JP2014189788A - Active energy ray-curable adhesive composition, polarization film and manufacturing method thereof, optical film and picture display unit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active energy ray-curable adhesive composition capable of providing an adhesive layer for laminating at least two components and capable of providing an adhesive agent having excellent waterproofness, exerting adhesive property after immersion in normal temperature water for several hours.SOLUTION: An active energy ray-curable adhesive composition includes: a radical-polymerizable compound (A); a radical generator (B); an optical acid generator (C); and an amino compound (D) including an alkoxy group.

Description

  The present invention relates to an active energy ray-curable adhesive composition for forming an adhesive layer for adhering two or more members, particularly an active energy ray-curable adhesive for forming an adhesive layer between a polarizer and a transparent protective film. The present invention relates to a composition and a polarizing film. The polarizing film can form an image display device such as a liquid crystal display device (LCD), an organic EL display device, a CRT, or a PDP alone or as an optical film obtained by laminating the polarizing film. Furthermore, this invention relates to the manufacturing method of this polarizing film, an optical film, and an image display apparatus.

  Liquid crystal display devices are rapidly expanding in watches, mobile phones, PDAs, notebook computers, personal computer monitors, 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 TV, higher brightness, higher contrast, and wider viewing angle are required, and polarizing films are also required to have higher transmittance, higher degree of polarization, and higher color reproducibility.

  As the polarizer, since it has a high transmittance and a high degree of polarization, for example, an iodine-based polarizer having a stretched structure by adsorbing iodine to polyvinyl alcohol (hereinafter also simply referred to as “PVA”) is most widely used. It is used. In general, a polarizing film in which a transparent protective film is bonded to both surfaces of a polarizer by a so-called aqueous adhesive in which a polyvinyl alcohol-based material is dissolved in water is used (Patent Document 1 and Patent Document 2 below). ). As the transparent protective film, triacetyl cellulose having a high moisture permeability is used.

  When manufacturing a polarizing film, when a water-based adhesive such as a polyvinyl alcohol-based adhesive is used (so-called wet lamination), a drying step is required after the polarizer and the transparent protective film are bonded together. . In order to improve the productivity of the polarizing film, it is desirable to shorten the drying process or employ another bonding method that does not require the drying process.

  In addition, when using a water-based adhesive, in order to enhance the adhesion with the polarizer, the water content of the polarizer must be relatively high (usually the water content of the polarizer is about 30%). A polarizing film with good adhesion cannot be obtained. However, the polarizing film obtained in this way has problems such as large dimensional changes and poor optical properties at high temperatures and high temperatures and high humidity. On the other hand, in order to suppress a dimensional change, the moisture content of a polarizer can be reduced or a transparent protective film with low moisture permeability can be used. However, when such a polarizer and a transparent protective film are bonded together using a water-based adhesive, drying efficiency decreases, polarization characteristics decrease, or appearance defects occur, and a substantially useful polarizing film is obtained. I can't.

  Further, as represented by TV in particular, as the screen size of image display devices has been increasing in recent years, the enlargement of the polarizing film has become very important from the viewpoint of productivity and cost (yield and increase in number of products). Yes. However, in the polarizing film using the above-mentioned aqueous adhesive, the so-called light omission (unevenness) that the polarizing film causes a dimensional change due to the heat of the backlight, which becomes uneven and a black display appears white in a part of the entire screen. ) Becomes prominent.

  In order to solve the above-described problems in wet lamination, an active energy ray-curable adhesive that does not contain water or an organic solvent has been proposed. For example, in the following Patent Document 3, (A) a radical polymerizable compound containing a polar group and having a molecular weight of 1,000 or less, and (B) a radical polymerizable compound containing no polar group and having a molecular weight of 1,000 or less, An active energy ray-curable adhesive containing (D) a radical generator is disclosed. However, the combination of radically polymerizable compounds (monomers) constituting such an adhesive is designed particularly for the purpose of improving the adhesion to norbornene-based resin films, and therefore tends to have poor adhesion to the polarizing film. It was.

  Patent Document 4 listed below discloses an active energy ray-curable adhesive comprising a radical generator having a molar extinction coefficient of 400 or more at a wavelength of 360 to 450 nm and an ultraviolet curable compound as essential components. However, since the combination of monomers constituting such an adhesive is designed mainly for the purpose of preventing warpage and deformation when adhering an optical disk or the like, when used for a polarizing film, There was a tendency to be inferior in adhesiveness.

  In the following Patent Document 5, (a) a (meth) acrylic compound having two or more (meth) acryloyl groups in the molecule in a total amount of 100 parts by weight of the (meth) acrylic compound, and (b) a hydroxyl group in the molecule. And an active energy ray-curable adhesive containing (meth) acrylic compound having only one polymerizable double bond and (c) phenolethylene oxide-modified acrylate or nonylphenolethylene oxide-modified acrylate ing. However, there is a concern that the combination of monomers constituting such an adhesive has relatively low compatibility between the monomers, phase separation proceeds accordingly, and transparency of the adhesive layer decreases. Further, such an adhesive is intended to improve adhesion by softening a cured product (adhesive layer) (lowering Tg), and there is a concern that durability such as crack resistance is deteriorated. The crack resistance can be evaluated by a thermal shock test (heat shock test).

  The present inventors have developed an active energy ray-curable adhesive containing a radical polymerizable compound, a photo radical generator and a photo acid generator (Patent Document 6 and Patent Document 7 below). Furthermore, the present inventors have developed an active energy ray-curable adhesive composition containing at least three radically polymerizable compounds having different SP values (Patent Document 8 below).

JP 2006-220732 A JP 2001-296427 A JP 2008-009329 A JP 09-31416 A JP 2008-174667 A JP 2012-67260 A JP 2012-68593 A JP 2012-144690 A

  The adhesives described in Patent Documents 6-8 are excellent in adhesiveness and water resistance, but in recent years, they can exhibit adhesiveness even after being immersed in room temperature water for several hours, and are extremely excellent in water resistance. Adhesives are required. On the other hand, in the adhesive described in Patent Documents 6-8, there is room for further contrivance in order to increase the water resistance to a level where the adhesiveness can be exhibited even after being immersed in room temperature water for several hours.

  The present invention has been made in view of the above problems, and an object thereof is an active energy ray-curable adhesive composition capable of providing an adhesive layer for laminating at least two members, Another object of the present invention is to provide an active energy ray-curable adhesive composition capable of providing an adhesive layer with extremely excellent water resistance that can exhibit adhesiveness even after being immersed in an aqueous solution for several hours. Furthermore, an object of this invention is to provide a polarizing film provided with the adhesive bond layer excellent in water resistance, its manufacturing method, an optical film, and an image display apparatus.

  The above object can be achieved by the present invention as described below. That is, the active energy ray-curable adhesive composition according to the present invention includes a radical polymerizable compound (A), a radical generator (B), a photoacid generator (C), and an alkoxy group-containing amino compound (D), It is characterized by containing.

  In the active energy ray-curable adhesive composition, the alkoxy group-containing amino compound (D) is preferably an alkoxy group-containing aminosilane coupling agent (D1).

  In the active energy ray-curable adhesive composition, when the total amount of the radical polymerizable compound (A) is 100 parts by weight, the content of the alkoxy group-containing aminosilane coupling agent (D1) is 0.1 to 20. It is preferable that it is a weight part.

In the above active energy ray-curable adhesive composition, as the photoacid generator (C), a photoacid having at least one selected from the group consisting of PF ₆ ⁻ , SbF ₆ ^— and AsF ₆ ^— as a counter anion. It is preferable to contain a generator.

  In the active energy ray-curable adhesive composition, the radical polymerizable compound (A) preferably contains an acrylamide derivative.

  In the active energy ray-curable adhesive composition, the radical polymerizable compound (A) is at least one selected from the group consisting of hydroxyethylacrylamide, N-methylolacrylamide, acryloylmorpholine, and N-methoxymethylacrylamide. Preferably there is.

In the active energy ray-curable adhesive composition, as the generator (B), a compound represented by the following general formula (1);

(Wherein R ¹ and R ² represent —H, —CH ₂ CH ₃ , —iPr or Cl, and R ¹ and R ² may be the same or different).

In the active energy ray-curable adhesive composition, as the radical generator (B), a compound represented by the following general formula (2);

Wherein R ³ , R ⁴ and R ⁵ represent —H, —CH ₃ , —CH ₂ CH ₃ , —iPr or Cl, and R ³ , R ⁴ and R ⁵ may be the same or different. It is preferable to contain.

  The polarizing film according to the present invention is a polarizing film in which a transparent protective film having a light transmittance of a wavelength of 365 nm of less than 5% is provided on at least one surface of a polarizer via an adhesive layer. The said adhesive bond layer is formed by the hardened | cured material layer formed by irradiating an active energy ray to the active energy ray hardening-type adhesive composition in any one of Claims 1-10, It is characterized by the above-mentioned. .

  In the polarizing film, a glass transition temperature (Tg) of the adhesive layer is preferably 20 ° C. or higher.

In the polarizing film, it is preferable moisture permeability of the transparent protective film is not more than 150g ^/ m 2 ^/ 24h.

In the polarizing film, the transparent protective film preferably has an SP value of 29.0 (kJ / m ³ ) ^1/2 or more and less than 33.0 (kJ / m ³ ) ^1/2 .

In the polarizing film, the transparent protective film preferably has an SP value of 18.0 (kJ / m ³ ) ^1/2 or more and less than 24.0 (kJ / m ³ ) ^1/2 .

  Moreover, the manufacturing method of the polarizing film which concerns on this invention is a polarizing film with which the transparent protective film whose light transmittance of wavelength 365nm is less than 5% is provided in the at least one surface of the polarizer through the adhesive bond layer. It is a manufacturing method of this, Comprising: The coating process which coats the active energy ray hardening-type adhesive composition in any one of Claims 1-10 on at least one surface of the said polarizer or the said transparent protective film, , A bonding step of bonding the polarizer and the transparent protective film, and irradiating active energy rays from the polarizer surface side or the transparent protective film surface side to thereby form the active energy ray-curable adhesive composition. A bonding step of bonding the polarizer and the transparent protective film through an adhesive layer obtained by curing.

  In the manufacturing method of the polarizing film, before the coating step, at least one surface of the polarizer or the transparent protective film, on the surface on which the active energy ray-curable adhesive composition is coated. Corona treatment, plasma treatment, flame treatment or excimer treatment is preferably performed.

  In the manufacturing method of the said polarizing film, it is preferable that the moisture content of the said polarizer at the time of the said bonding process is less than 15%.

  In the manufacturing method of the said polarizing film, it is preferable to have a heating process at the time of the said adhesion process at the time of active energy ray irradiation or after irradiation.

  Furthermore, the present invention provides an optical film in which at least one polarizing film as described above is laminated, and an image using the polarizing film as described above and / or the optical film as described above. The present invention relates to a display device.

  In the active energy ray-curable adhesive composition according to the present invention, when the active energy ray is irradiated, the radical generator (B) generates radicals, and the radical polymerizable compound (A) undergoes radical polymerization. An adhesive layer composed of a cured product layer can be formed. In the present invention, the active energy ray-curable adhesive composition comprises a photoacid generator (C) and an alkoxy group-containing amino compound (D) in addition to the radical polymerizable compound (A) and the radical generator (B). Since it contains, compared with the case where a photo-acid generator (C) and an alkoxy-group containing amino compound (D) are not contained, the water resistance and adhesiveness of an adhesive bond layer can be improved significantly. In the present invention, the reason why the water resistance and adhesiveness of the adhesive layer are improved is not clear, but is presumed as follows.

