which the compatible layer in which these compositions changed continuously between the transparent protective film and the adhesive layer was formed. An easily adhesive layer containing at least the compound represented by the general formula (6) may be formed on the surface on the adhesive layer side of the polarizer. In addition, a functional film may be laminated on the side of the adhesive layer opposite to the polarizer, and an adhesive layer may be laminated on the side of the transparent protective film opposite to the adhesive layer.

(Pattern 4)
A laminated optical film in which at least two transparent protective films are laminated via an adhesive layer, and a phase in which the composition continuously changes between the at least one transparent protective film and the adhesive layer. A laminated optical film in which a solution layer is formed. The transparent protective films to be laminated may be the same type of transparent protective films or may be different types of transparent optical films. In addition, an adhesive layer may be laminated on the surface of the transparent protective film opposite to the adhesive layer.

(Pattern 5)
A polarizing film comprising a transparent protective film laminated on both sides of a polarizer via an adhesive layer formed by curing an adhesive composition, comprising at least one transparent protective film and an adhesive layer In the meantime, a compatible layer in which the composition changes continuously is formed, and a transparent protective film is further laminated on the side opposite to the adhesive layer of at least one transparent protective film through the adhesive layer. Polarized film. A pressure-sensitive adhesive layer may be laminated on the surface of the outermost transparent protective film opposite to the adhesive layer.

(Pattern 6)
A transparent protective film is laminated on one side of a polarizer via an adhesive layer formed by curing an adhesive composition, and adhesion is made on the side of the transparent protective film opposite to the adhesive layer. A transparent protective film is further laminated via an adhesive layer, and a functional film is laminated on the other surface of the polarizer via an adhesive layer, and at least one of the transparent protective film and the adhesive layer And a polarizing film in which a compatible layer in which the composition continuously changes is formed. A functional film may be laminated on the side of the adhesive layer opposite to the polarizer, and an adhesive layer may be laminated on the side of the transparent protective film opposite to the adhesive layer.

  The polarizing film or the optical film of the present invention can be preferably used for forming various devices such as liquid crystal display devices. The formation of the liquid crystal display can be performed according to the prior art. That is, in general, a liquid crystal display device is formed by appropriately assembling components such as a liquid crystal cell, a polarizing film or an optical film, and an illumination system as necessary, and incorporating a drive circuit. There is no particular limitation except that the polarizing film according to the invention or the optical film / BR> crystal is used, and may be in accordance with the prior art. The liquid crystal cell may also be of any type such as TN type, STN type, or π type.

  It is possible to form a suitable liquid crystal display device such as a liquid crystal display device in which a polarizing film or an optical film is disposed on one side or both sides of a liquid crystal cell, or a lighting system using a backlight or a reflector. In that case, the polarizing film or the optical film according to the present invention can be disposed on one side or both sides of the liquid crystal cell. When providing a polarizing film or an optical film on both sides, they may be the same or different. Furthermore, when forming a liquid crystal display device, for example, one or more appropriate components such as a diffusion plate, antiglare layer, anti-reflection film, protective plate, prism array, lens array sheet, light diffusion plate, and back light at appropriate positions. Two or more layers can be arranged.

  Examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

  In the present invention, the SP value and the SP value distance were determined by the following method.

<Method of estimating SP value of active energy ray-curable adhesive composition>
The SP value of the active energy ray-curable adhesive composition was calculated using the Hansen Solubility Parameter in Practice (HSPiP) Y-MB method for each of the constituent materials of the composition, and the Hansen solubility parameter (SP value) was calculated. It calculated | required by taking an average value according to the molar ratio of.

<Method of estimating SP value of organic solvent>
The SP value of the organic solvent is the Hansen Solubility Parameter in Practice (HSPiP) ver. Official values were obtained from Hansen's solubility parameter (SP value) database stored in 4.1.07. In the case where two or more types of organic solvents are mixed and used, it is determined by taking an average value according to the molar ratio.

