KR101779685B1 - Active-energy-ray-curable adhesive agent composition, polarizing film and method for producing same, optical film, and image display device - Google Patents

Abstract

An active energy ray-curable adhesive composition capable of providing an adhesive layer for laminating at least two members is provided with an active energy ray curable adhesive composition capable of exhibiting adhesiveness even after immersing in hot water for several hours and having an active energy (A), a radical generator (B), a photoacid generator (C), and an alkoxy group-containing amino compound (D) in order to provide an active energy ray curable adhesive composition. do.

Description

Technical Field [0001] The present invention relates to an active energy ray curable adhesive composition, a polarizing film, a method for producing the same, an optical film, and an image display device.

The present invention relates to an active energy ray curable adhesive composition for forming an adhesive layer for bonding two or more members, in particular, an active energy ray curable adhesive composition for forming an adhesive layer of a polarizer and a transparent protective film, and a polarizing film. The polarizing film can be used alone or as an optical film laminated thereon to form an image display apparatus such as a liquid crystal display (LCD), an organic EL display, a CRT, or a PDP. The present invention also relates to a method for producing the polarizing film, an optical film and an image display apparatus.

Liquid crystal display devices are rapidly developing on the market in watches, mobile phones, PDAs, notebook PCs, PC monitors, DVD players, TVs, and the like. A liquid crystal display device is one in which a polarization state due to switching of liquid crystal is visualized. In the principle of display, a polarizer is used. Particularly in applications such as TVs, higher brightness, higher contrast, and a wider viewing angle are required, and polarizing films are required to have higher transmittance, higher polarization degree, and higher color reproducibility.

As a polarizer, an iodine-based polarizer having a stretched structure by adsorbing iodine to, for example, polyvinyl alcohol (hereinafter simply referred to as " PVA ") in view of high transmittance and high polarization degree is most widely used. In general, a polarizing film is obtained by adhering a transparent protective film to both surfaces of a polarizer by an aqueous adhesive agent in which a polyvinyl alcohol-based material is dissolved in water (see Patent Documents 1 and 2) . As the transparent protective film, triacetyl cellulose having a high moisture permeability is used.

In the case of using a water-based adhesive such as a polyvinyl alcohol-based adhesive (so-called wet lamination) in producing a polarizing film, a drying step is necessary after a polarizer and a transparent protective film are laminated. In order to improve the productivity of the polarizing film, it is preferable to shorten the drying step or employ another bonding method which does not require a drying step.

If a water-based adhesive is used, a polarizing film having good adhesiveness can not be obtained unless the moisture content of the polarizer is made relatively high (usually, the water content of the polarizer is about 30%) in order to improve the adhesiveness with the polarizer . However, the polarizing film thus obtained has problems such as a large dimensional change under high temperature and high temperature and high humidity, and poor optical characteristics. On the other hand, in order to suppress the dimensional change, the moisture content of the polarizer may be lowered or a transparent protective film having a low moisture permeability may be used. However, when such a polarizer and transparent protective film are attached using an aqueous adhesive, the drying efficiency is lowered, the polarization characteristic is lowered, or the appearance problem occurs, and thus a polarizing film useful in practical use can not be obtained.

In recent years, as the image display device has become larger in size, particularly, as represented by TVs, the size of the polarizing film has become very important in terms of productivity and cost (yield, cavity up). However, in the polarizing film using the water-based adhesive described above, the so-called light leakage (nonuniformity) that the polarizing film changes dimension due to the heat of the backlight and becomes nonuniform and the black display is whitish in a part of the whole screen becomes remarkable .

In order to solve the problems in the wet lamination described above, active energy ray curable adhesives that do not contain water or an organic solvent have been proposed. For example, the following Patent Document 3 discloses that (A) a radically polymerizable compound having a molecular weight of 1,000 or less containing a polar group, (B) a radically polymerizable compound having a molecular weight of 1,000 or less, An active energy ray curable adhesive containing a radical generator is disclosed. However, the combination of the radically polymerizable compound (monomer) constituting such an adhesive tends to be inferior in adhesion to the polarizing film, especially since it is designed for the purpose of improving the adhesion to the norbornene resin film.

Patent Document 4 discloses an active energy ray curable adhesive comprising a radical generator having a molar extinction coefficient at a wavelength of 360 to 450 nm of 400 or more and an ultraviolet ray curable compound as essential components. However, since the combination of monomers constituting such an adhesive is designed mainly for the purpose of preventing warping and deformation when an optical disk or the like is adhered, the adhesive property with the polarizing film tends to be inferior when used for a polarizing film .

(Meth) acrylic compound having two or more (meth) acryloyl groups in the molecule and (b) a (meth) acrylic compound having a hydroxyl group in the molecule and having a polymerizable (Meth) acryl-based compound having only one double bond and (c) a phenol ethylene oxide-modified acrylate or nonylphenol ethylene oxide-modified acrylate. However, the combination of monomers constituting such an adhesive is concerned that the compatibility of the respective monomers is relatively low, the phase separation progresses, and the transparency of the adhesive layer is lowered. Further, such an adhesive tends to improve the adhesiveness by softening the cured product (adhesive layer) (lowering the Tg), and it is feared that the durability such as crack resistance is deteriorated. The crack resistance can be evaluated by a cold shock test (heat shock test).

The present inventors have developed an active energy ray curable adhesive containing a radical polymerizing compound, a photo radical generator, and a photoacid generator (Patent Documents 6 and 7). Further, the inventors of the present invention have developed active energy ray-curable adhesive compositions containing at least three radically polymerizable compounds having different SP values (Patent Document 8).

Japanese Patent Application Laid-Open No. 2006-220732 Japanese Patent Application Laid-Open No. 2001-296427 Japanese Patent Application Laid-Open No. 2008-009329 Japanese Laid-Open Patent Publication No. 09-31416 Japanese Patent Application Laid-Open No. 2008-174667 Japanese Laid-Open Patent Publication No. 2012-67260 Japanese Laid-Open Patent Publication No. 2012-68593 Japanese Laid-Open Patent Publication No. 2012-144690

The adhesives described in the above Patent Documents 6-8 are excellent in adhesiveness and water resistance, but in recent years, there has been a demand for adhesives having excellent water resistance, which can exhibit adhesiveness even after being immersed in hot water for several hours. On the other hand, in the adhesives described in Patent Documents 6-8, there was room for further research in order to improve the water resistance to such a level that the adhesive property can be exhibited even after immersing in normal temperature water for several hours.

The present invention has been made in view of the above problems, and an object of the present invention is to provide an active energy ray curable adhesive composition capable of providing an adhesive layer for laminating at least two members, which can exhibit adhesiveness even after immersing in normal temperature water for several hours Which is capable of providing an adhesive layer having a very high water resistance. Another object of the present invention is to provide a polarizing film having an adhesive layer having an excellent water resistance, a method for producing the polarizing film, an optical film and an image display device.

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

In the above active energy ray-curable adhesive composition, it is preferable that the alkoxy group-containing amino compound (D) is an alkoxy group-containing amino silane coupling agent (D1).

When the total amount of the radically polymerizable compound (A) in the active energy ray-curable adhesive composition is 100 parts by weight, the content of the alkoxyl group-containing aminosilane coupling agent (D1) is preferably 0.1 to 20 parts by weight .

The active energy ray-curable adhesive composition according to any one of claims 1 to 3, wherein the photoacid generator (C) contains a photoacid generator having at least one selected from the group consisting of PF ₆ ^- , SbF ₆ ^- and AsF ₆ ^- .

In the above active energy ray-curable adhesive composition, it is preferable that the radically polymerizable compound (A) contains an acrylamide derivative.

In the above active energy ray-curable adhesive composition, the radically polymerizable compound (A) is at least one compound selected from the group consisting of hydroxyethyl acrylamide, N-methylol acrylamide, acryloylmorpholine and N-methoxymethylacrylamide At least one kind selected from the group consisting of

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

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

(2)

(Wherein, R ^3, R ⁴ and R ⁵ are _{-H, -CH 3, -CH 2 CH} 3, or -iPr represents Cl, R ^3, R ⁴ and R ⁵ are the same or different) a .

The polarizing film according to the present invention is a polarizing film having a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm formed on at least one surface of a polarizer with an adhesive layer interposed therebetween, Characterized in that the active energy ray curable adhesive composition according to any one of claims 1 to 10 is formed from a cured layer formed by irradiating an active energy ray.

In the polarizing film, it is preferable that the glass transition temperature (Tg) of the adhesive layer is 20 DEG C or more.

In the polarizing film, the transparent protective film preferably has a moisture permeability of 150 g / m 2/24 h or less.

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

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

The method for producing a polarizing film according to the present invention is a method for producing a polarizing film in which a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm is formed on at least one surface of a polarizer through an adhesive layer, A coating step of applying the active energy ray-curable adhesive composition according to any one of claims 1 to 10 on at least one surface of the polarizer or the transparent protective film; An adhesive bonding step of bonding the polarizer and the transparent protective film via an adhesive layer obtained by irradiating an active energy ray from the side of the polarizer surface or the surface of the transparent protective film and curing the active energy ray curable adhesive composition, The process comprising the steps of:

Wherein at least one surface of the polarizer or the transparent protective film is subjected to a corona treatment, a plasma treatment, a frame treatment, or a coating treatment on the side to which the active energy ray curable adhesive composition is applied, It is preferable to carry out treatment or excimer treatment.