  When the photoacid generator (C) and the alkoxy group-containing amino compound (D) coexist in the active energy ray-curable adhesive composition, the amino group in the alkoxy group-containing amino compound (D) is derived from the photoacid generator. At the same time, the alkoxy group in the amino group-containing amino compound (D) is hydrolyzed by moisture to produce a reactive hydroxyl group. Thereby, the reactive hydroxyl group in the alkoxy group-containing amino compound (D) forms a hydrogen bond with the hydroxyl group present on the surface of the polarizer. Furthermore, the reactive hydroxyl group in the alkoxy group-containing amino compound (D) can directly react with the hydroxyl group present on the surface of the polarizer to form a covalent bond. As a result, when the photoacid generator (C) and the alkoxy group-containing amino compound (D) coexist in the active energy ray-curable adhesive composition, the interaction between the adhesive layer and the polarizer is significantly increased. The water resistance of the adhesive layer and the adhesiveness between the adhesive layer and the polarizer are dramatically improved.

  When the alkoxy group-containing amino compound (D) is an alkoxy group-containing aminosilane coupling agent (D1), when the alkoxy group is hydrolyzed by moisture, a more reactive silanol group is generated. Thereby, the silanol group in the alkoxy group-containing aminosilane coupling agent (D1) and the hydroxyl group present on the surface of the polarizer can interact more strongly through hydrogen bonds and / or covalent bonds. As a result, the water resistance of the adhesive layer and the adhesiveness between the adhesive layer and the polarizer are further dramatically improved.

  The adhesive layer of the active energy ray-curable adhesive composition according to the present invention is excellent in adhesiveness and durability, particularly excellent in water resistance that can exhibit adhesiveness even after being immersed in room temperature water for several hours. It is. For this reason, the laminated body by which at least 2 member was laminated | stacked through this adhesive bond layer can be used conveniently for various uses. For example, in the case of a polarizing film provided with the adhesive layer according to the present invention, since the dimensional change is very small, it is possible to easily cope with an increase in the size of the polarizing film, and to suppress the production cost from the viewpoint of yield and number of production. In addition, it is possible to suppress the occurrence of unevenness in the image display device due to the external heat of the backlight.

  The active energy ray-curable adhesive composition according to the present invention contains a radical polymerizable compound (A), a radical generator (B), a photoacid generator (C), and an alkoxy group-containing amino compound (D). To do.

The radical polymerizable compound (A) acts as a curable component that undergoes radical polymerization, particularly photoradical polymerization in the presence of radicals generated by irradiating the radical generator (B) with active energy rays. Therefore, in the present invention, the radical polymerizable compound (A) can be used without any particular limitation as long as it is a compound having a vinyl group containing at least one carbon-carbon double bond, a (meth) acryloyl group, or the like. is there. However, in the present invention, among the radical polymerizable compounds (A), the following general formula (1):
^{_{CH 2 = C (R 1)}} -CONH 2-m - (X-O-R 2) m (1)
(R ¹ represents a hydrogen atom or a methyl group, X represents a —CH ₂ — group or a —CH ₂ CH ₂ — group, R ² represents a — (CH ₂ ) _n —H group (where n is 0, 1 Or an acrylamide derivative represented by 2), wherein m represents 1 or 2.

  Specific examples of the acrylamide derivative represented by the general formula (1) include, for example, N-hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N-ethoxymethyl. (Meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide and the like can be mentioned. These acrylamide derivatives can be used alone or in combination of two or more.

  As the acrylamide derivative represented by the general formula (1), a commercially available product can also be suitably used. Specifically, for example, N-hydroxyethyl acrylamide (trade name “HEAA”, manufactured by Kojin Co., Ltd.), N-methoxymethyl acrylamide (trade name “NMMA”, manufactured by MRC Unitech Co., Ltd.), N-butoxymethyl acrylamide (trade name) “NBMA” (manufactured by MRC Unitech), N-methoxymethylmethacrylamide (trade name “Wassmer 2MA”, manufactured by Kasano Kosan Co., Ltd.), and the like.

  As the acrylamide derivative represented by the general formula (1), N-hydroxyethyl (meth) acrylamide is preferable. Acrylamide derivatives show good adhesion to low-moisture polarizers and transparent protective films using materials with low moisture permeability. Among the monomers exemplified above, N-hydroxyethylacrylamide is Particularly good adhesion is exhibited.

  The active energy ray-curable adhesive composition according to the present invention includes, as the radical polymerizable compound (A), a monofunctional compound having an acrylamide derivative other than that represented by the general formula (1), various aromatic rings, and a hydroxy group. (Meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, compounds having various (meth) acryloyl groups, and the like may be contained. However, in consideration of the adhesiveness and water resistance of the adhesive layer, when the total amount of the radical polymerizable compound (A) is 100 parts by weight, the ratio of the acrylamide derivative represented by the general formula (1) is 1 It is preferably ˜50 parts by weight, and more preferably 3 to 30 parts by weight.

  Examples of acrylamide derivatives other than those represented by the general formula (1) include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-isopropyl. Acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, mercaptomethyl (meth) acrylamide, mercaptoethyl (meth) acrylamide, N-acryloyl Examples include morpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine and the like.

  As the monofunctional (meth) acrylate having an aromatic ring and a hydroxy group, various monofunctional (meth) acrylates having an aromatic ring and a hydroxy group can be used. The hydroxy group may exist as a substituent of the aromatic ring, but in the present invention, it exists as an organic group (bonded to a hydrocarbon group, particularly an alkylene group) that bonds the aromatic ring and the (meth) acrylate. Those that do are preferred.

  Examples of the monofunctional (meth) acrylate having an aromatic ring and a hydroxy group include a reaction product of a monofunctional epoxy compound having an aromatic ring and (meth) acrylic acid. Examples of the monofunctional epoxy compound having an aromatic ring include phenyl glycidyl ether, t-butylphenyl glycidyl ether, and phenyl polyethylene glycol glycidyl ether. Specific examples of the monofunctional (meth) acrylate having an aromatic ring and a hydroxy group include, for example, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3-t-butylphenoxypropyl (meth) Acrylate, 2-hydroxy-3-phenyl polyethylene glycol propyl (meth) acrylate, etc. are mentioned.

  Moreover, as said urethane (meth) acrylate, the hydroxyl group of the one end of diol compounds, such as (meth) acrylate which has an isocyanate group, and polyalkylene glycols, such as polyurethane diol, polyester diol, polyether diol, polyethylene glycol, polypropylene glycol, etc. And a reaction product thereof.

  As a compound having a (meth) acryloyl group, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate C 1-12 alkyl (meth) acrylates such as lauryl (meth) acrylate; (meth) acrylic acid alkoxyalkyl monomers such as (meth) acrylic acid methoxyethyl and (meth) acrylic acid ethoxyethyl; ) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, (meta Acrylic acid Hydroxyl group-containing monomers such as 0-hydroxydecyl, 12-hydroxylauryl (meth) acrylate and (4-hydroxymethylcyclohexyl) -methyl acrylate; Acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; acrylic acid Caprolactone adducts: styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid And sulfonic acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate and the like. (Meth) acrylamide; maleimide, N-cyclohexylmaleimide, N-phenylmaleimide, etc .; aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate , (Meth) acrylic acid alkylaminoalkyl monomers such as (meth) acrylic acid t-butylaminoethyl, 3- (3-pyridinyl) propyl (meth) acrylate; N- (meth) acryloyloxymethylene succinimide and N- ( And nitrogen-containing monomers such as succinimide monomers such as (meth) acryloyl-6-oxyhexamethylene succinimide and N- (meth) acryloyl-8-oxyoctamethylene succinimide.

  The active energy ray-curable adhesive composition according to the present invention includes, as the radical polymerizable compound (A), in addition to the monomer having one carbon-carbon double bond described above, and further two or more carbon-carbons. A monomer having a double bond, particularly preferably a polyfunctional (meth) acrylate monomer, is preferable because the water resistance of the adhesive layer is improved. In consideration of the water resistance of the adhesive layer, the monomer having two or more carbon-carbon double bonds is more preferably hydrophobic. Monomers having two or more hydrophobic carbon-carbon double bonds, particularly hydrophobic polyfunctional (meth) acrylate monomers include, for example, tricyclodecane dimethanol diacrylate, divinylbenzene, N, N′-methylene. Bisacrylamide, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) Acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol glycol di (meth) acrylate, glycerin di (meth) acrylate, EO modified glycerin tri (meth) acrylate, EO modified diglycerin tetra ( (Meth) acrylate, (meth) acrylic acid 2- (2-vinyloxyethoxy) ethyl, bisphenol A-EO adduct di (meth) acrylate, trimethylolpropane tri (meth) acrylate, hydroxypivalate neopentyl glycol (meth) Acrylic acid adduct, EO-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, iso Anuric acid EO-modified di (meth) acrylate, isocyanuric acid EO-modified tri (meth) acrylate, ε-caprolactone-modified tris ((meth) acryloxyethyl) isocyanurate, 1,1-bis ((meth) acryloyloxymethyl) ethyl Examples include isocyanate, a polymer of 2-hydroxyethyl (meth) acrylate and 1,6-diisocyanate hexane, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, and the like.

  In this invention, it is preferable that the ratio of the monomer which has a 2 or more carbon-carbon double bond with respect to the total amount of a radically polymerizable compound (A) is 5-80 weight part, and is 10-70 weight part. More preferably. If this proportion is less than 5 parts by weight, sufficient water resistance may not be obtained, whereas if it exceeds 80 parts by weight, sufficient adhesion may not be obtained.

  In the present invention, since the photoacid generator (C) and the alkoxy group-containing amino compound (D) coexist in the active energy ray-curable adhesive composition, the alkoxy group in the alkoxy group-containing amino compound (D) It is characterized in that it is hydrolyzed by moisture and, as a result, forms hydrogen bonds and / or covalent bonds with hydroxyl groups present on the surface of the polarizer. Therefore, if the photoacid generator (C) is consumed in the cationic photopolymerization of the epoxy group-containing compound, the water resistance and durability of the adhesive layer described above are not sufficiently improved, which is not preferable. For this reason, in the active energy ray-curable adhesive composition, the ratio of the epoxy group-containing compound to the total amount of the radical polymerizable compound (A) and the epoxy group-containing compound is preferably 5% by weight or less. % Or less is more preferable, and it is particularly preferable not to contain an epoxy group-containing compound.

  The active energy ray-curable adhesive composition according to the present invention contains a radical generator (B). The radical generator (B) generates radicals by irradiating active energy rays.

In the active energy ray-curable adhesive composition according to the present invention, a compound represented by the following general formula (1) as the radical generator (B);

(Wherein R ¹ and R ² represent —H, —CH ₂ CH ₃ , —iPr or Cl, and R ¹ and R ² may be the same or different), respectively, or a general formula ( It is preferable to use together the compound represented by 1) and a radical generator highly sensitive to light of 380 nm or more, which will be described later. When the compound represented by the general formula (1) is used, the adhesiveness is excellent as compared with a case where a radical generator sensitive to light of 380 nm or more is used alone. Among the compounds represented by the general formula (1), diethylthioxanthone in which R ¹ and R ² are —CH ₂ CH ₃ is particularly preferable. The composition ratio of the compound represented by the general formula (1) in the composition is preferably 0.5 to 10 parts by weight when the total amount of the radical polymerizable compound (A) is 100 parts by weight. It is more preferably ˜7 parts by weight, and even more preferably 1 to 5 parts by weight.