<Method of measuring SP value of transparent protective film>
The transparent protective film was prepared using 14 solvents having different solubilities, water, acetone, cyclopentanone, isopropyl alcohol, ethanol, methanol, toluene, p-xylene, cyclohexane, n-hexane, ethyl acetate, trichlorobenzene, anisole and the like. It was immersed in the mixed solvent for 10 minutes. The appearance of the transparent protective film after immersion for 10 minutes was classified into three stages of (1) dissolution, (2) swelling, and (3) insoluble. Based on the information of the solubility in each solvent thus obtained, Hansen Solubility Parameter in Practice (HSPiP) ver. Hansen's solubility parameter (SP value) was calculated by 4.1.07 (http://www.hansen-solubility.com/index.php).

<SP value distance (Ra-1) between SP value of transparent protective film and SP value of adhesive composition>
The dispersion term of Hansen's solubility parameter of the transparent protective film is σd, the polar term is σp, and the hydrogen bond term is σh, and the dispersion term of Hansen's solubility parameter of the active energy ray-curable adhesive composition is σAd, the polar term is σAp When the hydrogen bond term is σAh, the following formula; Ra-1 = [4 × (σd−σAd) ² + 2 × (σp−σAp) ² + 2 × (σh−σAh) ² ] ^1/2 “transparent protection It was defined as "the SP value distance (= Ra-1) between the SP value of the film and the SP value of the adhesive composition. It was calculated using the Hansen solubility parameter of the transparent protective film and active energy ray-curable adhesive composition calculated by the method described above.

<SP Value Distance Ra-2 Between SP Value of Transparent Protective Film and SP Value of Organic Solvent>
The dispersion term of Hansen's solubility parameter of transparent protective film is σd, the polar term is σp, the hydrogen bond term is σh, the dispersion term of Hansen's solubility parameter of organic solvent is σBd, the polar term is σBp, and the hydrogen bond term is σBh when, following equation; Ra-2 = [4 × (σd-σBd) 2 + 2 × (σp-σBp) 2 + 2 × (σh-σBh) 2] SP value and organic solvent ^1/2 "transparent protective film It was defined as "SP value distance" (= Ra-2) between SP values of. It calculated using the Hansen's solubility parameter of the transparent protective film and organic solvent calculated by the above-mentioned method.

  In the present invention, a compatible layer (in Tables 1 to 8 simply referred to as “compatible layer”) in which these layers continuously change is formed between the transparent protective film and the adhesive layer. The following method was used to determine the presence or absence.

<Confirmation of compatible layer>
In order to observe the cross section of the film, the test piece prepared by the ultrathin section method is observed at an accelerating voltage of 100 kV using a transmission electron microscope (TEM) (product name “H-7650” manufactured by Hitachi, Ltd.) A TEM picture was taken. The case where the compatible layer was formed was referred to as "present", and the case where the compatible layer was not formed was referred to as "absent".

Example 1-1 to Example 1-9 and Comparative Example 1-1 to Comparative Example 1-6
<Fabrication of Polarizer>
A polyvinyl alcohol film having a degree of polymerization of 2400 and a degree of saponification of 99.9 mol% and a thickness of 45 μm was immersed in warm water at 30 ° C. for 60 seconds for swelling. Then, the film was dyed while being immersed in an aqueous solution of 0.3% concentration of iodine / potassium iodide (weight ratio = 0.5 / 8) and stretched to 3.5 times. Thereafter, in a boric acid ester aqueous solution at 65 ° C., stretching was performed so that the total stretching magnification was 6 times. After stretching, drying was performed in an oven at 40 ° C. for 3 minutes to obtain a polyvinyl alcohol-based polarizer X (thickness 18 μm). Next, an adhesive composition containing 1% by weight of 4-vinylphenylboronic acid and 99% by weight of isopropyl alcohol on both sides of the polarizer X using a wire bar (No. 2 manufactured by Daiichi Rika Co., Ltd.) The solvent was removed by air-drying at 60 ° C. for 1 minute to prepare a polarizer with an easy-adhesion layer having a thickness of 1 nm after drying of the easy-adhesion layer.