In the method for producing a polarizing film, it is preferable that the water content of the polarizer in the bonding step is less than 15%.

In the method for producing a polarizing film, it is preferable to have a heating step during or after irradiation with active energy rays in the adhering step.

The present invention also relates to an optical film in which at least one polarizing film described above is laminated, a polarizing film described in any of the above, and / or an image display apparatus using the optical film described above.

The active energy ray-curable adhesive composition according to the present invention is characterized in that the radical generator (B) generates a radical and the radical polymerizing compound (A) performs radical polymerization by irradiating an active energy ray, Can be formed. In the present invention, since the active energy ray curable adhesive composition contains the photoacid generator (C) and the alkoxy group-containing amino compound (D) in addition to the radical polymerizable compound (A) and the radical generator (B) The water resistance and adhesiveness of the adhesive layer can be dramatically improved as compared with the case of not containing the generator (C) and the alkoxy group-containing amino compound (D). In the present invention, the reason why the water resistance and adhesiveness of the adhesive layer is improved is not clear, but it 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 reaction between the amino group in the alkoxy group-containing amino compound (D) and the acid derived from the photoacid generator proceeds, At the same time, the alkoxy group in the alkoxy group-containing amino compound (D) is hydrolyzed by moisture to form a reactive hydroxyl group. As a result, 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. Further, the reactive hydroxyl group in the alkoxy group-containing amino compound (D) can directly react with the hydroxyl group existing 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 becomes remarkably high, The adhesion between the layer and the polarizer is remarkably 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, silanol groups with higher reactivity are produced. Thereby, the silanol group in the alkoxyl group-containing aminosilane coupling agent (D1) and the hydroxyl group present on the surface of the polarizer can interact more strongly via hydrogen bonding and / or covalent bonding. As a result, the water resistance of the adhesive layer and the adhesiveness of the adhesive layer and the polarizer are further improved remarkably.

The adhesive layer of the active energy ray-curable adhesive composition according to the present invention is excellent in adhesiveness and durability, and is particularly excellent in water resistance, which can exhibit adhesiveness even after immersion in room temperature water for several hours. Therefore, the laminate in which at least two members are laminated via such an adhesive layer can be suitably used for various purposes. For example, in the case of the polarizing film provided with the adhesive layer related to the present invention, since the dimensional change is very small, it is possible to easily cope with the enlargement of the polarizing film, and it is possible to suppress the production cost from the viewpoint of the yield and the number of faces , And it is also possible to suppress the occurrence of unevenness of 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 radically polymerizable compound (A), a radical generator (B), a photoacid generator (C), and an alkoxy group-containing amino compound (D).

The radical polymerizable compound (A) serves as a curing component that undergoes radical polymerization, in particular, photo radical polymerization, in the presence of a radical generated by irradiating the radical generator (B) with an active energy ray. Therefore, in the present invention, any compound having a vinyl group, at least one carbon-carbon double bond-containing vinyl group, (meth) acryloyl group or the like as the radical polymerizable compound (A) can be used without particular limitation. However, in the present invention, among the radical polymerizable compound (A), the following general formula (1):

CH ₂ = C (R ¹ ) -CONH _2-m - (XOR ² ) _m (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group, X represents a -CH ₂ - group or a -CH ₂ CH ₂ - group, and R ² represents a - (CH ₂ ) _n -H group ), And m represents 1 or 2, is preferable.

Specific examples of the acrylamide derivative represented by the above general formula (1) include N-hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) , N-ethoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide and N-ethoxyethyl (meth) acrylamide. These acrylamide derivatives may be used singly or in combination of two or more.

As the acrylamide derivative represented by the general formula (1), a commercially available product can also be preferably used. Specifically, there may be mentioned, for example, N-hydroxyethylacrylamide (trade name "HEAA", Kyocin Co.), N-methoxymethylacrylamide (trade name "NMMA" Amide (trade name "NBMA", manufactured by MRC Unitech Co., Ltd.) and N-methoxymethyl methacrylamide (trade name "WASMA 2MA", manufactured by Kasano Chemical Co., Ltd.).

As the acrylamide derivative represented by the above general formula (1), N-hydroxyethyl (meth) acrylamide is preferable. Acrylamide derivative exhibits good adhesion even to a transparent protective film using a polarizer having a low water content or a material having a low moisture permeability. Of the monomers exemplified above, N-hydroxyethyl acrylamide has particularly good adhesion .

The active energy ray-curable adhesive composition according to the present invention is characterized in that as the radical polymerizable compound (A), an acrylamide derivative other than that represented by the general formula (1), a monofunctional (meth) acrylate having various aromatic rings and a hydroxyl group ) Acrylate, urethane (meth) acrylate, polyester (meth) acrylate, and compounds having various (meth) acryloyl groups. When the total amount of the radical polymerizable compound (A) is 100 parts by weight, the proportion of the acrylamide derivative represented by the general formula (1) is preferably 1 to 50 parts by weight More preferably 3 to 30 parts by weight.

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

The monofunctional (meth) acrylate having an aromatic ring and a hydroxyl group may use various monofunctional (meth) acrylates having aromatic rings and hydroxy groups. The hydroxy group may be present as a substituent on the aromatic ring. In the present invention, however, it is preferable that the hydroxy group is present as an organic group (bonded to a hydrocarbon group, particularly an alkylene group) bonding the aromatic ring and (meth) acrylate.

Examples of the monofunctional (meth) acrylate having an aromatic ring and a hydroxyl 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, phenylpolyethylene glycol glycidyl ether, and the like. 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- Phenoxypropyl (meth) acrylate, 2-hydroxy-3-phenylpolyethylene glycol propyl (meth) acrylate, and the like.

Examples of the urethane (meth) acrylate include diol compounds such as (meth) acrylates having isocyanate groups and polyalkylene glycols such as polyurethane diols, polyester diols, polyether diols, polyethylene glycols and polypropylene glycols And a reaction product with a terminal hydroxyl group.

Examples of the compound having a (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylates such as methyl (meth) acrylate and ethoxyethyl (meth) acrylate, alkyl (meth) acrylates having 1 to 12 carbon atoms such as isopropyl Hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ) Containing hydroxyl groups such as 8-hydroxyoctyl acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate or (4-hydroxymethylcyclohexyl) -methylacrylate; Maleic anhydride, itacon anhydride (Meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate and the like; , (Meth) acryloyloxynaphthalenesulfonic acid, and the like; and phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate and the like. (Meth) acrylamide, maleimide, N-cyclohexylmaleimide and N-phenylmaleimide; aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N, N-dimethylaminoethyl , Alkylaminoalkyl (meth) acrylate monomers such as t-butylaminoethyl (meth) acrylate and 3- (3-pyrimidyl) propyl (meth) acrylate; N- (meth) acryloyloxymethylene succinimide Nitrogen-containing monomers such as succinimide-based monomers such as N- (meth) acryloyl-6-oxyhexamethylene succinimide and N- (meth) acryloyl-8-oxyoctamethylene succinimide. have.

The active energy ray-curable adhesive composition according to the present invention may further comprise, as the radically polymerizable compound (A), a monomer having one carbon-carbon double bond as described above and a monomer having two or more carbon- , Particularly preferably a polyfunctional (meth) acrylate-based monomer, 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. Examples of the hydrophobic monomers having two or more carbon-carbon double bonds, particularly hydrophobic polyfunctional (meth) acrylate monomers include tricyclodecane dimethanol diacrylate, divinylbenzene, N, N'-methylene (Meth) acrylate, diethyleneglycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di 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 Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol glycol di (meth) acrylate, glycerin di (meth) acrylate, EO- Acrylate, EO-modified diglycerin tetra (meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, bisphenol A-EO adduct di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, diethylene glycol di (meth) acrylate, (Meth) acrylate, isocyanuric acid EO modified di (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, epsilon -caprolactone modified tris ((meth) acryloxyethyl) Isocyanurate, a polymer of 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate, 2-hydroxyethyl (meth) acrylate and 1,6-diisocyanate hexane, 4- (2- (meth) The reels one oxy, and the like) phenyl] fluorene.

In the present invention, the ratio of the monomer having two or more carbon-carbon double bonds to the total amount of the radical polymerizable compound (A) is preferably 5 to 80 parts by weight, more preferably 10 to 70 parts by weight. When the proportion is less than 5 parts by weight, sufficient water resistance may not be obtained. On the other hand, when 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) , And as a result, hydrogen bonding and / or covalent bonding to the hydroxyl groups present on the surface of the polarizer. Therefore, when the photoacid generator (C) is consumed in the photo cationic polymerization of the epoxy group-containing compound, the water resistance and durability of the above-described adhesive layer are not sufficiently improved, which is not preferable. Therefore, the proportion of the epoxy group-containing compound to the total amount of the radical polymerizable compound (A) and the epoxy group-containing compound in the active energy ray-curable adhesive composition is preferably 5% by weight or less, more preferably 1% , And it is particularly preferable that it does not 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 a radical by irradiating the active energy ray.