  Moreover, it is preferable to add a polymerization initiation assistant as required. Examples of polymerization initiators include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and the like. Among them, ethyl 4-dimethylaminobenzoate is particularly preferable. When using a polymerization initiation assistant, the amount added is usually 0 to 5 parts by weight, preferably 0 to 4 parts by weight, most preferably 0 when the total amount of the radical polymerizable compound (A) is 100 parts by weight. ~ 3 parts by weight.

  Moreover, a well-known radical generator 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 radical generator that is highly sensitive to light of 380 nm or more as the radical generator. 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-trimethylbenzoyl) -phenylphosphine oxide, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) 1-yl) -phenyl) titanium and the like.

In particular, as a radical generator, in addition to the radical generator of the general formula (1), a compound represented by the following general formula (2);

Wherein R ³ , R ⁴ and R ⁵ represent —H, —CH ₃ , —CH ₂ CH ₃ , —iPr or Cl, and R ³ , R ⁴ and R ⁵ may be the same or different. It is preferable to use it. As the compound represented by the general formula (2), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: IRGACURE907 manufacturer: BASF) which is also a commercially available product is suitable. Can be used. In addition, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369 manufacturer: BASF), 2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE379 manufacturer: BASF) is preferable because of its high sensitivity.

  The content of the radical generator (B) is preferably 0.5 to 10 parts by weight and preferably 1 to 7 parts by weight when the total amount of the radical polymerizable compound (A) is 100 parts by weight. More preferably, it is 1 to 5 parts by weight.

  In the present invention, the active energy ray-curable adhesive composition comprises a photoacid generator (C) and an alkoxy group-containing amino compound (D) in addition to the radical polymerizable compound (A) and the radical generator (B). contains. As a result, the water resistance and durability of the adhesive layer can be dramatically improved as compared with the case where the photoacid generator (C) and the alkoxy group-containing amino compound (D) are not contained. The photoacid generator (C) can be represented by the following general formula (3).

General formula (3)

(However, L ⁺ represents an arbitrary 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).

Preferred examples of the onium cation structure as the onium cation L ⁺ constituting the general formula (3) include onium cations selected from the following general formulas (4) to (12).

General formula (4)

General formula (5)

General formula (6)

General formula (7)

General formula (8)

General formula (9)

General formula (10)

Formula (11)

Formula (12)

(In the above general formulas (4)-(12), R ¹ , R ² and R ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted group. Aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted acyl group, substituted or R ⁴ represents a group selected from an unsubstituted carbonyloxy group, a substituted or unsubstituted oxycarbonyl group, or a halogen atom, and R ⁴ represents a group similar to the groups described in R ¹ , R ^2, and R ^{3. 5} is a substituted or unsubstituted alkyl group, is .R ⁶ and R ⁷ represents a substituted or unsubstituted alkylthio group, each independently represent a substituted or unsubstituted Represents a substituted alkyl group, a substituted or unsubstituted alkoxyl group, and R represents a halogen atom, a hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a nitro group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted alkyl group. Substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic ring Oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted acyl group, substituted or unsubstituted carbonyloxy group, substituted or unsubstituted the ^.Ar 4, Ar ⁵ to the representative of either oxycarbonyl group, location Alternatively, it represents an unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, X represents an oxygen or sulfur atom, i represents an integer of 0 to 5, j represents an integer of 0 to 4. K represents an integer of 0 to ^3. Adjacent Rs, Ar ⁴ and Ar ⁵ , R ² and R ³ , R ² and R ⁴ , R ³ and R ⁴ , R ¹ and R ² , R ¹ And R ³ , R ¹ and R ⁴ , R ¹ and R, or R ¹ and R ⁵ may be a cyclic structure bonded to each other.)

Onium cation (sulfonium cation) corresponding to general formula (4):
Dimethylphenylsulfonium, dimethyl (o-fluorophenyl) sulfonium, dimethyl (m-chlorophenyl) sulfonium, dimethyl (p-bromophenyl) sulfonium, dimethyl (p-cyanophenyl) sulfonium, dimethyl (m-nitrophenyl) sulfonium, dimethyl ( 2,4,6-tribromophenyl) sulfonium, dimethyl (pentafluorophenyl) sulfonium, dimethyl (p- (trifluoromethyl) phenyl) sulfonium, dimethyl (p-hydroxyphenyl) sulfonium, dimethyl (p-mercaptophenyl) sulfonium , Dimethyl (p-methylsulfinylphenyl) sulfonium, dimethyl (p-methylsulfonylphenyl) sulfonium, dimethyl (o-acetylphenyl) sulfonium Dimethyl (o-benzoylphenyl) sulfonium, dimethyl (p-methylphenyl) sulfonium, dimethyl (p-isopropylphenyl) sulfonium, dimethyl (p-octadecylphenyl) sulfonium, dimethyl (p-cyclohexylphenyl) sulfonium, dimethyl (p-methoxy) Phenyl) sulfonium, dimethyl (o-methoxycarbonylphenyl) sulfonium, dimethyl (p-phenylsulfanylphenyl) sulfonium, (7-methoxy-2-oxo-2H-chromen-4-yl) dimethylsulfonium, (4-methoxynaphthalene- 1-yl) dimethylsulfonium, dimethyl (p-isopropoxycarbonylphenyl) sulfonium, dimethyl (2-naphthyl) sulfonium, dimethyl (9-anthryl) Rufonium, diethylphenylsulfonium, methylethylphenylsulfonium, methyldiphenylsulfonium, triphenylsulfonium, diisopropylphenylsulfonium, diphenyl (4-phenylsulfanyl-phenyl) -sulfonium, 4,4′-bis (diphenylsulfonium) diphenyl sulfide, 4, 4′-bis [di [(4- (2-hydroxy-ethoxy) -phenyl)] sulfonium]] diphenyl sulfide, 4,4′-bis (diphenylsulfonium) biphenylene, diphenyl (o-fluorophenyl) sulfonium, diphenyl ( m-chlorophenyl) sulfonium, diphenyl (p-bromophenyl) sulfonium, diphenyl (p-cyanophenyl) sulfonium, diphenyl (m-nitrophenyl) ) Sulfonium, diphenyl (2,4,6-tribromophenyl) sulfonium, diphenyl (pentafluorophenyl) sulfonium, diphenyl (p- (trifluoromethyl) phenyl) sulfonium, diphenyl (p-hydroxyphenyl) sulfonium, diphenyl (p -Mercaptophenyl) sulfonium, diphenyl (p-methylsulfinylphenyl) sulfonium, diphenyl (p-methylsulfonylphenyl) sulfonium, diphenyl (o-acetylphenyl) sulfonium, diphenyl (o-benzoylphenyl) sulfonium, diphenyl (p-methylphenyl) ) Sulfonium, diphenyl (p-isopropylphenyl) sulfonium, diphenyl (p-octadecylphenyl) sulfonium, diphenyl (p-si Rohexylphenyl) sulfonium, diphenyl (p-methoxyphenyl) sulfonium, diphenyl (o-methoxycarbonylphenyl) sulfonium, diphenyl (p-phenylsulfanylphenyl) sulfonium, (7-methoxy-2-oxo-2H-chromene-4- Yl) diphenylsulfonium, (4-methoxynaphthalen-1-yl) diphenylsulfonium, diphenyl (p-isopropoxycarbonylphenyl) sulfonium, diphenyl (2-naphthyl) sulfonium, diphenyl (9-anthryl) sulfonium, ethyldiphenylsulfonium, methyl Ethyl (o-tolyl) sulfonium, methyldi (p-tolyl) sulfonium, tri (p-tolyl) sulfonium, diisopropyl (4-phenylsulfanyl) Nyl) sulfonium, diphenyl (2-thienyl) sulfonium, diphenyl (2-furyl) sulfonium, diphenyl (9-ethyl-9Hcarbazol-3-yl) sulfonium, and the like, but are not limited thereto. .

Onium cation corresponding to general formula (5) (sulfoxonium cation):
Dimethylphenylsulfoxonium, dimethyl (o-fluorophenyl) sulfoxonium, dimethyl (m-chlorophenyl) sulfoxonium, dimethyl (p-bromophenyl) sulfoxonium, dimethyl (p-cyanophenyl) sulfoxonium, dimethyl (M-nitrophenyl) sulfoxonium, dimethyl (2,4,6-tribromophenyl) sulfoxonium, dimethyl (pentafluorophenyl) sulfoxonium, dimethyl (p- (trifluoromethyl) phenyl) sulfoxonium , Dimethyl (p-hydroxyphenyl) sulfoxonium, dimethyl (p-mercaptophenyl) sulfoxonium, dimethyl (p-methylsulfinylphenyl) sulfoxonium, dimethyl (p-methylsulfonylphenyl) sulfoxo , Dimethyl (o-acetylphenyl) sulfoxonium, dimethyl (o-benzoylphenyl) sulfoxonium, dimethyl (p-methylphenyl) sulfoxonium, dimethyl (p-isopropylphenyl) sulfoxonium, dimethyl (p- Octadecylphenyl) sulfoxonium, dimethyl (p-cyclohexylphenyl) sulfoxonium, dimethyl (p-methoxyphenyl) sulfoxonium, dimethyl (o-methoxycarbonylphenyl) sulfoxonium, dimethyl (p-phenylsulfanylphenyl) sulfo Xonium, (7-methoxy-2-oxo-2H-chromen-4-yl) dimethylsulfoxonium, (4-methoxynaphthalen-1-yl) dimethylsulfoxonium, dimethyl (p-isopropoxyca) Bonylphenyl) sulfoxonium, dimethyl (2-naphthyl) sulfoxonium, dimethyl (9-anthryl) sulfoxonium, diethylphenylsulfoxonium, methylethylphenylsulfoxonium, methyldiphenylsulfoxonium, triphenylsulfoxonium Ni, diisopropylphenylsulfoxonium, diphenyl (4-phenylsulfanyl-phenyl) -sulfoxonium, 4,4′-bis (diphenylsulfoxonium) diphenyl sulfide, 4,4′-bis [di [(4- ( 2-hydroxy-ethoxy) -phenyl)] sulfoxonium] diphenyl sulfide, 4,4′-bis (diphenylsulfoxonium) biphenylene, diphenyl (o-fluorophenyl) sulfoxonium, diphenyl (m-chloro) Phenyl) sulfoxonium, diphenyl (p-bromophenyl) sulfoxonium, diphenyl (p-cyanophenyl) sulfoxonium, diphenyl (m-nitrophenyl) sulfoxonium, diphenyl (2,4,6-tribromophenyl) ) Sulfoxonium, diphenyl (pentafluorophenyl) sulfoxonium, diphenyl (p- (trifluoromethyl) phenyl) sulfoxonium, diphenyl (p-hydroxyphenyl) sulfoxonium, diphenyl (p-mercaptophenyl) sulfoxo Ni, diphenyl (p-methylsulfinylphenyl) sulfoxonium, diphenyl (p-methylsulfonylphenyl) sulfoxonium, diphenyl (o-acetylphenyl) sulfoxonium, diphenyl (o-benzoy) Ruphenyl) sulfoxonium, diphenyl (p-methylphenyl) sulfoxonium, diphenyl (p-isopropylphenyl) sulfoxonium, diphenyl (p-octadecylphenyl) sulfoxonium, diphenyl (p-cyclohexylphenyl) sulfoxonium, Diphenyl (p-methoxyphenyl) sulfoxonium, diphenyl (o-methoxycarbonylphenyl) sulfoxonium, diphenyl (p-phenylsulfanylphenyl) sulfoxonium, (7-methoxy-2-oxo-2H-chromene-4- Yl) diphenylsulfoxonium, (4-methoxynaphthalen-1-yl) diphenylsulfoxonium, diphenyl (p-isopropoxycarbonylphenyl) sulfoxonium, diphenyl (2-naphthyl) Sulfoxonium, diphenyl (9-anthryl) sulfoxonium, ethyldiphenylsulfoxonium, methylethyl (o-tolyl) sulfoxonium, methyldi (p-tolyl) sulfoxonium, tri (p-tolyl) sulfoxonium , Diisopropyl (4-phenylsulfanylphenyl) sulfoxonium, diphenyl (2-thienyl) sulfoxonium, diphenyl (2-furyl) sulfoxonium, diphenyl (9-ethyl-9Hcarbazol-3-yl) sulfoxonium, etc. However, it is not limited to these.