<Transparent Protective Film 1>
In a reaction vessel equipped with a stirrer, 2.70 kg of 2,2-bis (4-hydroxyphenyl) -4-methylpentane and 0.06 kg of tetrabutylammonium chloride were dissolved in 25 liters of 1 M sodium hydroxide solution. A solution of 1.22 kg of terephthalic acid chloride and 0.81 kg of isophthalic acid chloride in 30 L of toluene was added to this solution with stirring, and stirred at room temperature for 90 minutes. Thereafter, the polymerization solution was allowed to stand and separated, and the toluene solution containing the polymer was separated, and then washed with aqueous acetic acid, washed with ion exchanged water, and then poured into methanol to precipitate the polymer. The precipitated polymer was filtered and dried under reduced pressure to obtain 3.41 kg (yield 92%) of a white polymer.

  The obtained polymer was dissolved in toluene, coated on biaxially oriented polypropylene, dried at 80 ° C. for 5 minutes, and then dried at 110 ° C. for 5 minutes to prepare a laminated film having a coating film of 15 μm. The obtained laminated film is stretched 1.2 times in the width direction at 145 ° C. while being conveyed using a simultaneous biaxial stretching machine, and is shrunk so as to be 0.75 times in MD. The polyarylate transparent protective film 1 was obtained. The obtained transparent protective film 1 had a thickness of 15.0 μm, Re = 275 nm, Rth = 138 nm, and Nz coefficient = 0.5.

  Using a wire bar (No. 3 manufactured by Daiichi Rika Co., Ltd.) on the side of the transparent protective film 1 on which the adhesive layer is to be formed, the SP value distance to the transparent protective film 1 is Ra described in Table 1 A pretreatment was performed to apply an organic solvent having a composition of -1. Then, on the contact surface of the transparent protective film 1 with the organic solvent, an adhesive composition having a composition such that the SP value distance to the transparent protective film 1 is Ra-2 described in Table 1 is used. Using a mechanical company (cell shape: honeycomb, gravure roll wire number: 1000 / inch, rotational speed 140% / vs. Line speed), coat to a thickness of 1 μm, It stuck with the roll machine. Thereafter, the visible light beam is irradiated on both sides by the active energy ray irradiation device from the transparent protective film 1 side (both sides) bonded to cure the curable adhesive, and then hot air drying at 70 ° C. for 3 minutes, The polarizing film which has the transparent protective film 1 in the both sides of a polarizer was obtained. The line speed of bonding was 25 m / min.

  The adhesion of the obtained polarizing film was evaluated by the following method.

<Initial adhesive strength>
The polarizing film was cut out in a size of 200 mm parallel to the stretching direction of the polarizer and 15 mm in the orthogonal direction, and the polarizing film was bonded to a glass plate. Then, a cut is made between the transparent protective film and the polarizer with a cutter knife, and the protective film and the polarizer are peeled at a peeling speed of 300 mm / min in a 90 degree direction with a tensilon, and the peeling strength (N / 15 mm) It was measured. Moreover, the infrared absorption spectrum of the peeling surface after peeling was measured by ATR method, and the peeling form was evaluated based on the following reference | standard. The results are shown in Table 1-8. In Table 1-8, those in which the peel strength is described as "broken" mean that the base material is broken when the peel strength is measured because the adhesive strength is superior to that of the base material. .
○: When the material of the transparent protective film breaks or when the material of the polarizer breaks Δ: When material destruction of the transparent protective film and interfacial peeling between the transparent protective film and the adhesive layer are mixed, or the material of the polarizer When destruction and interfacial peeling between the polarizer and the adhesive layer are mixed ×: When interfacial peeling between the transparent protective film and the adhesive layer or interfacial peeling between the polarizer and the adhesive layer occurs