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

(3)

(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) ) Is preferably used in combination with a radical-generating agent having a high sensitivity to a light having a wavelength of 380 nm or more, which will be described later. When the compound represented by the general formula (1) is used, the adhesiveness is superior to the case where a radical-generating agent having high sensitivity to light of 380 nm or more is used alone. Of the compounds represented by the general formula (1), diethyl thioxanthone in which R ¹ and R ² are -CH ₂ CH ₃ are 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, more preferably 1 to 7 parts by weight, based on 100 parts by weight of the total amount of the radical polymerizable compound (A) , And more preferably 1 to 5 parts by weight.

It is also preferable to add a polymerization initiator as needed. Examples of the polymerization initiator include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, Wheat, and the like, and ethyl 4-dimethylaminobenzoate is particularly preferable. When the polymerization initiator is used, the addition amount is usually 0 to 5 parts by weight, preferably 0 to 4 parts by weight, and most preferably 0 to 5 parts by weight, based on 100 parts by weight of the total amount of the radical polymerizable compound (A) 0 to 3 parts by weight.

If necessary, known radical generators may be used in combination. 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-generating agent having high sensitivity to light of 380 nm or more as the radical-generating agent. Specific examples thereof include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl- (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 (eta 5-2,4-cyclopentadien-1-yl) (1H-pyrrol-1-yl) -phenyl) titanium, and the like.

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

[Chemical Formula 4]

(Wherein, R ^3, R ⁴ and R ⁵ are _{-H, -CH 3, -CH 2 CH} 3, or -iPr represents Cl, R ^3, R ⁴ and R ⁵ are the same or different) a Is preferably used. As a compound represented by the general formula (2), commercially available 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (trade name: IRGACURE 907 manufactured by BASF) . In the same manner as in Example 1 except that 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: IRGACURE369 manufactured by BASF) ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: IRGACURE 379 manufactured by BASF) is preferred because of its high sensitivity.

The content of the radical generator (B) is preferably 0.5 to 10 parts by weight, more preferably 1 to 7 parts by weight, and more preferably 1 to 5 parts by weight, based on 100 parts by weight of the total amount of the radical polymerizable compound (A) It is more desirable to be negative.

In the present invention, the active energy ray-curable adhesive composition contains 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). As a result, the water resistance and durability of the adhesive layer can be remarkably improved as compared with the case of not containing the photoacid generator (C) and the alkoxy group-containing amino compound (D). The photoacid generator (C) can be represented by the following general formula (3).

In general formula (3)

[Chemical Formula 5]

(Wherein L ⁺ represents an arbitrary onium cation, and X ^- represents PF ₆ ^- , SbF ₆ ^- , AsF ₆ ^- , SbCl ₆ ^- , BiCl ₅ ^- , SnCl ₆ ^- , ClO ₄ ^- Oxycarbamate anion, SCN ^- , and the like.

Examples of the structure of the onium cation that is preferable as the onium cation L ⁺ in the general formula (3) include onium cation selected from the following general formulas (4) to (12).

In general formula (4)

[Chemical Formula 6]

In general formula (5)

(7)

In general formula (6)

[Chemical Formula 8]

(7)

[Chemical Formula 9]

In general formula (8)

[Chemical formula 10]

In general formula (9)

(11)

In general formula (10)

[Chemical Formula 12]

In general formula (11)

[Chemical Formula 13]

In general formula (12)

[Chemical Formula 14]

(Wherein R ¹ , R ² and R ³ are each independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted A substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted acyl group, a substituted or unsubstituted aryloxy group, A substituted or unsubstituted oxycarbonyl group, or a halogen atom, R ⁴ represents the same group as the groups described for R ¹ , R ² and R ³ , R ⁵ represents a group selected from the group consisting of a substituted or unsubstituted carbonyl group, R ⁶ and R ⁷ each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkoxyl group, R represents a halogen atom, a hydroxyl group, a substituted or unsubstituted alkylthio 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, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted A substituted or unsubstituted alkoxy group, an alkoxyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted heterocyclic thio group, A substituted or unsubstituted acyl group, a substituted or unsubstituted carbonyloxy group, or a substituted or unsubstituted oxycarbonyl group, Ar ⁴ and Ar ^{5 each} represent a substituted or unsubstituted aryl group, a substituted or unsubstituted Heterocyclic group, X represents oxygen or sulfur atom, i represents an integer of 0 to 5, j represents an integer of 0 to 4, and k represents an integer of 0 to 3. In addition, Adjacent R , 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 the general formula (4):

(P-chlorophenyl) sulfonium, dimethyl (p-cyanophenyl) sulfonium, dimethyl (p-chlorophenyl) sulfonium, dimethyl (pentafluorophenyl) sulfonium, dimethyl (p- (trifluoromethyl) phenyl) sulfonium, dimethyl (2,4,6-tribromophenyl) sulfonium, (p-hydroxyphenyl) sulfonium, dimethyl (p-mercaptophenyl) sulfonium, dimethyl (p-methylsulfonylphenyl) (P-isopropylphenyl) sulfonium, dimethyl (p-octadecylphenyl) sulfonium, dimethyl (p-methylphenyl) sulfonium, (P-phenylsulfanylphenyl) sulfonium, dimethyl (p-methoxyphenyl) sulfonium, dimethyl (p-methoxycarbonylphenyl) sulfonium, -Oxo-2H-chromen-4-yl) dimethylsulfonium, (4- Dimethyl (2-naphthyl) sulfonium, dimethyl (9-anthryl) sulfonium, diethylphenylsulfonium (4-phenylsulfanyl-phenyl) -sulfonium, 4,4'-bis (diphenylsulfanyl) phenylsulfonium chloride, diphenylsulfonium Diphenylsulfide, 4,4'-bis [di [4- (2-hydroxy-ethoxy) -phenyl]] sulfonium]] diphenylsulfide, (P-chlorophenyl) sulfonium, diphenyl (p-cyanophenyl) sulfonium, diphenyl (p-cyanophenyl) (P- (tri (trifluoromethyl) phenyl) sulfonium, diphenyl (m-nitrophenyl) sulfonium, diphenyl (P-hydroxyphenyl) sulfonium, diphenyl (p-mercaptophenyl) sulfonium, diphenyl (p-methylsulfonylphenyl) sulfonium, diphenyl (o-benzoylphenyl) sulfonium, diphenyl (p-methylsulfonylphenyl) (P-cyclohexylphenyl) sulfonium, diphenyl (p-methoxyphenyl) sulfonium, diphenyl (p- (P-phenylsulfanylphenyl) sulfonium, (7-methoxy-2-oxo-2H-chromen-4-yl) sulfonium, diphenyl (omethoxycarbonylphenyl) (4-methoxynaphthalen-1-yl) diphenylsulfonium, diphenyl (p-isopropoxycarbonylphenyl) sulfonium, diphenyl (2-naphthyl) (P-tolyl) sulfonium, diisopropyl (4-phenylsulfanyl) sulfonium, diethyl Phenyl) sulfonium, diphenyl (2-thienyl) sulfonium, diphenyl (2-furyl) sulfonium and diphenyl (9-ethyl-9Hcarbazol- But it is not limited to these.

Onium cation (sulfomethionium cation) corresponding to the general formula (5):

(P-cyanophenyl) sulfone, dimethyl (p-bromophenyl) sulfoxonium, dimethyl (p-cyanophenyl) sulfone, dimethyl (Pentafluorophenyl) sulfoxonium, dimethyl (p- (trifluoromethylphenyl) sulfone, dimethyl (p-nitrophenyl) sulfoxonium, (P-methylphenyl) sulfoxonium, dimethyl (p-methylphenyl) sulfoxonium, dimethyl (p-hydroxyphenyl) sulfoxonium, (P-methylphenyl) sulfoxonium, dimethyl (p-isopropylphenyl) sulfoxonium, dimethyl (p-isopropylphenyl) sulfoxonium, (P-cyclohexylphenyl) sulfoxonium, dimethyl (p-octadecylphenyl) sulfoxonium, dimethyl (p-cyclohexylphenyl) sulfoxonium, dimethyl (P-phenylsulfanylphenyl) sulfoxonium, ( (4-methoxynaphthalen-1-yl) dimethyl sulfoxonium, dimethyl (p-isopropoxycarbonylphenyl) (2-naphthyl) sulfoxonium, dimethyl (9-anthryl) sulfoxonium, diethylphenylsulfoxonium, methylethylphenylsulfoxonium, methyldiphenyl sulfoxonium, (4-phenylsulfanyl-phenyl) sulfoxonium, 4,4'-bis (diphenylsulfoxonium) diphenylsulfide, 4,4'- Bis (diphenylsulfoxonium) biphenylene, diphenyl (o (phenyl) sulfone] diphenyl sulfide, 4,4'-bis (P-chlorophenyl) sulfoxonium, diphenyl (p-cyanophenyl) sulfoxonium, diphenyl (p- (triphenylphosphine) sulfone, diphenyl (p-triflate), triphenylphosphine (triphenylphosphine) (P-methoxyphenyl) sulfoxonium, diphenyl (p-methoxyphenyl) sulfoxonium, diphenyl (p-hydroxyphenyl) sulfoxonium, diphenyl (O-benzoylphenyl) sulfoxonium, diphenyl (p-methylphenyl) sulfoxonium, diphenyl (o-acetylphenyl) sulfoxonium, diphenyl (p-isopropylphenyl) sulfoxonium, diphenyl (p-octadecylphenyl) sulfoxonium, diphenyl (p-cyclohexylphenyl) sulfoxonium, diphenyl Diphenyl (p-phenylsulfanylphenyl) sulfoxonium, (7-methoxy-2-oxo-2H-chromen-4-yl) diphenyl (4-methoxynaphthalen-1-yl) diphenylsulfoxonium, diphenyl (p-isopropoxycarbonylphenyl) sulfoxonium, diphenyl (2-naphthyl) sulfoxonium, di (P-tolyl) sulfoxonium, methyl (p-tolyl) sulfoxonium, methyl (p-tolyl) sulfoxonium, (2-thienyl) sulfoxonium, diphenyl (2-furyl) sulfoxonium, diphenyl (9-ethyl-9H-carbaldehyde, 3-yl) sulfoxonium, and the like, but the present invention is not limited thereto.