Onium cation (phosphonium cation) corresponding to the general formula (6):
Examples of phosphonium cations:
Trimethylphenylphosphonium, triethylphenylphosphonium, tetraphenylphosphonium, triphenyl (p-fluorophenyl) phosphonium, triphenyl (o-chlorophenyl) phosphonium, triphenyl (m-bromophenyl) phosphonium, triphenyl (p-cyanophenyl) phosphonium , Triphenyl (m-nitrophenyl) phosphonium, triphenyl (p-phenylsulfanylphenyl) phosphonium, (7-methoxy-2-oxo-2H-chromen-4-yl) triphenylphosphonium, triphenyl (o-hydroxyphenyl) ) Phosphonium, triphenyl (o-acetylphenyl) phosphonium, triphenyl (m-benzoylphenyl) phosphonium, triphenyl (p-methylphenyl) phospho Phonium, triphenyl (p-isopropoxyphenyl) phosphonium, triphenyl (o-methoxycarbonylphenyl) phosphonium, triphenyl (1-naphthyl) phosphonium, triphenyl (9-anthryl) phosphonium, triphenyl (2-thienyl) phosphonium , Triphenyl (2-furyl) phosphonium, triphenyl (9-ethyl-9Hcarbazol-3-yl) phosphonium, and the like, but are not limited thereto.

Onium cation corresponding to general formula (7) (pyridinium cation):
Examples of pyridinium cations:
N-phenylpyridinium, N- (o-chlorophenyl) pyridinium, N- (m-chlorophenyl) pyridinium, N- (p-cyanophenyl) pyridinium, N- (o-nitrophenyl) pyridinium, N- (p-acetylphenyl) ) Pyridinium, N- (p-isopropylphenyl) pyridinium, N- (p-octadecyloxyphenyl) pyridinium, N- (p-methoxycarbonylphenyl) pyridinium, N- (9-anthryl) pyridinium, 2-chloro-1- Phenylpyridinium, 2-cyano-1-phenylpyridinium, 2-methyl-1-phenylpyridinium, 2-vinyl-1-phenylpyridinium, 2-phenyl-1-phenylpyridinium, 1,2-diphenylpyridinium, 2-methoxy- 1-phenylpi Dinium, 2-phenoxy-1-phenylpyridinium, 2-acetyl-1- (p-tolyl) pyridinium, 2-methoxycarbonyl-1- (p-tolyl) pyridinium, 3-fluoro-1-naphthylpyridinium, 4-methyl Examples thereof include, but are not limited to, -1- (2-furyl) pyridinium, N-methylpyridinium, N-ethylpyridinium, and the like.

Onium cation (quinolinium cation) corresponding to general formula (8):
Examples of quinolinium cations:
N-methylquinolinium, N-ethylquinolinium, N-phenylquinolinium, N-naphthylquinolinium, N- (o-chlorophenyl) quinolinium, N- (m-chlorophenyl) quinolinium, N- (p -Cyanophenyl) quinolinium, N- (o-nitrophenyl) quinolinium, N- (p-acetylphenyl) quinolinium, N- (p-isopropylphenyl) quinolinium, N- (p-octadecyloxyphenyl) quinolinium, N- ( p-methoxycarbonylphenyl) quinolinium, N- (9-anthryl) quinolinium, 2-chloro-1-phenylquinolinium, 2-cyano-1-phenylquinolinium, 2-methyl-1-phenylquinolinium, 2-vinyl-1-phenylquinolinium, 2-phenyl-1-phenyl Norinium, 1,2-diphenylquinolinium, 2-methoxy-1-phenylquinolinium, 2-phenoxy-1-phenylquinolinium, 2-acetyl-1-phenylquinolinium, 2-methoxycarbonyl-1 -Phenylquinolinium, 3-fluoro-1-phenylquinolinium, 4-methyl-1-phenylquinolinium, 2-methoxy-1- (p-tolyl) quinolinium, 2-phenoxy-1- (2- Furyl) quinolinium, 2-acetyl-1- (2-thienyl) quinolinium, 2-methoxycarbonyl-1-methylquinolinium, 3-fluoro-1-ethylquinolinium, 4-methyl-1-isopropylquinolinium However, it is not limited to these.

Onium cation (isoquinolinium cation) corresponding to the general formula (9):
Examples of isoquinolinium cations:
N-phenylisoquinolinium, N-methylisoquinolinium, N-ethylisoquinolinium, N- (o-chlorophenyl) isoquinolinium, N- (m-chlorophenyl) isoquinolinium, N- (p-cyanophenyl) Isoquinolinium, N- (o-nitrophenyl) isoquinolinium, N- (p-acetylphenyl) isoquinolinium, N- (p-isopropylphenyl) isoquinolinium, N- (p-octadecyloxyphenyl) isoquinolinium, N- (p-methoxycarbonyl) Phenyl) isoquinolinium, N- (9-anthryl) isoquinolinium, 1,2-diphenylisoquinolinium, N- (2-furyl) isoquinolinium, N- (2-thienyl) isoquinolinium, N-naphthylisoquinolinium, etc. To mention Kill, but is not limited to these.

Onium cation corresponding to general formula (10) (benzoxazolium cation, benzothiazolium cation):
Examples of benzoxazolium cations:
N-methylbenzoxazolium, N-ethylbenzoxazolium, N-naphthylbenzoxazolium, N-phenylbenzoxazolium, N- (p-fluorophenyl) benzoxazolium, N- (p- Chlorophenyl) benzoxazolium, N- (p-cyanophenyl) benzoxazolium, N- (o-methoxycarbonylphenyl) benzoxazolium, N- (2-furyl) benzoxazolium, N- (o -Fluorophenyl) benzoxazolium, N- (p-cyanophenyl) benzoxazolium, N- (m-nitrophenyl) benzoxazolium, N- (p-isopropoxycarbonylphenyl) benzoxazolium, N- (2-thienyl) benzoxazolium, N- (m-carboxyphenyl) ben Oxazolium, 2-mercapto-3-phenylbenzoxazolium, 2-methyl-3-phenylbenzoxazolium, 2-methylthio-3- (4-phenylsulfanylphenyl) benzoxazolium, 6-hydroxy-3- (P-tolyl) benzoxazolium, 7-mercapto-3-phenylbenzoxazolium, 4,5-difluoro-3-ethylbenzoxazolium, and the like can be mentioned, but are not limited thereto. Absent.

Examples of benzothiazolium cations:
N-methylbenzothiazolium, N-ethylbenzothiazolium, N-phenylbenzothiazolium, N- (1-naphthyl) benzothiazolium, N- (p-fluorophenyl) benzothiazolium, N -(P-chlorophenyl) benzothiazolium, N- (p-cyanophenyl) benzothiazolium, N- (o-methoxycarbonylphenyl) benzothiazolium, N- (p-tolyl) benzothiazolium, N- (o-fluorophenyl) benzothiazolium, N- (m-nitrophenyl) benzothiazolium, N- (p-isopropoxycarbonylphenyl) benzothiazolium, N- (2-furyl) benzothia Zorium, N- (4-methylthiophenyl) benzothiazolium, N- (4-phenylsulfanylphenyl) benzothiazo , N- (2-naphthyl) benzothiazolium, N- (m-carboxyphenyl) benzothiazolium, 2-mercapto-3-phenylbenzothiazolium, 2-methyl-3-phenylbenzothiazolium 2-methylthio-3-phenylbenzothiazolium, 6-hydroxy-3-phenylbenzothiazolium, 7-mercapto-3-phenylbenzothiazolium, 4,5-difluoro-3-phenylbenzothiazolium However, it is not limited to these.

Onium cation corresponding to general formula (11) (furyl or thienyl iodonium cation):
Difuryl iodonium, dithienyl iodonium, bis (4,5-dimethyl-2-furyl) iodonium, bis (5-chloro-2-thienyl) iodonium, bis (5-cyano-2-furyl) iodonium, bis (5- Nitro-2-thienyl) iodonium, bis (5-acetyl-2-furyl) iodonium, bis (5-carboxy-2-thienyl) iodonium, bis (5-methoxycarbonyl-2-furyl) iodonium, bis (5-phenyl) -2-furyl) iodonium, bis (5- (p-methoxyphenyl) -2-thienyl) iodonium, bis (5-vinyl-2-furyl) iodonium, bis (5-ethynyl-2-thienyl) iodonium, bis ( 5-cyclohexyl-2-furyl) iodonium, bis (5-hydroxy-2-thio) Nyl) iodonium, bis (5-phenoxy-2-furyl) iodonium, bis (5-mercapto-2-thienyl) iodonium, bis (5-butylthio-2-thienyl) iodonium, bis (5-phenylthio-2-thienyl) Although iodonium etc. can be mentioned, it is not limited to these.

Onium cation corresponding to general formula (12) (diaryliodonium cation):
Diphenyliodonium, bis (p-tolyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium, bis (p-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (P-octadecyloxyphenyl) iodonium, 4-isopropyl-4′-methyldiphenyliodonium, (4-isobutylphenyl) -p-tolyliodonium, bis (1-naphthyl) iodonium, bis (4-phenylsulfanylphenyl) iodonium, Phenyl (6-benzoyl-9-ethyl-9H-carbazol-3-yl) iodonium, (7-methoxy-2-oxo-2H-chromen-3-yl) -4'-isopropylphenyliodonium And the like can be mentioned, but not limited thereto.

Next, the counter anion X ⁻ in the general formula (3) will be described.

The counter anion X ⁻ in the general formula (3) is not particularly limited in principle, but a non-nucleophilic anion is preferable. When the counter anion X ⁻ is a non-nucleophilic anion, the nucleophilic reaction in the cation coexisting in the molecule and various materials used in combination is unlikely to occur, and as a result, the photoacid generator itself represented by the general formula (3) It is possible to improve the aging stability of a composition using the same. The non-nucleophilic anion here refers to an anion having a low ability to cause a nucleophilic reaction. Examples of such anions include PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, SCN ^{− and the} like.

Among the exemplified anions described above, PF ₆ ⁻ , SbF ₆ ⁻ , and AsF ₆ ⁻ are particularly preferable as the counter anion X ⁻ in the general formula (3), and PF ₆ ⁻ , SbF ₆ ^- is mentioned.

Therefore, as a specific example of a preferable onium salt constituting the photoacid generator (C) of the present invention, a specific example of the structure of the onium cation represented by the above general formula (3) to general formula (12) An onium salt composed of an anion selected from PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, and SCN ⁻ .