  <Adhesive force after 85 ° C 85RH-48h> A polarizing film is cut out to a size of 200 mm parallel to the stretching direction of the polarizer and 15 mm in the orthogonal direction, the polarizing film is bonded to a glass plate, and 85 ° C. 85% RH environment Exposure for 48 hours. Thereafter, the same evaluation as in the initial adhesion evaluation was performed to evaluate the peel strength and the peel form. The results are shown in Table 1.

Example 2-1 to Example 2-12 and Comparative Example 2-1 to Comparative Example 2-8
A polarizing film was produced and evaluated in the same manner as in Example 1 except that the transparent protective film was changed to a polycarbonate shown below, and the organic solvent and the adhesive composition were changed to those shown in Table 2.

<Transparent Protective Film 2>
The polymerization was carried out using a batch polymerization apparatus consisting of two vertical reactors equipped with stirring blades and a reflux condenser controlled at 100 ° C. 29.60 parts by mass (0.046 mol) of bis [9- (2-phenoxycarbonylethyl) fluoren-9-yl] methane, 29.21 parts by mass (0.200 mol) of ISB, 42.28 parts by mass of SPG (0. 139 mol), DPC
63.77 parts by mass (0.298 mol) and 1.19.times.10@-2 parts by mass (6.78.times.10@-5 mol) of calcium acetate monohydrate were charged as a catalyst. After the inside of the reactor was purged with nitrogen under reduced pressure, heating was performed with a heat medium, and when the internal temperature reached 100 ° C., stirring was started. The internal temperature was allowed to reach 220 ° C. 40 minutes after the start of heating and controlled to maintain this temperature, and at the same time depressurization was started, and it reached 13.3 kPa in 90 minutes after reaching 220 ° C. The phenol vapor by-produced together with the polymerization reaction was led to a 100 ° C. reflux condenser, the monomer components contained in a small amount in the phenol vapor were returned to the reactor, and the non-condensed phenol vapor was led to a 45 ° C. condenser and recovered. Nitrogen was introduced into the first reactor and the pressure was once reduced to atmospheric pressure, and then the oligomerized reaction liquid in the first reactor was transferred to the second reactor. Subsequently, the temperature rise and pressure reduction in the second reactor were started, and the internal temperature was 240 ° C. and the pressure was 0.2 kPa in 50 minutes. Thereafter, polymerization was allowed to proceed until a predetermined stirring power was reached. When a predetermined power was reached, nitrogen was introduced into the reactor to repressurize, the produced polyester carbonate was extruded into water, and the strands were cut to obtain pellets.

  The obtained polycarbonate resin is vacuum dried at 80 ° C. for 5 hours, and then a single screw extruder (manufactured by Toshiba Machine Co., Ltd., cylinder set temperature: 250 ° C.), T die (width 200 mm, set temperature: 250 ° C.), chill roll ( A resin film having a thickness of 135 μm was produced using a film production apparatus equipped with a set temperature of 120 to 130 ° C. and a winder.

  A stretched film is obtained by stretching the obtained long resin film in the width direction at a stretching temperature of 134 ° C. and a stretching ratio of 2.8 times and subsequently subjecting the stretched film in the width direction to a relaxation treatment. Was produced. The relaxation treatment conditions were a relaxation temperature of 130 ° C. and a relaxation rate of 4.5%. A polycarbonate-based transparent protective film 2 having a thickness of 48 μm was obtained.

Example 3-1 to Example 3-11 and Comparative Example 3-1 to Comparative Example 3-3
A polarizing film was produced and evaluated in the same manner as in Example 1, except that the transparent protective film was changed to an acrylic shown below and the organic solvent and adhesive composition were changed to those shown in Table 3.