Onium cation (Phosphonium cation) corresponding to the general formula (6):

Examples of phosphonium cation:

(P-fluorophenyl) phosphonium, triphenyl (o-chlorophenyl) phosphonium, triphenyl (m-bromophenyl) phosphonium (P-cyanophenyl) phosphonium, triphenyl (m-nitrophenyl) phosphonium, triphenyl (p-phenylsulfanylphenyl) phosphonium, (7-methoxy- (O-acetylphenyl) phosphonium, triphenyl (m-benzoylphenyl) phosphonium, triphenyl (o-hydroxyphenyl) phosphonium, Triphenyl (triphenylphosphine) phosphonium, triphenyl (p-isopropoxyphenyl) phosphonium, triphenyl (o-methoxycarbonylphenyl) (9-ethyl-9Hcarbazol-3-yl) phosphonium, and the like can be given. Limited The.

Onium cation (Pyridinium Cation) corresponding to the general formula (7):

Examples of pyridinium cation:

N-phenylpyridinium, N- (o-chlorophenyl) pyridinium, N- (m-chlorophenyl) , N- (p-acetylphenyl) pyridinium, N- (p-isopropylphenyl) pyridinium, N- 1-phenylpyridinium, 2-methyl-1-phenylpyridinium, 2-vinyl-1-phenyl Phenyl-1-phenylpyridinium, 2-methoxy-1-phenylpyridinium, 2-phenoxy-1-phenylpyridinium, 2- (p-tolyl) pyridinium, 2-methoxycarbonyl-1- (p-tolyl) , N-methylpyridinium, N-ethylpyridinium, and the like, but are not limited thereto.

Onium cation (Quinolinium cation) corresponding to the general formula (8):

Examples of quinolinium cations:

(O-chlorophenyl) quinolinium, N- (m-chlorophenyl) quinolinium, N- Quinolinium, N- (p-cyanophenyl) quinolinium, N- (p-cyanophenyl) quinolinium, N- (P-methoxycarbonylphenyl) quinolinium, N- (9-anthryl) quinolinium, 2-chloro-1-phenyl 1-phenylquinolinium, 2-phenyl-1-phenylquinolinium, 1-phenylquinolinium, 2-phenyl-1-phenylquinolinium, , 2-diphenylquinolinium, 2-methoxy-1-phenylquinolinium, 2-phenoxy-1-phenylquinolinium, 2-acetyl-1-phenylquinolinium, 2-methoxycarbonyl 1-phenylquinolinium, 2-methoxy-1- (p-tolyl) quinolinium, 2-phenoxyquinolinium, 2-acetyl-1- (2-thienyl) quinolinium, 2-methoxycarbonyl-1-methylquinolinium, 3- Oro-1-ethyl-quinolinyl titanium, and the like, but 4-methyl-1-isopropyl-quinolinyl titanium, but is not limited to these.

Onium cateoin (isoquinolinium cate ion) corresponding to the general formula (9):

Examples of isoquinolinium cateons:

N-phenylisoquinolinium, N-phenylisoquinolinium, N-methylisoquinolinium, N-ethylisoquinolinium, N- (o- chlorophenyl) isoquinolinium, N- Isoquinolinium, N- (p-cyanophenyl) isoquinolinium, N- (p-cyanophenyl) (P-methoxycarbonylphenyl) isoquinolinium, N- (9-anthryl) isoquinolinium, 1, (2-thienyl) isoquinolinium, N-naphthylisoquinolinium, and the like can be given. Among these, But is not limited thereto.

Onium cation (benzooxazolium cation, benzothiazolium cation) corresponding to the general formula (10):

Examples of benzooxazolium cation:

(P-fluorophenyl) benzooxazolium, N- (p-chlorophenyl) benzooxazolium, N-methylbenzooxazolium, N- Benzooxazolium, N- (p-cyanophenyl) benzoxazolium, N- (o-methoxycarbonylphenyl) benzoxazolium, N- Phenylphenyl) benzoxazolium, N- (p-cyanophenyl) benzoxazolium, N- (m-nitrophenyl) benzoxazolium, N- (p-isopropoxycarbonylphenyl) benzoxazolium, N- 3-phenylbenzoxazolium, 2-methyl-3-phenylbenzoxazolium, 2-methylthio-3 (2-methylthio) benzooxazolium, - (4-phenylsulfanylphenyl) benzoxazolium, 6-hydroxy-3- (p-tolyl) benzoxazolium, 7-mercapto-3-phenylbenzoxazolium, 4,5- -Ethylbenzoxazolium, and the like, but are not limited thereto.

Examples of benzothiazolium cation:

N-methylbenzothiazolium, N-ethylbenzothiazolium, N-phenylbenzothiazolium, N- (1-naphthyl) benzothiazolium, N- (p-fluorophenyl) benzothiazolium, N- (P-cyanophenyl) benzothiazolium, N- (o-methoxycarbonylphenyl) benzothiazolium, N- (p- tolyl) benzothiazolium, N- N- (2-furyl) benzothiazolium, N (p-isopropoxycarbonylphenyl) benzothiazolium, N- (4-methylthiophenyl) benzothiazolium, N- (4-phenylsulfanylphenyl) benzothiazolium, N- (2-naphthyl) benzothiazolium, N- 2-methyl-3-phenylbenzothiazolium, 6-hydroxy-3-phenylbenzothiazolium, 7-mercury-3-phenylbenzothiazolium, 3-phenylbenzothiazolium, 4,5-difluoro-3-phenylbenzothiazolium, and the like, but are not limited thereto All.

Onium cation (furyl or thienyl iodonium cation) corresponding to the general formula (11):

(5-chloro-2-thienyl) iodonium, bis (5-cyano-2-furyl) iodonium, bis Iodonium, bis (5-nitro-2-thienyl) iodonium, bis (5-acetyl- Iodonium, bis (5-phenyl-2-furyl) iodonium, bis (5-methoxyphenyl) Iodonium, bis (5-hydroxy-2-thienyl) iodonium, bis (2-furyl) Iodonium, bis (5-phenylthio-2-thienyl) iodonium, bis (5-phenoxy- Thio-2-thienyl) iodonium, and the like, but are not limited thereto.

Onium cation (diaryl iodonium cation) corresponding to the general formula (12):

(P-octylphenyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octylphenyl) iodonium, (4-isopropylphenyl) iodonium, phenyl (p-octadecyloxyphenyl) iodonium, 4-isopropyl-4'- methyldiphenyliodonium, Iodonium, 1-naphthyl) iodonium, bis (4-phenylsulfanylphenyl) iodonium, phenyl (6-benzoyl- Oxo-2H-chromen-3-yl) -4'-isopropylphenyliodonium, and the like.

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 is preferably an anion-nucleophilic anion. In the case of the counteranion X ^- in the case of the non-nucleophilic anion, it is difficult for the nucleophilic reaction to occur in various materials to be used together with cationic coexisting in the molecule. As a result, the photoacid generator itself represented by the general formula (3) It is possible to improve the time-course stability of the composition using it. The non-nucleophilic anion, as used herein, refers to anion with 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.

Of the above exemplified anions, PF ₆ ^- , SbF ₆ ^- , and AsF ₆ ^- are particularly preferable as the counter anion X ^- in the general formula (3), and particularly preferable examples thereof include PF ₆ ^- SbF ₆ ^- .

Therefore, specific examples of preferable onium salts constituting the photoacid generator (C) of the present invention include the specific examples of the structure of the onium cation represented by the general formulas (3) to (12) and PF ₆ ^- , SbF _{Is an} onium salt comprising an anion selected from the group consisting of ₆ ^- , AsF ₆ ^- , SbCl ₆ ^- , BiCl ₅ ^- , SnCl ₆ ^- , ClO ₄ ^- , dithiocarbamate anion and SCN ^- .