  Specifically, “Syracure UVI-6922”, “Syracure UVI-6974” (above, manufactured by Dow Chemical Japan Co., Ltd.), “Adekaoptomer SP150”, “Adekaoptomer SP152”, “Adekaoptomer” “SP170”, “Adekaoptomer SP172” (manufactured by ADEKA Corporation), “IRGACURE250” (manufactured by Ciba Specialty Chemicals), “CI-5102”, “CI-2855” (manufactured by Nippon Soda Co., Ltd.), “Sun-Aid SI-60L”, “Sun-Aid SI-80L”, “Sun-Aid SI-100L”, “Sun-Aid SI-110L”, “Sun-Aid SI-180L” (above, manufactured by Sanshin Chemical Co., Ltd.), “CPI-100P”, “CPI-100A” (San Apro Co., Ltd.), “WPI-069 , “WPI-113”, “WPI-116”, “WPI-041”, “WPI-044”, “WPI-054”, “WPI-055”, “WPAG-281”, “WPAG-567”, “ “WPAG-596” (manufactured by Wako Pure Chemical Industries, Ltd.) is a preferred specific example of the photoacid generator (C) of the present invention.

  The content of the photoacid generator (C) is preferably 0.01 to 10 parts by weight, and 0.05 to 5 parts by weight with respect to the total amount of the active energy ray-curable adhesive composition. More preferably, it is 0.1-3 weight part, More preferably, it is 0.8-2 weight part.

  In addition, in the active energy ray-curable adhesive composition according to the present invention, in addition to the photo radical generator, a sensitizer that increases the curing rate and sensitivity by an electron beam typified by a carbonyl compound may be added. Good.

  Examples of the sensitizer include anthracene, phenothiazene, perylene, thioxanthone, and benzophenone thioxanthone. Further, sensitizing dyes include thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes. And pyrylium salt pigments.

  As specific anthracene compounds, dibutoxyanthracene, dipropoxyanthraquinone (Anthracure UVS-1331, 1221 manufactured by Kawasaki Kasei Co., Ltd.) and the like are effective.

  When a sensitizer is added, the content thereof is preferably 0.01 to 20 parts by weight, and preferably 0.01 to 10 parts by weight with respect to the total amount of the active energy ray-curable adhesive composition. Is more preferable, and 0.1 to 3 parts by weight is particularly preferable.

  The present invention is characterized in that the photoacid generator (C) and the alkoxy group-containing amino compound (D) coexist in the active energy ray-curable adhesive composition. Examples of the alkoxy group-containing amino compound (D) include an alkoxy group-containing aminosilane coupling agent (D1) and an alkylated urea (D2). Among these, the alkoxy group-containing aminosilane coupling agent (D1) can be particularly preferably used from the viewpoint of improving the water resistance and adhesiveness of the adhesive layer. When calculating the glass transition temperature Tg of the adhesive layer, the alkoxy group-containing amino compound (D) is not included in the calculation.

  Examples of the alkoxy group-containing aminosilane coupling agent (D1) include N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2 (amino Ethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N- Phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3- Mercaptopropylmethyldimethoxysilane 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanate propyltriethoxysilane, etc. imidazole silane. These may be used alone or in combination of two or more. In order to further improve the water resistance and adhesiveness of the adhesive layer, when the total amount of the radical polymerizable compound (A) is 100 parts by weight, the content of the alkoxy group-containing aminosilane coupling agent (D1) is 0.1. It is preferably ˜20 parts by weight, more preferably 0.2 to 12 parts by weight, and even more preferably 0.5 to 3 parts by weight.

  In the present invention, in addition to the alkoxy group-containing aminosilane coupling agent (D1), an active energy ray-curable silane coupling agent such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3 -Methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimeth Such as may be used in combination Shishiran.

  As the alkylated urea (D2), those having an alkylol group such as methylol and ethylol, an alkoxyalkyl group such as methoxymethyl group and ethoxymethyl group, an alkyl group and / or a hydrogen atom on the nitrogen atom of urea. Can be mentioned. In order to further improve the water resistance and adhesiveness of the adhesive layer, when the total amount of the radical polymerizable compound (A) is 100 parts by weight, the content of the alkylated urea (D2) is 0.1 to 30 parts by weight. It is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, and particularly preferably 8 to 12 parts by weight.

  As the alkylated urea (D2), commercially available products can also be suitably used, and examples thereof include Nikarac MX-270, Nikalac MX280, and Nikalac MX-290 manufactured by Sanwa Chemical Co., Ltd. The alkylated urea (D2) may be a resin (urea resin).

  The urea resin is a kind of amine resin, but other amine resins may be used as the alkoxy group-containing compound (D).

  Moreover, the active energy ray hardening-type adhesive composition which concerns on this invention can mix | blend various additives as another arbitrary component in the range which does not impair the objective and effect of this invention. Such additives include polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, silicone-based oligomer. Polymers such as polysulfide oligomers or oligomers; Polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; Examples include an agent, an ultraviolet absorber inorganic filler, a pigment, and a dye. However, in the active energy ray-curable adhesive composition, the content of the above-described additive is preferably 0.005 to 20 parts by weight with respect to the total amount of the active energy ray-curable adhesive composition. More preferably, it is 01-10 weight part, It is especially preferable that it is 0.1-5 weight part.

  The active energy ray-curable adhesive composition according to the present invention can be used in an electron beam curable type using an electron beam as an active energy ray and an ultraviolet curable type using ultraviolet rays.

  In the electron beam curable type, any appropriate condition can be adopted as the electron beam irradiation condition as long as the active energy ray curable adhesive composition can be cured. 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 cured product layer and may be insufficiently cured. If the acceleration voltage exceeds 300 kV, the penetrating force through the sample is too strong and the electron beam rebounds to each member. There is a risk of damage. The irradiation dose is 5 to 100 kGy, more preferably 10 to 75 kGy. When the irradiation dose is less than 5 kGy, the fallout layer becomes insufficiently cured, and when it exceeds 100 kGy, each member is damaged, mechanical strength is lowered and yellowing occurs, and predetermined optical characteristics cannot be obtained.

  Electron beam irradiation is usually performed in an inert gas, but if necessary, it may be performed in the atmosphere or under a condition in which a small amount of oxygen is introduced. Depending on the material of the member to be laminated, by introducing oxygen as appropriate, the surface of the member that is initially exposed to the electron beam may be obstructed to prevent oxygen damage and prevent damage to this member. Can be irradiated with an electron beam.

  On the other hand, in the ultraviolet curable type, when a member having an ultraviolet absorbing ability that absorbs light having a wavelength shorter than about 380 nm is used, the light having a wavelength shorter than 380 nm does not reach the active energy ray curable adhesive composition. Does not contribute to the polymerization reaction. Further, light having a wavelength shorter than 380 nm absorbed by the member is converted into heat, and the member itself generates heat, which causes defects such as curling and wrinkling of a laminate provided with the member. Therefore, when the ultraviolet curable type is adopted in the present invention, it is preferable to use an apparatus that does not emit light having a wavelength shorter than 380 nm as the ultraviolet ray generating apparatus, and more specifically, the integrated illuminance and wavelength in the wavelength range of 380 to 440 nm. The ratio with the integrated illuminance in the range of 250 to 370 nm is preferably 100: 0 to 100: 50, and more preferably 100: 0 to 100: 40. As the ultraviolet ray satisfying such a relationship of integrated illuminance, a gallium-filled metal halide lamp and an LED light source that emits light in the wavelength range of 380 to 440 nm are preferable. Alternatively, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra 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 as the light source, It is also possible to use a light having a wavelength shorter than 380 nm by using a band pass filter.

  The adhesive layer obtained by the present invention is formed by irradiating an active energy ray-curable adhesive composition with active energy rays. Various laminates can be produced by laminating at least two members via the adhesive layer. Below, the example of the polarizing film in which the transparent protective film is provided in the at least one surface of the polarizer through the adhesive bond layer as an example of a laminated body is shown. In the polarizing film, the adhesive layer is formed of a cured product layer formed by irradiating an active energy ray-curable adhesive composition with active energy rays. However, the active energy ray-curable adhesive composition according to the present invention can form adhesive layers of various laminates other than the polarizing film, and is not limited to the polarizing film application.

  The curable component (radically polymerizable compound (A) excluding the alkoxy group-containing amino compound (D)) used in the active energy ray-curable adhesive composition has a Tg of 20 ° C. or higher in the adhesive layer formed thereby. It is preferable that it is selected so as to improve durability. From the viewpoint of durability, it is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further 70 ° C. or higher, and further preferably 85 ° C. or higher. On the other hand, if the Tg of the cured product layer becomes too high, the flexibility of the polarizing film is lowered. Therefore, the Tg of the cured product layer is preferably 120 ° C. or less, more preferably 110 ° C. or less, and even more preferably 100 ° C. or less.

  The cured product layer formed by the active energy ray-curable adhesive composition has higher durability than the aqueous adhesive layer. When used for a polarizing film, it is preferable to use an adhesive layer having a Tg of 20 ° C. or higher and to control the thickness of the adhesive layer to be 300 nm to 1 μm. When the thickness of the adhesive layer is less than 300 nm, the cohesive force of the adhesive force itself cannot be obtained, and the adhesive strength may not be obtained. On the other hand, if the thickness of the adhesive layer exceeds 1 μm, the water resistance of the polarizing film may be deteriorated.

  In the polarizing film according to the present invention, a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm is provided on at least one surface of a polarizer via an adhesive layer. In particular, since the adhesive layer is formed by a cured product layer formed by irradiating the active energy ray-curable adhesive composition described above with active energy rays, it is between the polarizer and the transparent protective film. Excellent adhesion and extremely excellent water resistance.

  The manufacturing method of the polarizing film which can use the active energy ray hardening-type adhesive composition which concerns on this invention suitably is demonstrated below.

  The manufacturing method of the polarizing film which concerns on this invention manufactures the polarizing film by which the transparent protective film whose light transmittance of wavelength 365nm is less than 5% is provided in the at least one surface of the polarizer through the adhesive bond layer. A method of applying a coating step of applying the active energy ray-curable adhesive composition described above to at least one surface of a polarizer or a transparent protective film, and bonding the polarizer and the transparent protective film together Through the adhesive layer obtained by irradiating the active energy ray from the polarizer side or the transparent protective film side and curing the active energy ray-curable adhesive composition, the polarizer and the transparent And an adhesion process for adhering the protective film.

  The polarizer and the transparent protective film may be subjected to a surface modification treatment before applying the active energy ray-curable adhesive composition. Specifically, corona treatment, plasma treatment, flame treatment, or excimer treatment is performed on at least one surface of the polarizer or the transparent protective film on the surface on which the active energy ray-curable adhesive composition is applied. You may go.

  The coating method that can be used in the coating process of the active energy ray-curable adhesive composition is appropriately selected depending on the viscosity of the composition and the target thickness. Examples of coating methods include reverse coaters, gravure coaters (direct, reverse and offset), bar reverse coaters, roll coaters, die coaters, bar coaters, rod coaters and the like. In addition, for coating, a method such as a dapping method can be appropriately used.

  A polarizer and a transparent protective film are bonded together through the adhesive applied as described above (bonding step). Bonding of the polarizer and the transparent protective film can be performed with a roll laminator or the like.

  After bonding a polarizer and a transparent protective film, an active energy ray (an electron beam, ultraviolet rays, etc.) is irradiated, an active energy ray hardening-type adhesive composition is hardened and an adhesive bond layer is formed (adhesion process). The irradiation direction of active energy rays (electron beam, ultraviolet ray, 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 deteriorated by active energy rays (electron beams, ultraviolet rays, etc.).