<Transparent Protective Film 3>
Transparent protective film A (containing glutarimide unit): MS resin (MS-200; copolymer of methyl methacrylate / styrene (molar ratio) = 80/20, manufactured by Nippon Steel Chemical Co., Ltd.) is imide with monomethylamine (Imidation ratio: 5%). The resulting imidized MS resin is a glutarimide unit represented by the general formula (1) described in JP-A-2016-139027 (wherein, R ¹ and R ³ are methyl groups and R ² is a hydrogen atom) (Meth) acrylic acid ester units represented by the general formula (2) described in JP-A-2016-139027 (R ⁴ is a hydrogen atom, R ⁵ and R ⁶ are methyl groups), and a styrene unit Have. In addition, the intermeshing type co-rotating twin-screw extruder with a bore of 15 mm was used for the imidization. The set temperature of each temperature control zone of the extruder was 230 ° C, screw rotation number 150 rpm, and MS resin was supplied at 2.0 kg / hr. The amount of monomethylamine supplied was 2 parts by weight with respect to 100 parts by weight of MS resin. . The MS resin was charged from the hopper, and the resin was melted and filled with a kneading block, and then monomethylamine was injected from the nozzle. A seal ring was placed at the end of the reaction zone to fill the resin. Byproducts after reaction and excess methylamine were removed by reducing the pressure at the vent port to -0.08 MPa. The resin which came out as a strand from the die provided at the extruder outlet was pelletized with a pelletizer after being cooled in a water bath. The imidized MS resin was formed by melt extrusion. At this time, an ultraviolet absorber ("T-712" manufactured by ADEKA Corporation) was supplied at 0.66 parts by weight with respect to 100 parts by weight of the MS resin. Then, an acrylic transparent protective film 3 (thickness 40 μm, Re = 2 nm, Rth = 2 nm) biaxially stretched to 2 × in length and 2 × in width was produced.

Examples 4-1 to 4-7 and comparative examples 4-1 to 4-8
A polarizing film was produced in the same manner as in Example 1, except that the transparent protective film was changed to triacetyl cellulose (TAC) shown below, and the organic solvent and adhesive composition were changed to those shown in Table 4. And evaluated.

<Transparent Protective Film 2>
60 um thick triacetyl cellulose film Name: TG60UL Fujifilm Corporation

Examples 5-1 to 5-4 and Comparative Example 5-1
A polarizing film was manufactured and evaluated in the same manner as in Example 1 except that the pretreatment for applying the organic solvent was not performed.

Examples 6-1 to 6-6 and comparative examples 6-1 to 6-2
A polarizing film was manufactured and evaluated in the same manner as in Example 2 except that the pretreatment for applying the organic solvent was not performed.

Examples 7-1 to 7-3 and Comparative Example 7-1
A polarizing film was manufactured and evaluated in the same manner as in Example 3 except that the pretreatment for applying the organic solvent was not performed.

Examples 8-1 to 8-7 and Comparative Example 8-1
A polarizing film was manufactured and evaluated in the same manner as in Example 4 except that the pretreatment for applying the organic solvent was not performed.