Concretely, "SAIRACURE UVI-6992", "SAIRACURE UVI-6974" (manufactured by Dow Chemical Co., Ltd.), "Adeka Optomer SP150", "Adeka Optomer SP152" CI-2855 " (manufactured by NIPPON SODA CO., LTD.) (Trade name, manufactured by Nippon Soda Co., Ltd.), " DECA OPTOMER SP170 ", " ADEKA OPTOMER SP172 " San Aid SI-180L "(manufactured by SANSHIN CHEMICAL INDUSTRIES, LTD.)," SANEADE SI-80L "," SANEADE SI-80L " CPI-100P, CPI-100A, WPI-069, WPI-113, WPI-116, WPI-041, WPI- WPAG-567 ", and" WPAG-596 "(all manufactured by Wako Pure Chemical Industries, Ltd.) are added to the preferred specific examples of the photoacid generator (C) .

The content of the photoacid generator (C) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, further preferably 0.1 to 3 parts by weight, based on the total amount of the active energy ray curable adhesive composition, And particularly preferably 0.8 to 2 parts by weight.

In addition, in the active energy ray-curable adhesive composition according to the present invention, in addition to the above photo-radical generating agent, a sensitizer for increasing the curing speed and sensitivity by electron beams represented by carbonyl compounds and the like may be added.

Examples of the sensitizer include anthracene, phenothiazine, perylene, thioxanthone, benzophenantioxanthone, and the like. Examples of the sensitizing dye include thiopyrylium salt dye, merocyanine dye, quinoline dye, styrylquinoline dye, ketokmarine dye, thioxanthate dye, xanthene dye, oxolin dye, cyanine dye Pigments, rhodamine-based pigments, pyrylium-based pigments, and the like.

Specific examples of the anthracene compound include dibutoxyanthracene and dipropoxyanthraquinone (Anthracure UVS-1331, 1221, manufactured by Kawasaki Chemical Co., Ltd.).

When the sensitizer is added, the content thereof is preferably 0.01 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, particularly preferably 0.1 to 3 parts by weight, based on the total amount of the active energy ray curable adhesive composition .

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 amino silane coupling agent (D1) and an alkylated urea (D2). Of these, the alkoxyl group-containing aminosilane coupling agent (D1) is particularly preferably usable from the viewpoint of improving the water resistance and adhesion of the adhesive layer. Further, 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 alkoxyl group-containing aminosilane coupling agent (D1) include N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) -3-aminopropyltrimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl- Aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltriethoxysilane , 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane , Imidazole silane, and the like. 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, the content of the alkoxy group-containing aminosilane coupling agent (D1) is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of the radical polymerizable compound (A) More preferably 0.2 to 12 parts by weight, and still more preferably 0.5 to 3 parts by weight.

In the present invention, in addition to the alkoxyl 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- 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane , 3-acryloxypropyltrimethoxysilane, or the like may be used in combination.

Examples of the alkylated urea (D2) include those having an alkyl group such as methylol and ethylol, an alkoxyalkyl group such as methoxymethyl and ethoxymethyl, an alkyl group and / or a hydrogen atom on the nitrogen atom of urea. The content of the alkylated urea (D2) is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the total amount of the radical polymerizable compound (A) More preferably from 1 to 15 parts by weight, and particularly preferably from 8 to 12 parts by weight.

As the alkylated urea (D2), commercially available products are also preferably used, and examples thereof include NIKARAK MX-270, NIKARAK MX280 and NIKARAK MX-290 manufactured by Sanwa Chemical Co., The alkylated urea (D2) may be a resinized (urea resin).

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

In the active energy ray-curable adhesive composition according to the present invention, various additives may be added as other arbitrary components in the range not impairing the purpose and effect of the present invention. Examples of such additives include polyamides, polyamideimides, polyurethanes, polybutadienes, polychloroprenes, polyethers, polyesters, styrene-butadiene block copolymers, petroleum resins, xylene resins, ketone resins, Polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol, polymerization initiators, leveling agents, wettability improvers, surfactants, A plasticizer, an ultraviolet absorber inorganic filler, a pigment, and a dye. However, the content of the above-described additives in the active energy ray-curable adhesive composition is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight based on the total amount of the active energy ray- Particularly preferable is a weight part.

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

In the electron beam hardening type, the irradiation condition of the electron beam may be any appropriate condition as long as the condition is such that the active energy ray hardening type 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. When the acceleration voltage is less than 5 kV, the electron beam does not reach the cured layer and the curing may be insufficient. When the acceleration voltage exceeds 300 kV, the penetration force through the specimen is too strong and the electron beam splashes, It may cause 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 dropping layer becomes insufficient in curing. When the irradiation dose exceeds 100 kGy, damage to each member is given to decrease mechanical strength and yellowing, and desired optical characteristics can not be obtained.

The electron beam irradiation is usually carried out in an inert gas atmosphere, but it may be carried out under a condition where air or oxygen is slightly introduced, if necessary. Although oxygen depending on the material of the member to be laminated is suitably introduced, oxygen can be inhibited forcibly on the surface of the member which is first contacted by the electron beam, so that damage to this member can be prevented, .

On the other hand, in the ultraviolet curing type, when a member having an ultraviolet ray absorbing ability to absorb light having a shorter wavelength than 380 nm is used, light having a shorter wavelength than 380 nm does not reach the active energy ray curable adhesive composition and contributes to the polymerization reaction I never do that. Further, the light having a wavelength shorter than 380 nm absorbed by this member is converted into heat, and this member itself generates heat, which causes defects such as curling and wrinkling of the laminate which provides such a member. Therefore, when the ultraviolet curing type is employed in the present invention, it is preferable to use an apparatus which does not emit light having a shorter wavelength than 380 nm as the ultraviolet ray generating apparatus, and more specifically, And the integrated illuminance in the wavelength 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 the relationship of the integrated illuminance, a gallium-encapsulated metal halide lamp and an LED light source emitting light in a wavelength range of 380 to 440 nm are preferable. Alternatively, the light source may be a metal halide lamp, a fluorescent lamp, a tungsten lamp, a gallium lamp, an excimer laser or solar light as a light source, such as a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, an incandescent lamp, a xenon lamp, a halogen lamp, It is also possible to cut off light of a shorter wavelength than 380 nm by using a pass filter.

The adhesive layer obtained in the present invention is obtained by irradiating the active energy ray-curable adhesive composition with active energy rays. By laminating at least two members with such an adhesive layer interposed therebetween, various laminated bodies can be produced. Hereinafter, as an example of a laminate, an example of a polarizing film in which a transparent protective film is formed on at least one surface of a polarizer with an adhesive layer interposed therebetween is shown. In the polarizing film, the adhesive layer is formed by a cured layer formed by irradiating the 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 an adhesive layer of various laminated bodies other than the polarizing film, and is not limited to a polarizing film.

The curable component (radically polymerizable compound (A) other than the alkoxy group-containing amino compound (D)) used in the active energy ray-curable adhesive composition is selected so that the Tg of the adhesive layer thus formed is 20 ° C or higher, It is preferable. In view of durability, it is preferable that the temperature is 50 DEG C or higher, more preferably 60 DEG C or higher, further 70 DEG C or higher, and furthermore, 85 DEG C or higher. On the other hand, the Tg of the cured layer is preferably 120 占 폚 or lower, more preferably 110 占 폚 or lower, further preferably 100 占 폚 or lower, because the flexibility of the polarizing film is lowered when the Tg of the cured layer is too high.

The cured layer formed by the active energy ray-curable adhesive composition has higher durability than the water-based adhesive layer. When it is used for a polarizing film, it is preferable to use an adhesive layer having a Tg of 20 DEG C or more and to control the thickness of the adhesive layer to be 300 nm to 1 mu m. When the thickness of the adhesive layer is thinner than 300 nm, the cohesive force of the adhesive force itself can not be obtained, and the adhesive strength may not be obtained. On the other hand, if the thickness of the adhesive layer exceeds 1 탆, the water resistance of the polarizing film may deteriorate.

In the polarizing film related to the present invention, a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm is formed on at least one surface of a polarizer through an adhesive layer. In particular, since the adhesive layer is formed by a cured layer formed by irradiating an active energy ray to the above-mentioned active energy ray curable adhesive composition, the adhesive property between the polarizer and the transparent protective film is excellent and the water resistance is excellent Do.

A method for producing a polarizing film, which can preferably use the active energy ray-curable adhesive composition according to the present invention, will be described below.

A production method of a polarizing film according to the present invention is a production method of a polarizing film in which a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm is formed on at least one surface of a polarizer through an adhesive layer, An application step of applying the active energy ray-curable adhesive composition described above to at least one surface of the transparent protective film, an adhesion step of bonding the polarizer and the transparent protective film, and a step of applying an active energy ray from the side of the polarizer surface or the transparent protective film And adhering the polarizer and the transparent protective film to each other through the adhesive layer obtained by irradiating the active energy ray-curable adhesive composition and curing the active energy ray ray-curable adhesive composition.

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, a corona treatment, a plasma treatment, a frame treatment, or an excimer treatment may be applied to at least one side of the polarizer or the transparent protective film on the side to which the active energy ray curable adhesive composition is applied.