  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, but is preferably 1 to 500 m / min, more preferably 5 to 300 m / min, and still more preferably 10 to 100 m / min. min. When the line speed is too low, the productivity is poor, or the damage to the transparent protective film is too great, and a polarizing film that can withstand the durability test cannot be produced. When the line speed is too high, the adhesive is not sufficiently cured, and the target adhesiveness may not be obtained.

  As described above, when the photoacid generator (C) and the alkoxy group-containing amino compound (D) coexist in the active energy ray-curable adhesive composition, the amino group in the alkoxy group-containing amino compound (D), and light The reaction with the acid derived from the acid generator proceeds, and at the same time, the alkoxy group in the alkoxy group-containing amino compound (D) is hydrolyzed by moisture to produce a reactive hydroxyl group. Thereby, the reactive hydroxyl group in the alkoxy group-containing amino compound (D) can form a hydrogen bond and / or a covalent bond with the hydroxyl group present on the surface of the polarizer. In the present invention, at the time of the bonding step, when there is a heating step at the time of irradiation with active energy rays or after irradiation, the hydrolysis reaction of the alkoxy group in the alkoxy group-containing amino compound (D), and the hydroxyl group produced after the hydrolysis reaction And a hydroxyl group present on the surface of the polarizer promotes a reaction to form a hydrogen bond and / or a covalent bond. Thereby, the polarizing film which has an adhesive bond layer in which water resistance was further improved dramatically can be manufactured.

  In the manufacturing method of the said polarizing film, it is preferable that the moisture content of the said polarizer at the time of the said bonding process is less than 15%. According to this manufacturing method, the adhesive load between the polarizer and the transparent protective film is excellent, and the durability and water resistance of the adhesive layer are reduced while reducing the drying load of the polarizing film obtained after the bonding step (laminating). A polarizing film provided with an excellent adhesive layer can be produced.

  In the polarizing film of the present invention, a polarizer and a transparent protective film are bonded together via an adhesive layer formed by a cured layer of the active energy ray-curable adhesive composition. An easily adhesive layer can be provided between the adhesive layer and the adhesive layer. The easy adhesion layer can be formed of, for example, various resins having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a silicone-based, a polyamide skeleton, a polyimide skeleton, a polyvinyl alcohol skeleton, and the like. These polymer resins can be used alone or in combination of two or more. Moreover, you may add another additive for formation of an easily bonding layer. Specifically, a stabilizer such as a tackifier, an ultraviolet absorber, an antioxidant, and a heat resistance stabilizer may be used.

  The easy adhesion layer is usually provided in advance on a transparent protective film, and the easy adhesion layer side of the transparent protective film and the polarizer are bonded together with an adhesive layer. The easy-adhesion layer is formed by coating and drying the material for forming the easy-adhesion layer on the transparent protective film by a known technique. The material for forming the easy-adhesion layer is usually adjusted as a solution diluted to an appropriate concentration in consideration of the thickness after drying and the smoothness of coating. The thickness of the easy adhesion layer after drying is preferably 0.01 to 5 μm, more preferably 0.02 to 2 μm, and still more preferably 0.05 to 1 μm. Note that a plurality of easy-adhesion layers can be provided, but also in this case, the total thickness of the easy-adhesion layers is preferably in the above range.

  In the polarizing film of the present invention, a transparent protective film is bonded to at least one surface of a polarizer via an adhesive layer formed by a cured product layer of the active energy ray-curable adhesive composition.

  The polarizer is not particularly limited, and various types can be used. Examples of the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film, and two colors such as iodine and dichroic dye. And polyene-based oriented films such as those obtained by adsorbing a functional material and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 80 μm or less.

  A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous solution of iodine and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of boric acid or potassium iodide. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.

  As the polarizer, a thin polarizer having a thickness of 10 μm or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.

  As the thin polarizer, representatively, JP-A-51-069644, JP-A-2000-338329, WO2010 / 100917 pamphlet, PCT / JP2010 / 001460 specification, or Japanese Patent Application 2010- The thin polarizing film described in 269002 specification and Japanese Patent Application No. 2010-263692 specification can be mentioned. These thin polarizing films can be obtained by a production method including a step of stretching a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state and a step of dyeing. With this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.

  As the thin polarizing film, among the production methods including the step of stretching in the state of a laminate and the step of dyeing, WO2010 / 100917 pamphlet, PCT / PCT / PCT / JP 2010/001460 specification, or Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692 as described in the manufacturing method including a step of stretching in a boric acid aqueous solution is preferable. What is obtained by the manufacturing method including the process of extending | stretching in the air auxiliary | assistant before extending | stretching in the boric acid aqueous solution as described in Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692 is preferable.

  The thin high-performance polarizing film described in the specification of PCT / JP2010 / 001460 is a thin film having a thickness of 7 μm or less made of a PVA-based resin oriented with a dichroic material, which is integrally formed on a resin base material. It is a high-functional polarizing film, and has optical properties such as a single transmittance of 42.0% or more and a polarization degree of 99.95% or more.

  The thin high-performance polarizing film generates a PVA-based resin layer by applying and drying a PVA-based resin on a resin substrate having a thickness of at least 20 μm, and the generated PVA-based resin layer is used as a dichroic dyeing solution. So that the dichroic substance is adsorbed on the PVA resin layer, and the PVA resin layer on which the dichroic substance is adsorbed is integrated with the resin base material in the boric acid aqueous solution so that the total draw ratio is the original length. It can manufacture by extending | stretching so that it may become 5 times or more.

  Moreover, it is a method for producing a laminate film including a thin high-performance polarizing film in which a dichroic substance is oriented, and includes a resin base material having a thickness of at least 20 μm and a PVA resin on one side of the resin base material. The said laminated body containing the process of producing | generating the laminated body film containing the PVA-type resin layer formed by apply | coating and drying aqueous solution, and the PVA-type resin layer formed in the single side | surface of the resin base material A step of adsorbing the dichroic substance to the PVA resin layer contained in the laminate film by immersing the film in a dye solution containing the dichroic substance, and a PVA resin adsorbing the dichroic substance A step of stretching the laminate film including a layer in a boric acid aqueous solution so that the total stretching ratio is 5 times or more of the original length, and a PVA resin layer on which a dichroic substance is adsorbed Stretched together with As a result, a thickness of 7 μm or less, a single transmittance of 42.0% or more, and a degree of polarization of 99.95% or more are formed of a PVA resin layer in which a dichroic material is oriented on one side of a resin base material. The thin high-performance polarizing film can be manufactured by including a step of manufacturing a laminate film on which a thin high-performance polarizing film having the above optical characteristics is formed.

The above-mentioned Japanese Patent Application Nos. 2010-269002 and 2010-263692 are thin polarizing films, which are polarizing films of a continuous web made of a PVA-based resin in which a dichroic material is oriented, and are amorphous esters. A laminate including a PVA-based resin layer formed on a thermoplastic resin base material is stretched in a two-stage stretching process consisting of air-assisted stretching and boric acid-water stretching to a thickness of 10 μm or less. It is. Such a thin polarizing film has P> − (100.929T-42.4-1) × 100 (where T <42.3) and P ≧ 99, where T is the single transmittance and P is the polarization degree. .9 (where T ≧ 42.3) is preferable.

  Specifically, the thin polarizing film is a stretch intermediate formed of an oriented PVA resin layer by high-temperature stretching in the air with respect to the PVA resin layer formed on the amorphous ester thermoplastic resin substrate of the continuous web. A colored intermediate product comprising a PVA-based resin layer in which a dichroic material (preferably iodine or a mixture of iodine and an organic dye) is oriented by adsorption of the dichroic material to the stretched intermediate product and a step of generating the product. A thin polarizing film comprising a step of forming a product, and a step of generating a polarizing film having a thickness of 10 μm or less comprising a PVA-based resin layer in which a dichroic material is oriented by stretching in a boric acid solution with respect to a colored intermediate product It can be manufactured by a manufacturing method.

In this production method, the total draw ratio of the PVA resin layer formed on the amorphous ester thermoplastic resin base material by high-temperature drawing in air and drawing in boric acid solution should be 5 times or more. desirable. The liquid temperature of the boric acid aqueous solution for boric-acid water extending | stretching can be 60 degreeC or more. Before stretching the colored intermediate product in the aqueous boric acid solution, it is desirable to insolubilize the colored intermediate product. In this case, the colored intermediate product is added to the aqueous boric acid solution whose liquid temperature does not exceed 40 ° C. It is desirable to do so by dipping. The amorphous ester-based thermoplastic resin base material is amorphous polyethylene containing copolymerized polyethylene terephthalate copolymerized with isophthalic acid, copolymerized polyethylene terephthalate copolymerized with cyclohexanedimethanol, or other copolymerized polyethylene terephthalate. It can be terephthalate and is preferably made of a transparent resin, and the thickness thereof can be 7 times or more the thickness of the PVA resin layer to be formed. Moreover, the draw ratio of the high temperature stretching in the air is preferably 3.5 times or less, and the stretching temperature of the high temperature stretching in the air is preferably not less than the glass transition temperature of the PVA resin, specifically in the range of 95 ° C to 150 ° C. When performing high temperature stretching in the air by free end uniaxial stretching, the total stretching ratio of the PVA resin layer formed on the amorphous ester thermoplastic resin base material is preferably 5 to 7.5 times . In addition, when performing high-temperature stretching in the air by uniaxial stretching at the fixed end, the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin base material is 5 times or more and 8.5 times or less. Is preferred.
More specifically, a thin polarizing film can be produced by the following method.

  A base material of a continuous web of isophthalic acid copolymerized polyethylene terephthalate (amorphous PET) in which 6 mol% of isophthalic acid is copolymerized is prepared. The glass transition temperature of amorphous PET is 75 ° C. A laminate comprising a continuous web of amorphous PET substrate and a polyvinyl alcohol (PVA) layer is prepared as follows. Incidentally, the glass transition temperature of PVA is 80 ° C.

  A 200 μm-thick amorphous PET base material and a 4-5% concentration PVA aqueous solution in which PVA powder having a polymerization degree of 1000 or more and a saponification degree of 99% or more are dissolved in water are prepared. Next, a PVA aqueous solution is applied to a 200 μm thick amorphous PET substrate and dried at a temperature of 50 to 60 ° C. to obtain a laminate in which a 7 μm thick PVA layer is formed on the amorphous PET substrate. .

  A laminated body including a PVA layer having a thickness of 7 μm is subjected to the following steps including a two-step stretching process of air-assisted stretching and boric acid water stretching to produce a thin high-functional polarizing film having a thickness of 3 μm. In the first-stage aerial auxiliary stretching step, the laminate including the 7 μm-thick PVA layer is integrally stretched with the amorphous PET substrate to produce a stretched laminate including the 5 μm-thick PVA layer. Specifically, in this stretched laminate, a laminate including a 7 μm-thick PVA layer is subjected to a stretching apparatus disposed in an oven set to a stretching temperature environment of 130 ° C. so that the stretching ratio is 1.8 times. Are stretched uniaxially at the free end. By this stretching treatment, the PVA layer contained in the stretched laminate is changed to a 5 μm thick PVA layer in which PVA molecules are oriented.