In Tables 1 to 8, the compounds used as the adhesive composition are shown below.
HEAA; hydroxyethyl acrylamide (made by Kojinsha)
DEAA; diethyl acrylamide (made by Kojinsha)
19ND-A; 1,9-nonanediol diacrylate (trade name "light acrylate 1, 9ND-A", manufactured by Kyoeisha Chemical Co., Ltd.)
HPAA; hydroxypivalic acid didiacrylate (trade name: Light acrylate HPPA, manufactured by Kyoeisha Chemical Co., Ltd.)
DCP-A; dimethylol-tricyclodecane diacrylate (trade name "light acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.)
M-220; tripropylene glycol diacrylate (trade name "ALONIX M-220" manufactured by Toagosei Co., Ltd. NP-A; neopentyl glycol diacrylate (trade name "light acrylate NP-A" manufactured by Kyoeisha Chemical Co., Ltd.)
ACMO: Acryloyl morpholine (made by Kojinsha)
Wasmar 2MA; N-methoxymethyl acrylamide (trade name "Wasmar 2MA", manufactured by Hino Kosan Co., Ltd.)
NVP; N-vinyl pyrrolidone (trade name "NVP", manufactured by Nippon Shokubai Co., Ltd.)
IB-XA; isobornyl acrylate (trade name "light acrylate IB-XA", manufactured by Kyoeisha Chemical Co., Ltd.)
GBLA; γ-butyrolactone acrylate (trade name "GBLA", manufactured by Osaka Organic Chemical Industry Ltd.)
M5700; 2-hydroxy-3-phenoxypropyl acrylate (trade name: Alonix M5700, manufactured by Toagosei Co., Ltd.)
APG 100; dipropylene glycol diacrylate (trade name APG 100, manufactured by Shin-Nakamura Chemical Co., Ltd.)
AAEA; 2-acetoacetoxyethyl acrylate (trade name AAEA, manufactured by Japan Synthetic Chemical Industry Co., Ltd.)
ISTA; isostearyl acrylate (trade name ISTA, manufactured by Osaka Organic Chemical Industry Ltd.)
Celloxide 2021 P; 3 ', 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate (trade name Celoxide 2021 P, manufactured by Daicel Corporation)
FA513AS; dicyclopentanyl acrylate (trade name Funcryl FA513AS, manufactured by Hitachi Chemical Co., Ltd.) GBL; γ-butyrolactone (manufactured by Mitsubishi Chemical Corporation) propylene carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) anisole (manufactured by Tokyo Chemical Industry Co., Ltd.)

Claims (7)

A method for producing a laminated optical film, wherein a transparent protective film is laminated on at least one surface of an optical film via an adhesive layer formed by curing an adhesive composition,
A pretreatment step of bringing an organic solvent having an SP value distance of 12 or less to the transparent protective film into contact with the surface of the transparent protective film on which the adhesive layer is to be formed;
A coating step of directly coating the adhesive composition on at least one surface of the transparent protective film in contact with the organic solvent and the surface of the optical film on the transparent protective film side;
A compatible layer in which the composition continuously changes between the transparent protective film and the adhesive layer by laminating the transparent protective film and the optical film via the adhesive composition. Bonding process to form
The optical film and the transparent protective film are provided via an adhesive layer formed by irradiating the active energy ray from the optical film side or the transparent protective film side to cure the adhesive composition. And a bonding step of bonding.   The method for producing a laminated optical film according to claim 1, wherein an SP value distance between an SP value of the transparent protective film and an SP value of the adhesive composition is 12 or less. The coating step is a step of applying the adhesive composition to the surface on the transparent protective film side of the optical film, and the bonding step is the optical film coated with the adhesive composition. The method for producing a laminated optical film according to claim 1 or 2, wherein the method is a step of laminating a surface of the adhesive composition on the side to which the adhesive composition is applied to the surface of the transparent protective film in contact with the organic solvent. The application step is a step of applying the adhesive composition on both the contact surface of the transparent protective film with the organic solvent and the surface of the optical film on the transparent protective film side, method for producing focus process, the laminated optical film according to claim 1 or 2 from both the coated surface side of a step of bonding the said optical film and the transparent protective film.   The method for producing a laminated optical film according to any one of claims 1 to 4, wherein the adhesive composition is an active energy ray-curable adhesive composition containing a monomer having a polymerizable group.   The method for producing a laminated optical film according to any one of claims 1 to 5, wherein the optical film is a polyvinyl alcohol-based polarizer.   The production of the laminated optical film according to any one of claims 1 to 6, wherein the transparent protective film is at least one thermoplastic resin selected from the group consisting of polyarylate, polycarbonate, acrylic polymer and triacetyl cellulose. Method.