The coating method usable in the application step of the active energy ray-curable adhesive composition is appropriately selected depending on the viscosity of the composition and the desired thickness. Examples of the coating method include a reverse coater, a gravure coater (direct, reverse or offset), a varibus coater, a roll coater, a die coater, a bar coater and a rod coater. In addition, a coating method such as a dipping method can be suitably used.

The polarizer and the transparent protective film are bonded to each other through the adhesive thus applied (bonding step). The polarizer and the transparent protective film can be bonded by a roll laminator or the like.

After the polarizer and the transparent protective film are laminated, an active energy ray (electron beam, ultraviolet ray, or the like) is irradiated, and the active energy ray curable adhesive composition is cured to form an adhesive layer. The irradiation direction of the active energy ray (electron beam, ultraviolet ray, etc.) can be irradiated from any appropriate direction. Preferably, it is irradiated from the side of the transparent protective film. When irradiated from the side of the polarizer, there is a fear that the polarizer is deteriorated by an active energy ray (electron beam, ultraviolet ray, or the like).

In the case of producing the polarizing film according to the present invention as a continuous line, the line speed varies depending on the curing time of the adhesive, but is preferably 1 to 500 m / min, more preferably 5 to 300 m / min, Is 10 to 100 m / min. When the line speed is too small, a polarizing film which can not withstand a durability test or the like can not be produced because the productivity is insufficient or the damage to the transparent protective film is too large. If the line speed is too large, the curing of the adhesive becomes insufficient, and the desired adhesiveness may not be obtained.

As described above, when the photoacid generator (C) and the amino group-containing amino compound (D) coexist in the active energy ray-curable adhesive composition, the reaction between the amino group in the alkoxy group-containing amino compound (D) At the same time, the alkoxy group in the alkoxy group-containing amino compound (D) is hydrolyzed by moisture to form a reactive hydroxyl group. As a result, the reactive hydroxyl group in the alkoxy group-containing amino compound (D) can form a hydrogen bond and / or a covalent bond with a hydroxyl group existing on the surface of the polarizer. In the present invention, in the case of having the heating step during or after the irradiation with the active energy ray in the adhering step, the hydrolysis reaction of the alkoxy group in the alkoxy group-containing amino compound (D) And the hydroxyl group present on the surface of the polarizer are promoted to form a hydrogen bond and / or a covalent bond. This makes it possible to produce a polarizing film having an adhesive layer whose water resistance is remarkably improved.

In the method for producing a polarizing film, it is preferable that the water content of the polarizer in the bonding step is less than 15%. According to such a manufacturing method, a polarizing film having an adhesive layer that is excellent in adhesion between a polarizer and a transparent protective film and excellent in durability and water resistance of an adhesive layer while reducing a drying load of a polarizing film obtained after an adhesion process (lamination) Can be prepared.

In the polarizing film of the present invention, the polarizer and the transparent protective film are adhered via the adhesive layer formed by the cured layer of the active energy ray-curable adhesive composition. However, between the transparent protective film and the adhesive layer, Layer can be formed. The adhesion facilitating layer can be formed by various resins having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a silicone type, a polyamide skeleton, a polyimide skeleton, and a polyvinyl alcohol skeleton, for example . These polymer resins may be used singly or in combination of two or more. Further, other additives may be added to form the adhesion-facilitating layer. Specifically, stabilizers such as a tackifier, ultraviolet absorber, antioxidant, heat stabilizer and the like may be used.

The easy-to-adhere layer is usually formed in advance on a transparent protective film, and the easy-to-adhere side of the transparent protective film and the polarizer are bonded together by the adhesive layer. The easy-to-adhere layer is formed by applying the forming material of the easy-to-adhere layer onto a transparent protective film by a known technique and drying it. The forming material of the easy-to-adhere layer is usually adjusted as a solution diluted to an appropriate concentration in consideration of the thickness after drying, the original activity of the coating, and the like. The thickness of the facilitating layer after drying is preferably 0.01 to 5 占 퐉, more preferably 0.02 to 2 占 퐉, and still more preferably 0.05 to 1 占 퐉. Further, although a plurality of layers can be formed for facilitating the adhesion, it is preferable that the total thickness of the easy-to-adhere layer is also 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 with an adhesive layer formed by a cured layer of the active energy ray-curable adhesive composition interposed therebetween.

The polarizer is not particularly limited and various kinds of polarizers can be used. As the polarizer, for example, a hydrophilic polymer film such as a polyvinyl alcohol film, a partially porous polyvinyl alcohol film, or an ethylene / vinyl acetate copolymerization system partial saponification film is used to adsorb a dichroic material such as iodine or a dichromatic dye And polyene-based oriented films such as polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochloric acid treated products. Among them, a polarizer comprising a polyvinyl alcohol film and a dichromatic material such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 80 占 퐉 or less.

A polarizer obtained by dying a polyvinyl alcohol film with iodine and uniaxially stretching can be produced by, for example, dying polyvinyl alcohol in an aqueous solution of iodine and stretching it to 3 to 7 times its original length. If necessary, it may be immersed in an aqueous solution of boric acid, potassium iodide or the like. If necessary, the polyvinyl alcohol film may be dipped in water and washed with water before dyeing. The polyvinyl alcohol film is washed with water to clean the surface of the polyvinyl alcohol film and to prevent unevenness such as uneven dyeing by swelling the polyvinyl alcohol film. The stretching may be carried out after dyeing with iodine, followed by stretching while dyeing, or after stretching, followed by dyeing with iodine. It can be stretched in an aqueous solution such as boric acid or potassium iodide or in a water bath.

As the polarizer, a thin polarizer having a thickness of 10 占 퐉 or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 mu m. Such a thin polarizer is preferable because it is excellent in durability because thickness irregularity is small, visibility is excellent, and a dimensional change is small, and further thickness and thickness of a polarizing film are achieved.

Typical examples of the thin polarizer include those disclosed in Japanese Laid-Open Patent Publication Nos. 51-069644 and 2000-338329, pamphlets of WO2010 / 100917, PCT / JP2010 / 001460, and Japanese Patent Application No. 2010-269002 And a thin polarizing film described in the specification of Japanese Patent Application No. 2010-263692. These thin polarizing films can be obtained by a process comprising a step of stretching a layer of a polyvinyl alcohol resin (hereinafter also referred to as a PVA resin) and a lead resin base material in the form of a laminate, and a step of dyeing. With this method, even if the PVA resin layer is thin, it can be stretched without any problem such as breakage due to stretching because it is supported on the resin base material for drawing.

The thin polarizing film described in WO2010 / 100917 pamphlet, PCT / JP2010 / 01107, and the like can be used as the thin polarizing film in that the film can be stretched at a high magnification even in a process including a stretching process and a dyeing process in the state of a laminate, In a boric acid aqueous solution as described in Specification of Japanese Patent Application No. 2002-69002 or Specification of Japanese Patent Application No. 2010-269002 or Specification of Japanese Patent Application No. 2010-263692, and in particular, Japanese Patent Application No. 2010-269002 It is preferably obtained by a process including a step of auxiliary drawing publicly before drawing in an aqueous boric acid solution described in the specification or Japanese Patent Application No. 2010-263692.

The thin functional high-performance polarizing film described in the specification of PCT / JP2010 / 001460 is a thin, highly functional polarizing film having a thickness of 7 탆 or less and made of a PVA-based resin in which a dichromatic substance is aligned, Of 42.0% or more and a polarization degree of 99.95% or more.

The thin functional high-polarizability film is produced by applying a PVA resin to a resin base material having a thickness of at least 20 mu m to produce a PVA-based resin layer and immersing the resulting PVA-based resin layer in a dyeing solution of a dichroic substance , The PVA resin layer in which the dichroic substance is adsorbed to the PVA resin layer and the dichroic substance is adsorbed is stretched in the aqueous solution of boric acid together with the resin base so that the total draw ratio becomes 5 times or more the original length, Can be manufactured.

Also disclosed is a method for producing a laminated film comprising a thin functional high polarizing film in which a dichroic substance is oriented, comprising the steps of: applying a resin substrate having a thickness of at least 20 탆 and an aqueous solution containing a PVA- And a PVA resin layer formed on one side of the resin base material is immersed in a dyeing solution containing a dichroic substance so as to obtain a laminate film comprising a PVA resin layer, A step of adsorbing the dichroic substance to the PVA resin layer contained in the laminate film and a step of forming the laminated film including the PVA resin layer on which the dichroic substance is adsorbed by the adsorption of the dichroic substance in the aqueous boric acid solution And a step of stretching the PVA resin layer in which the dichroic substance is adsorbed so as to be at least 5 times the original length, A laminated film comprising a PVA-based resin layer having a dichroic substance oriented on one side and having a thickness of 7 탆 or less, a single-layer polarizing film having a single light transmittance of 42.0% or more and a polarization degree of 99.95% The thin, highly functional polarizing film can be produced.