  Next, a colored laminate in which iodine is adsorbed on a PVA layer having a thickness of 5 μm in which PVA molecules are oriented is generated by a dyeing process. Specifically, this colored laminate has a single layer transmittance of the PVA layer constituting the high-functional polarizing film that is finally produced by using the stretched laminate in a staining solution containing iodine and potassium iodide at a liquid temperature of 30 ° C. Iodine is adsorbed to the PVA layer contained in the stretched laminate by dipping for an arbitrary period of time so as to be 40 to 44%. In this step, the staining solution uses water as a solvent and an iodine concentration in the range of 0.12 to 0.30% by weight and a potassium iodide concentration in the range of 0.7 to 2.1% by weight. The concentration ratio of iodine and potassium iodide is 1 to 7. Incidentally, potassium iodide is required to dissolve iodine in water. More specifically, by immersing the stretched laminate in a dyeing solution having an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.1% by weight for 60 seconds, iodine is applied to a 5 μm-thick PVA layer in which PVA molecules are oriented. A colored laminate is adsorbed on the substrate.

  Further, the colored laminated body is further stretched integrally with the amorphous PET base material by the second stage boric acid underwater stretching step to produce an optical film laminate including a PVA layer constituting a highly functional polarizing film having a thickness of 3 μm. To do. Specifically, this optical film laminate is stretched by applying a colored laminate to a stretching apparatus provided in a treatment apparatus set to a boric acid aqueous solution having a liquid temperature range of 60 to 85 ° C. containing boric acid and potassium iodide. It is stretched uniaxially at the free end so that the magnification is 3.3 times. More specifically, the liquid temperature of the boric acid aqueous solution is 65 ° C. It also has a boric acid content of 4 parts by weight with respect to 100 parts by weight of water and a potassium iodide content of 5 parts by weight with respect to 100 parts by weight of water. In this step, the colored laminate with adjusted iodine adsorption amount is first immersed in a boric acid aqueous solution for 5 to 10 seconds. After that, the colored laminate is passed as it is between a plurality of sets of rolls having different peripheral speeds, which is a stretching apparatus provided in the processing apparatus, and the stretching ratio is freely increased to 3.3 times over 30 to 90 seconds. Stretch uniaxially. By this stretching treatment, the PVA layer contained in the colored laminate is changed into a PVA layer having a thickness of 3 μm in which the adsorbed iodine is oriented higher in one direction as a polyiodine ion complex. This PVA layer constitutes a highly functional polarizing film of the optical film laminate.

  Although not an indispensable step for the production of an optical film laminate, the optical film laminate was removed from the boric acid aqueous solution and adhered to the surface of the 3 μm-thick PVA layer formed on the amorphous PET substrate by the washing step. It is preferable to wash boric acid with an aqueous potassium iodide solution. Thereafter, the washed optical film laminate is dried by a drying process using hot air at 60 ° C. The cleaning process is a process for eliminating appearance defects such as boric acid precipitation.

  Similarly, it is not an indispensable process for producing an optical film laminate, but an adhesive is applied to the surface of a 3 μm-thick PVA layer formed on an amorphous PET substrate by a bonding and / or transfer process. However, after bonding the 80 μm thick triacetyl cellulose film, the amorphous PET substrate can be peeled off, and the 3 μm thick PVA layer can be transferred to the 80 μm thick triacetyl cellulose film.

[Other processes]
The manufacturing method of said thin-shaped polarizing film may include another process other than the said process. Examples of other steps include an insolubilization step, a crosslinking step, and a drying (adjustment of moisture content) step. The other steps can be performed at any appropriate timing.
The insolubilization step is typically performed by immersing the PVA resin layer in a boric acid aqueous solution. By performing the insolubilization treatment, water resistance can be imparted to the PVA resin layer. The concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water. The liquid temperature of the insolubilizing bath (boric acid aqueous solution) is preferably 20 ° C to 50 ° C. Preferably, the insolubilization step is performed after the laminate is manufactured and before the dyeing step and the underwater stretching step.
The crosslinking step is typically performed by immersing the PVA resin layer in an aqueous boric acid solution. By performing the crosslinking treatment, water resistance can be imparted to the PVA resin layer. The concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water. Moreover, when performing a bridge | crosslinking process after the said dyeing | staining process, it is preferable to mix | blend iodide further. By blending iodide, elution of iodine adsorbed on the PVA resin layer can be suppressed. The blending amount of iodide is preferably 1 part by weight to 5 parts by weight with respect to 100 parts by weight of water. Specific examples of the iodide are as described above. The liquid temperature of the crosslinking bath (boric acid aqueous solution) is preferably 20 ° C to 50 ° C. Preferably, the crosslinking step is performed before the second boric acid aqueous drawing step. In a preferred embodiment, the dyeing step, the crosslinking step, and the second boric acid aqueous drawing step are performed in this order.

As a material for forming a transparent protective film provided on one or both sides of the polarizer, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like is preferable. / ^m, more preferably not more 2 / 24h or less, particularly preferably those following 140 g ^/ m 2 / 24h, further preferably the following 120 g ^/ m 2 / 24h. The moisture permeability is determined by the method described in the examples.

  The thickness of the transparent protective film can be appropriately determined, but is generally about 1 to 500 μm, preferably 1 to 300 μm, more preferably 5 to 200 μm from the viewpoints of workability such as strength and handleability and thin layer properties. preferable. Furthermore, 20-200 micrometers is preferable and 30-80 micrometers is preferable.

  Examples of the material 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 Polyolefin polymers such as ethylene / propylene copolymers, cyclic olefin resins having a cyclo or norbornene structure, (meth) acrylic resins, or a mixture thereof can be used. Among the resins, polycarbonate resins, cyclic polyolefin resins, and (meth) acrylic resins are preferable, and cyclic polyolefin resins and (meth) acrylic resins are particularly preferable.

  A specific example of the cyclic polyolefin resin is preferably a norbornene resin. The cyclic olefin-based resin is a general term for resins that are polymerized using a cyclic olefin as a polymerization unit, and is described in, for example, JP-A-1-240517, JP-A-3-14882, JP-A-3-122137, and the like. Resin. Specific examples include ring-opening (co) polymers of cyclic olefins, addition polymers of cyclic olefins, cyclic olefins and α-olefins such as ethylene and propylene (typically random copolymers), And graft polymers obtained by modifying them with an unsaturated carboxylic acid or a derivative thereof, and hydrides thereof. Specific examples of the cyclic olefin include norbornene monomers.

  Various products are commercially available as the cyclic polyolefin resin. As specific examples, trade names “ZEONEX” and “ZEONOR” manufactured by ZEON CORPORATION, product names “ARTON” manufactured by JSR Corporation, “TOPAS” manufactured by TICONA, and product names manufactured by Mitsui Chemicals, Inc. “APEL”.

  The (meth) acrylic resin preferably has a Tg (glass transition temperature) of 115 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 125 ° C. or higher, and particularly preferably 130 ° C. or higher. When Tg is 115 ° C. or higher, the polarizing film can be excellent in durability. Although the upper limit of Tg of the (meth) acrylic resin is not particularly limited, it is preferably 170 ° C. or lower from the viewpoint of moldability and the like. From the (meth) acrylic resin, a film having in-plane retardation (Re) and thickness direction retardation (Rth) of almost zero can be obtained.

  As the (meth) acrylic resin, any appropriate (meth) acrylic resin can be adopted as long as the effects of the present invention are not impaired. For example, poly (meth) acrylic acid ester such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid ester- (Meth) acrylic acid copolymer, (meth) methyl acrylate-styrene copolymer (MS resin, etc.), polymer having an alicyclic hydrocarbon group (for example, methyl methacrylate-cyclohexyl methacrylate copolymer, Methyl methacrylate- (meth) acrylate norbornyl copolymer, etc.). Preferably, poly (meth) acrylate C1-6 alkyl such as poly (meth) acrylate methyl is used. More preferred is a methyl methacrylate resin containing methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight).

  Specific examples of (meth) acrylic resins include (meth) acrylic resins having a ring structure in the molecule described in, for example, Acrypet VH and Acrypet VRL20A manufactured by Mitsubishi Rayon Co., Ltd., and JP-A-2004-70296. And high Tg (meth) acrylic resins obtained by intramolecular crosslinking or intramolecular cyclization reaction.

  As the (meth) acrylic resin, a (meth) acrylic resin having a lactone ring structure can also be used. It is because it has high mechanical strength by high heat resistance, high transparency, and biaxial stretching.

  Examples of the (meth) acrylic resin having a lactone ring structure include JP 2000-230016, JP 2001-151814, JP 2002-120326, JP 2002-254544, and JP 2005. Examples thereof include (meth) acrylic resins having a lactone ring structure described in Japanese Patent No. 146084.

  In addition, the transparent protective film of the low moisture permeability provided on both surfaces of the polarizer may use a transparent protective film made of the same polymer material on the front and back, or may use a transparent protective film made of a different polymer material or the like. Good.

In the polarizing film, the transparent protective film preferably has an SP value of 29.0 (kJ / m ³ ) ^1/2 or more and less than 33.0 (kJ / m ³ ) ^1/2 . When the SP value of the transparent protective film is within the above range, the radical polymerizable compound (A) in the active energy ray-curable adhesive composition is, for example, hydroxyethyl acrylamide (SP value 29.6), N-methylol acrylamide. When it contains (SP value 31.5) etc., since it is very close to these SP values, the adhesiveness of a transparent protective film and an adhesive bond layer improves greatly. As the transparent protective film having an SP value of 29.0 (kJ / m ³ ) ^1/2 or more and less than 33.0 (kJ / m ³ ) ^1/2 , for example, saponified triacetyl cellulose (for example, SP value 32.7). ).

Further, in the polarizing film, it is preferable SP value of the transparent protective film is less than 18.0 ^(kJ / ^{m 3) 1/2} or more ^{24.0 (kJ / m 3) 1/2} . When the SP value of the transparent protective film is within the above range, the radical polymerizable compound (A) in the active energy ray-curable adhesive composition is, for example, acryloylmorpholine (SP value 22.9), N-methoxymethylacrylamide. (SP value 22.9), N-ethoxymethylacrylamide (SP value 22.3) and the like are very close to these SP values, so the adhesion between the transparent protective film and the adhesive layer is greatly improved. To do. As a transparent protective film whose SP value is 18.0 (kJ / m ³ ) ^1/2 or more and less than 24.0 (kJ / m ³ ) ^1/2 , for example, unsaponified triacetyl cellulose (SP value 23.3). ) And acrylic film (SP value 22.2).

  In addition, as the transparent protective film, a retardation plate having a retardation with a front retardation of 40 nm or more and / or a thickness direction retardation of 80 nm or more can be used. The front phase difference is usually controlled in the range of 40 to 200 nm, and the thickness direction phase difference is usually controlled in the range of 80 to 300 nm. When a retardation plate is used as the transparent protective film, the retardation plate functions also as a transparent protective film, so that the thickness can be reduced.

  Examples of the retardation plate include a birefringent film obtained by uniaxially or biaxially stretching a polymer material, a liquid crystal polymer alignment film, and a liquid crystal polymer alignment layer supported by a film. The thickness of the retardation plate is not particularly limited, but is generally about 20 to 150 μm.

  In addition, the film which has the said phase difference can be separately bonded to the transparent protective film which does not have a phase difference, and the said function can be provided.

  A functional layer such as a hard coat layer, an antireflection layer, an antisticking layer, a diffusion layer or an antiglare layer can be provided on the surface of the transparent protective film to which the polarizer is not adhered. The functional layers such as the hard coat layer, antireflection layer, antisticking layer, diffusion layer and antiglare layer can be provided on the transparent protective film itself, and separately provided separately from the transparent protective film. You can also

  The polarizing film of the present invention can be used as an optical film laminated with another optical layer in practical use. The optical layer is not particularly limited. For example, for forming a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), and a viewing angle compensation film. One or more optical layers that may be used can be used. In particular, a reflective polarizing film or semi-transmissive polarizing film in which a polarizing plate or a semi-transmissive reflecting plate is further laminated on the polarizing film of the present invention, an elliptical polarizing film or circularly polarizing film in which a retardation film is further laminated on a polarizing film. A wide viewing angle polarizing film obtained by further laminating a viewing angle compensation film on a film or a polarizing film, or a polarizing film obtained by further laminating a brightness enhancement film on the polarizing film is preferred.

  An optical film obtained by laminating the above optical layer on a polarizing film can be formed by a method of sequentially laminating separately in the manufacturing process of a liquid crystal display device or the like. It is excellent in stability and assembly work, and has the advantage of improving the manufacturing process of a liquid crystal display device and the like. Appropriate bonding means such as an adhesive layer can be used for lamination. When adhering the above polarizing film and other optical films, their optical axes can be set at an appropriate arrangement angle in accordance with the target retardation characteristics.

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

  The pressure-sensitive adhesive layer can 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 adhesive 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 according to the purpose of use and adhesive force, and is generally 1 to 500 μm, preferably 1 to 200 μm, and particularly preferably 1 to 100 μm.

  The exposed surface of the adhesive layer is temporarily covered with a separator for the purpose of preventing contamination until it is put into 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, an appropriate thin leaf body such as a plastic film, rubber sheet, paper, cloth, non-woven fabric, net, foamed sheet, metal foil, or a laminate thereof, and a silicone-based or long sheet as necessary. Appropriate ones according to the prior art, such as those coated with an appropriate release agent such as a chain alkyl type, fluorine type or molybdenum sulfide, can be used.

  The polarizing film or the optical film of the present invention can be preferably used for forming various devices such as a liquid crystal display device. The liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally 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 limitation in particular except the point which uses the polarizing film or optical film by invention, and it can apply according to the former. As the liquid crystal cell, any type such as a TN type, an STN type, or a π type can be used.

  An appropriate 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 backlight or a reflecting plate that is used in an illumination system can be formed. In that case, the polarizing film or optical film by this invention can be installed in the one side or both sides of a liquid crystal cell. When providing a polarizing film or an optical film on both sides, they may be the same or different. Further, when forming a liquid crystal display device, for example, a single layer or a suitable layer of a diffusion plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate, a backlight, etc. 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.

(Adjustment of active energy ray-curable adhesive composition)
Each component used is as follows.

(1) Radical polymerizable compound (A)
HEAA (hydroxyethyl acrylamide), SP value 29.6 (kJ / m ³ ) ^1/2 , Tg of homopolymer; 123 ° C., light acrylate 1.9ND-A (1.9-nonanediol diacrylate, manufactured by Kojin Co., Ltd. ), SP value 19.2 (kJ / m ³ ) ^1/2 , homopolymer Tg 69 ° C., Kyoeisha Chemical Co., Ltd. ACMO (acryloylmorpholine), SP value 22.9 (kJ / m ³ ) ^1/2 , homopolymer Tg: 150 ° C., manufactured by Kojin Co., Ltd. (2) Radical generator (B)
IRGACURE907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one), manufactured by BASF (3) Photogenerator (C)
CPI-101A (triarylsulfonium-SbF ₆ salt), manufactured by San Apro (4) alkoxy group-containing amino compound (D)
Alkoxy group-containing aminosilane coupling agent (D1): KBM603 (N-2 (aminoethyl) -3-aminopropyltrimethoxysilane), manufactured by Shin-Etsu Silicone

Example 1
Radical polymerizable compound (A) listed in Table 1 (when the total amount of radical polymerizable compound (A) is 100 parts by weight, HEAA 30 parts by weight, light acrylate 1.9ND-A 30 parts by weight, ACMO 40 parts by weight ) 1 part by weight of radical generator (B) (IRGACURE819), 1 part by weight of CPI-101A as photoacid generator (C), 100 parts by weight of alkoxy group-containing aminosilane coupling agent (D1) (KBM603) The adhesive composition which added 1 weight part of was adjusted. The thickness of the final adhesive layer on one side (bonding surface) of ^two untreated acrylic films (transparent protective film, SP value 22.2, moisture permeability 70 g / m 2/24 h) with a micro gravure coater The adhesive composition was applied so as to be 0.6 μm. Next, both sides of the polarizer were corona treated with a discharge amount of 100 W · min / m ² , and two transparent protective films coated with an adhesive composition were applied to both sides of the polarizer from the coated surface side. Combined. Furthermore, 700 mJ / cm < ² > of ultraviolet rays were each radiated | emitted from the transparent protective film side of the both sides bonded together, and the polarizing film which has a transparent protective film on both surfaces of a polarizer was manufactured.

Examples 2-3
A polarizing film was produced in the same manner as in Example 1 except that the amount of the alkoxy group-containing aminosilane coupling agent (D1) (KBM603) was changed to the amount shown in Table 1.

Comparative Examples 1-2
A polarizing film was produced in the same manner as in Example 1 except that either one of the photogenerator (C) and the alkoxy group-containing amino compound (D) was not used.

[Evaluation]
The following evaluation was performed about the polarizing film obtained by the Example and the comparative example. The results are shown in Table 1.

<Tg: Glass transition temperature>
Tg was measured under the following measurement conditions using a TA Instruments dynamic viscoelasticity measuring device RSAIII.
Sample size: width 10mm, length 30mm,
Clamp distance 20mm,
Measurement mode: Tensile, Frequency: 1 Hz, Temperature rising rate: 5 ° C./min Dynamic viscoelasticity was measured and adopted as the temperature Tg of tan δ peak top.

<Water vapor permeability of transparent protective film>
The moisture permeability was measured according to a moisture permeability test (cup method) of JIS Z0208. A sample cut to a diameter of 60 mm was set in a moisture permeable cup containing about 15 g of calcium chloride, and the temperature was 40 ° C. and the humidity was 90% R.D. H. The placed in a constant temperature machine, to determine the moisture permeability by measuring the weight increase of calcium chloride before and after allowing to stand for 24 hours ^{(g / m 2 / 24h)} .

<Water resistance test>
Regarding the water resistance test, the following three tests were performed.
[Test (1): 40 ° C., 92% R.D. H. , 500h]
92% R.O. at 40 ° C. H. Under the environment, the sample obtained by cutting the polarizing film into 1.5 cm × 15 cm squares was left for 500 hours, then taken out and immediately peeled at 90 ° at a peeling speed of 300 m / min, and the peel force was measured.
[Test (2): 40 ° C. warm water, 2 h]
A sample (a sample having the same shape as test (1)) was immersed in warm water of 40 ° C. for 2 hours, and immediately after taking out, 90 ° peeling was performed at a peeling speed of 300 m / min, and the peel force was measured.
[Test (3): 40 ° C. warm water, 2 hours, with aging]
Before the test, a sample (a sample having the same shape as that of the test (1)) was heated (aged) at 50 ° C. for 12 hours, immersed in warm water at 40 ° C. for 2 hours, and immediately after removal, a peeling speed of 300 m / min was obtained. The peel strength was measured at a rate of 90 ° and the peel force was measured.

In tests (1) to (3), the evaluation criteria for the measured peel force are as follows.
◎: Peel force 1.0N / 15mm or more ○: Peel force 0.5N or more, less than 1.0N / 15mm △: Peel force 0.2N or more, less than 0.5N / 15mm ×: Peel force 0.2N / 15mm or less

Claims (19)

  An active energy ray-curable adhesive composition comprising a radical polymerizable compound (A), a radical generator (B), a photoacid generator (C), and an alkoxy group-containing amino compound (D).   The active energy ray-curable adhesive composition according to claim 1, wherein the alkoxy group-containing amino compound (D) is an alkoxy group-containing aminosilane coupling agent (D1).   The active energy according to claim 2, wherein the content of the alkoxy group-containing aminosilane coupling agent (D1) is 0.1 to 20 parts by weight when the total amount of the radical polymerizable compound (A) is 100 parts by weight. A wire curable adhesive composition. The photoacid generator (C) containing a photoacid generator having at least one selected from the group consisting of PF ₆ ⁻ , SbF ₆ ^— and AsF ₆ ^— as a counter anion as the photo acid generator (C). An active energy ray-curable adhesive composition according to claim 1.   The active energy ray-curable adhesive composition according to claim 1, wherein the radical polymerizable compound (A) contains an acrylamide derivative.   The radically polymerizable compound (A) is at least one selected from the group consisting of hydroxyethylacrylamide, N-methylolacrylamide, acryloylmorpholine, and N-methoxymethylacrylamide. An active energy ray-curable adhesive composition. As the radical generator (B), a compound represented by the following general formula (1);

(Wherein R ¹ and R ² represent —H, —CH ₂ CH ₃ , —iPr or Cl, and R ¹ and R ² may be the same or different). The active energy ray-curable adhesive composition described. As the radical generator (B), a compound represented by the following general formula (2);

Wherein R ³ , R ⁴ and R ⁵ represent —H, —CH ₃ , —CH ₂ CH ₃ , —iPr or Cl, and R ³ , R ⁴ and R ⁵ may be the same or different. The active energy ray hardening-type adhesive composition of Claim 7 contained. A polarizing film in which a transparent protective film having a light transmittance of a wavelength of 365 nm of less than 5% is provided on at least one surface of a polarizer via an adhesive layer,
The polarized light, wherein the adhesive layer is formed by a cured product layer formed by irradiating the active energy ray-curable adhesive composition according to any one of claims 1 to 8 with active energy rays. the film.   The polarizing film according to claim 9, wherein the adhesive layer has a glass transition temperature (Tg) of 20 ° C. or higher. Polarizing film according to claim 9 or 10 moisture permeability is not more than 150g ^/ m 2 ^/ 24h of the transparent protective film. The polarizing film according to claim 9, wherein an SP value of the transparent protective film is 29.0 (kJ / m ³ ) ^1/2 or more and less than 33.0 (kJ / m ³ ) ^1/2 . The polarizing film according to claim 9, wherein the transparent protective film has an SP value of 18.0 (kJ / m ³ ) ^1/2 or more and less than 24.0 (kJ / m ³ ) ^1/2 . A method for producing a polarizing film, wherein a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm is provided on at least one surface of a polarizer via an adhesive layer,
A coating step of coating the active energy ray-curable adhesive composition according to any one of claims 1 to 8 on at least one surface of the polarizer or the transparent protective film;
A bonding step of bonding the polarizer and the transparent protective film;
Through the adhesive layer obtained by irradiating active energy rays from the polarizer surface side or the transparent protective film surface side and curing the active energy ray-curable adhesive composition, the polarizer and The manufacturing method of the polarizing film characterized by including the adhesion process which adheres the above-mentioned transparent protective film.   Before the coating step, at least one surface of the polarizer or the transparent protective film, on the surface on which the active energy ray-curable adhesive composition is coated, corona treatment, plasma treatment, frame The manufacturing method of the polarizing film of Claim 14 which performs a process or an excimer process.   The manufacturing method of the polarizing film according to claim 14 or 15 whose moisture content of said light polarizer at the time of said pasting process is less than 15%.   The manufacturing method of the polarizing film in any one of Claims 14-16 which has a heating process at the time of the said adhesion process at the time of active energy ray irradiation or after irradiation.   An optical film, wherein at least one polarizing film according to any one of claims 9 to 13 is laminated.   An image display device comprising the polarizing film according to claim 9 and / or the optical film according to claim 18.