The above-mentioned Japanese Patent Application No. 2010-269002 specification or Japanese Patent Application No. 2010-263692 specification

The thin polarizing film is a polarizing film of a continuous web made of a PVA-based resin in which a dichroic material is oriented, wherein a laminate including a PVA-based resin layer formed on a noncrystalline ester-based thermoplastic resin base is subjected to air- , And the thickness is 10 mu m or less. Such a thin polarizing film has P> - (100.929 T - 42.4 - 1) x 100 (where T <42.3) and P ≥99.9 (however, T ≥ 42.3) when the simple transmittance is T and the polarization degree is P It is preferable that the optical element has an optical characteristic that satisfies the condition.

Specifically, the thin polarizing film is a step of producing a drawn intermediate product comprising a PVA-based resin layer oriented by public high-temperature stretching to a PVA-based resin layer formed on a noncrystalline ester-based thermoplastic resin base material of a continuous web And a PVA-based resin layer in which a dichroic substance (preferably a mixture of iodine or iodine and an organic dye) is oriented by adsorption of a dichroic substance to the drawn intermediate product, And a step of producing a polarizing film having a thickness of 10 占 퐉 or less and comprising a PVA-based resin layer in which a dichroic substance is oriented by stretching boric acid in water to an intermediate product.

In this production method, it is preferable that the total draw ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin base material by public high-temperature stretching and boric acid in-water stretching is 5 times or more. The temperature of the boric acid aqueous solution for boric acid aqueous in-water elongation may be 60 占 폚 or higher. It is preferable to carry out the insolubilization treatment with respect to the colored intermediate before drawing the colored intermediate in the aqueous solution of boric acid. In this case, the colored intermediate is preferably immersed in an aqueous solution of boric acid whose solution temperature does not exceed 40 캜 desirable. The amorphous ester-based thermoplastic resin base material may be a copolymerized polyethylene terephthalate copolymerized with isophthalic acid, a copolymerized polyethylene terephthalate copolymerized with cyclohexane dimethanol, or an amorphous polyethylene terephthalate containing other copolymerized polyethylene terephthalate. The thickness of the PVA resin layer is preferably 7 times or more the thickness of the PVA resin layer to be produced. The stretching magnification of the air high-temperature stretching is preferably 3.5 times or less, and the stretching temperature of the public high-temperature stretching is preferably not lower than the glass transition temperature of the PVA-based resin, specifically 95 ° C to 150 ° C. It is preferable that the total draw ratio of the PVA resin layer formed on the amorphous ester based thermoplastic resin base material is not less than 5 times but not more than 7.5 times as long as the air high temperature stretching is performed by free uniaxial stretching. When the public high-temperature stretching is carried out by a fixed single uniaxial stretching, the total stretching magnification of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin base material is preferably 5 times or more and 8.5 times or less.

More specifically, a thin polarizing film can be produced by the following method.

A substrate of continuous web of isophthalic acid copolymerized polyethylene terephthalate (amorphous PET) in which 6 mol% of isophthalic acid is copolymerized is prepared. The amorphous PET has a glass transition temperature of 75 ° C. A laminate composed of a non-crystalline PET substrate and a polyvinyl alcohol (PVA) layer of a continuous web is produced as follows. In addition, the glass transition temperature of PVA is 80 ° C.

An amorphous PET substrate having a thickness of 200 탆 and a PVA aqueous solution having a polymerization degree of 1000 or more and a PVA powder having a degree of saponification of 99% or more dissolved in water at a concentration of 4 to 5% are prepared. Next, a PVA aqueous solution is applied to the amorphous PET substrate having a thickness of 200 mu m and dried at a temperature of 50 to 60 DEG C to obtain a laminate in which a PVA layer having a thickness of 7 mu m is formed on the amorphous PET substrate.

A laminate including a PVA layer having a thickness of 7 占 퐉 is subjected to the following steps including a two-step stretching process of air-assisted stretching and boric acid in-water stretching to prepare a thin, highly functional polarizing film having a thickness of 3 占 퐉. The laminate including the PVA layer having a thickness of 7 占 퐉 is integrally stretched with the amorphous PET substrate by the air assisted stretching process of the first stage to produce a stretched laminate including the PVA layer having a thickness of 5 占 퐉. Specifically, this stretched laminate was obtained by laminating a laminate including a PVA layer having a thickness of 7 탆 on a stretching device arranged in an oven set at a stretching temperature of 130 캜, It is an extension. By this stretching treatment, the PVA layer contained in the stretched laminate is changed to a PVA layer having a thickness of 5 탆 in which the PVA molecules are oriented.

Next, a colored layered product in which iodine is adsorbed to a PVA layer having a thickness of 5 占 퐉 in which PVA molecules are oriented is produced by a dyeing step. Specifically, this colored laminate is obtained by laminating the drawn laminate to a dyeing solution containing iodine and potassium iodide at a liquid temperature of 30 占 폚 in such a manner that the ultraviolet transmittance of the PVA layer constituting the ultimately produced functional polarizing film is 40 to 44% So that the iodine is adsorbed on the PVA layer contained in the drawn laminate. In the present step, the dyeing solution is prepared so that the concentration of iodine is within a range of 0.12 to 0.30% by weight, and the concentration of potassium iodide is within a range of 0.7 to 2.1% by weight with water as a solvent. The ratio of iodine to potassium iodide is 1 to 7. In addition, potassium iodide is required to dissolve iodine in water. More specifically, the drawn laminate was immersed 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 to obtain a colored laminate in which iodine was adsorbed on a PVA layer having a thickness of 5 탆 .

Further, the colored laminate is further stretched integrally with the amorphous PET substrate by a boric acid in-water stretching step of the second stage to produce an optical film laminate including a PVA layer constituting an advanced polarizing film having a thickness of 3 占 퐉. Specifically, this optical film laminate is obtained by laminating a colored laminate to a stretching device which is arranged in a treating device set in an aqueous boric acid solution containing boric acid and potassium iodide in a liquid temperature range of 60 to 85 캜, to give a draw ratio of 3.3 It is stretched to the free end single axis. More specifically, the liquid temperature of the aqueous boric acid solution is 65 캜. It is also made such that the content of boric acid is 4 parts by weight with respect to 100 parts by weight of water, and the content of potassium iodide is 5 parts by weight with respect to 100 parts by weight of water. In the present step, the colored laminate having the iodine adsorption amount adjusted is first immersed in an aqueous solution of boric acid for 5 to 10 seconds. Thereafter, the colored layered product is directly passed through a plurality of sets of rolls whose principal axes are different from that of the oriented device, which is a device oriented in the processing apparatus, and is uniaxially stretched so that the draw ratio becomes 3.3 times over 30 to 90 seconds. By this stretching treatment, the PVA layer contained in the colored laminate is changed to a PVA layer having a thickness of 3 占 퐉 in which iodine adsorbed is highly oriented in one direction as a polyiodide ion complex. This PVA layer constitutes a highly functional polarizing film of the optical film laminate.

The optical film laminate is taken out from the aqueous boric acid solution by a washing step and the boric acid attached to the surface of the 3 mu m thick PVA layer formed on the amorphous PET substrate is treated with potassium iodide It is preferable to wash it with an aqueous solution. Thereafter, the washed optical film laminate is dried by a drying process by hot air at 60 캜. The cleaning process is a process for eliminating appearance defects such as boric acid precipitation.

The adhesive is applied to the surface of the 3 占 퐉 -thick PVA layer formed on the amorphous PET substrate by the bonding and / or transferring process, while it is not essential for the production of the optical film laminate, After the triacetyl cellulose film is laminated, the amorphous PET substrate is peeled off, and a PVA layer having a thickness of 3 占 퐉 may be transferred to a triacetyl cellulose film having a thickness of 80 占 퐉.

[Other processes]

The thin polarizing film manufacturing method may include other steps besides the above-described steps. Examples of the other steps include an insolubilization step, a crosslinking step, and a drying step (controlling the water content). Other processes can be carried out at any appropriate timing.

The above-mentioned insolubilization step is typically performed by immersing a PVA-based resin layer in an aqueous solution of boric acid. By carrying out the insolubilization treatment, it is possible to impart water resistance to the PVA-based resin layer. The concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight based on 100 parts by weight of water. The solution temperature of the insolubilizing bath (boric acid aqueous solution) is preferably 20 ° C to 50 ° C. Preferably, the insolubilization step is carried out after the laminate is produced, before the dyeing step or the underwater stretching step.

Typically, the crosslinking step is carried out by immersing the PVA resin layer in an aqueous solution of boric acid. By carrying out the crosslinking treatment, it is possible to impart water resistance to the PVA-based resin layer. The concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight based on 100 parts by weight of water. Further, in the case of performing the crosslinking step after the dyeing step, it is preferable to further add iodide. By combining iodide, the elution of iodine adsorbed to the PVA-based resin layer can be suppressed. The blending amount of iodide is preferably 1 part by weight to 5 parts by weight based on 100 parts by weight of water. Specific examples of the iodide are as described above. The temperature of the crosslinking bath (boric acid aqueous solution) is preferably 20 占 폚 to 50 占 폚. Preferably, the crosslinking step is carried out before the stretching step in the second boric acid water. In a preferred embodiment, the dyeing step, the crosslinking step and the second boric acid in water step are carried out in this order.

The transparent protective film formed on one side or both sides of the polarizer preferably has excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like, and particularly preferably has a moisture permeability of 150 g / m 2/24 h or less More preferably 140 g / m 2/24 h or less, further preferably 120 g / m 2/24 h or less. The moisture permeability is obtained by the method described in the embodiment.

The thickness of the transparent protective film can be suitably determined, but is generally 1 to 500 탆, preferably 1 to 300 탆, and preferably 5 to 200 탆 in terms of workability such as strength and handling properties, More preferable. Further preferably 20 to 200 mu m, and more preferably 30 to 80 mu m.

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 polyamides ; Polyolefin-based polymers such as polyethylene, polypropylene and ethylene-propylene copolymer; cyclic olefin resins having a cyclo or norbornene structure; (meth) acrylic resins; or mixtures thereof. Among these resins, a polycarbonate resin, a cyclic polyolefin resin, and a (meth) acrylic resin are preferable, and a cyclic polyolefin resin and a (meth) acrylic resin are particularly preferable.

Specific examples of the cyclic polyolefin resin are preferably norbornene resins. The cyclic olefin-based resin is a generic name of a resin polymerized as a polymerization unit of a cyclic olefin, and examples of the cyclic olefin-based resin include those described in JP-B 1-240517, JP-A 3-14882, JP- 3-122137 and the like. Specific examples include ring-opened (co) polymers of cyclic olefins, addition polymers of cyclic olefins, copolymers of cyclic olefins and? -Olefins such as ethylene and propylene (typically, random copolymers) Graft polymers modified with a carboxylic acid or a derivative thereof, and hydrides thereof. Specific examples of cyclic olefins include norbornene monomers.

As the cyclic polyolefin resin, various products are commercially available. Specific examples include trade names "Zeonex" and "Zeonoa" manufactured by Nippon Zeon Co., Ltd., "Aton" manufactured by JSR Corporation, "Topaz" manufactured by TICONA, and "APEL" manufactured by Mitsui Chemicals, Inc. .

As the (meth) acrylic resin, the Tg (glass transition temperature) is preferably 115 ° C or more, more preferably 120 ° C or more, further preferably 125 ° C or more, particularly preferably 130 ° C or more. By having a Tg of 115 占 폚 or higher, the polarizing film can have excellent durability. The upper limit of the Tg of the (meth) acrylic resin is not particularly limited, but is preferably 170 占 폚 or less from the viewpoint of moldability and the like. (Meth) acryl-based resin, a film in which the in-plane retardation (Re) and the thickness direction retardation (Rth) are substantially zero can be obtained.

As the (meth) acrylic resin, any appropriate (meth) acrylic resin may be employed within the range not hindering the effect of the present invention. Examples thereof include poly (meth) acrylate esters such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylate ester copolymer, methyl methacrylate- (Meth) acrylic acid copolymer, a methyl methacrylate-styrene copolymer (MS resin, etc.), a polymer having an alicyclic hydrocarbon group (for example, methyl methacrylate-cyclohexyl methacrylate copolymer, methyl methacrylate - (meth) acrylate norbornyl copolymer). Preferably, poly (meth) acrylate C1-6 alkyl such as poly (meth) acrylate is exemplified. More preferably, the methyl methacrylate resin having methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight) is exemplified.

As specific examples of the (meth) acrylic resin, there can be mentioned, for example, (Acetipet VH manufactured by Mitsubishi Rayon Co., Ltd., Acryphet VRL20A, and (meth) acrylic resin having a ring structure in the molecule described in Japanese Patent Application Laid- Resins, and high-Tg (meth) acrylic resins obtained by intramolecular crosslinking or intramolecular cyclization.

As the (meth) acrylic resin, a (meth) acrylic resin having a lactone ring structure may be used. High heat resistance, high transparency, and high mechanical strength by biaxial stretching.

Examples of the (meth) acrylic resin having a lactone ring structure are disclosed in JP-A-2000-230016, JP-A-2001-151814, JP-A-2002-120326, JP- (Meth) acryl-based resin having a lactone ring structure described in Patent Publication No. 2005-146084.

The low-moisture-permeability transparent protective film formed on both sides of the polarizer may be a transparent protective film made of the same polymer material on its front and back sides, or a transparent protective film made of a different polymer material or the like.

In the polarizing film, the SP value of the transparent protective film is preferably 29.0 (MJ / m 3) ^1/2 or more and ^less than 33.0 (MJ / m 3) ^1/2 . When the SP value of the transparent protective film is within the above range, the radically polymerizable compound (A) in the active energy ray curable adhesive composition is, for example, hydroxyethyl acrylamide (SP value: 29.6), N-methylol acrylamide Value 31.5) or the like, the adhesiveness between the transparent protective film and the adhesive layer is greatly improved because it is very close to the SP value thereof. As the transparent protective film having an SP value of 29.0 (MJ / m 3) ^1/2 or more and ^less than 33.0 (MJ / m 3) ^1/2 , for example, saponified triacetyl cellulose (for example, SP value 32.7) can be mentioned.

In the polarizing film, the SP value of the transparent protective film is preferably 18.0 (MJ / m 3) ^1/2 or more and ^less than 24.0 (MJ / m 3) ^1/2 . When the SP value of the transparent protective film is within the above range, the radically polymerizable compound (A) in the active energy ray-curable adhesive composition is, for example, acryloylmorpholine (SP value: 22.9), N-methoxymethylacrylamide SP value of 22.9), N-ethoxymethylacrylamide (SP value of 22.3) and the like are very close to their SP values, adhesion between the transparent protective film and the adhesive layer is greatly improved. As the transparent protective film having an SP value of 18.0 (MJ / m 3) ^1/2 or more and ^less than 24.0 (MJ / m 3) ^1/2 , for example, unvarnated triacetylcellulose (SP value 23.3) and acrylic film (SP value 22.2) .

As the transparent protective film, a retardation film having a front retardation of 40 nm or more and / or a retardation in the thickness direction of 80 nm or more can be used. The front retardation is usually in the range of 40 to 200 nm and the retardation in the thickness direction is usually controlled in the range of 80 to 300 nm. When a retardation film is used as the transparent protective film, the retardation film also functions as a transparent protective film, so that it can be thinned.

Examples of the retardation film include a birefringent film obtained by uniaxially or biaxially stretching a polymer material, an orientation film of a liquid crystal polymer, and a film in which an orientation layer of a liquid crystal polymer is supported by a film. The thickness of the retarder is not particularly limited, but is generally about 20 to 150 mu m.

In addition, the film having the retardation may be separately attached to a transparent protective film having no retardation to impart the function.

On the surface of the transparent protective film on which the polarizer is not adhered, a functional layer such as a hard coat layer, an antireflection layer, a sticking prevention layer, a diffusion layer, or an antiglare layer can be formed. The functional layers such as the hard coat layer, the antireflection layer, the anti-sticking layer, the diffusion layer, and the antiglare layer may be formed on the transparent protective film itself or may be formed separately from the transparent protective film It is possible.

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, a liquid crystal display device such as a reflection plate, a semitransmissive plate, a retardation plate (including a wave plate of 1/2 or 1/4) One or more optical layers that may be used may be used. In particular, a reflection type polarizing film or a semi-transmission type polarizing film in which a reflection plate or a transflective reflection plate is further laminated on the polarizing film of the present invention, an elliptically polarizing film or a circularly polarizing film laminated with a retardation film in addition to the polarizing film, A polarizing film in which a time compensating film is further laminated, or a polarizing film in which a luminance improving film is laminated in addition to a polarizing film.

The optical film obtained by laminating the above optical layers on a polarizing film can be formed by sequentially laminating them separately in the course of production of a liquid crystal display device or the like. Is advantageous in that the manufacturing process of a liquid crystal display device and the like can be improved. Appropriate adhesion means such as an adhesive layer can be used for the lamination. In the above polarizing film and other optical films, their optical axes can be arranged at appropriate disposition angles in accordance with the objective retardation characteristics and the like.

An adhesive layer for adhering to other members such as a liquid crystal cell may be formed on the above-mentioned polarizing film or an optical film in which at least one polarizing film is laminated. The pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer is not particularly limited. For example, a polymer such as an acrylic polymer, a silicone polymer, a polyester, a polyurethane, a polyamide, a polyether, have. In particular, an acrylic pressure-sensitive adhesive which is excellent in optical transparency, exhibits appropriate wettability, cohesiveness and adhesive property, and has excellent weather resistance and heat resistance can be preferably used.

The adhesive layer may be formed on one side or both sides of a polarizing film or an optical film as a superposed layer of a different composition or kind. Further, in the case of being formed on both sides, it may be a pressure-sensitive adhesive layer such as a composition, a kind, a thickness, and the like which are different in the front and back of a polarizing film or an optical film. The thickness of the pressure-sensitive adhesive layer can be appropriately determined depending on the intended use and the adhesive force, and is generally 1 to 500 탆, preferably 1 to 200 탆, particularly preferably 1 to 100 탆.

The exposed surface of the adhesive layer is covered with a separator for the purpose of preventing contamination thereof until it is provided for practical use. This makes it possible to prevent contact with the adhesive layer in a conventional handling state. As the separator, a suitable thin film such as a plastic film, a rubber sheet, a paper, a cloth, a nonwoven fabric, a net, a foam sheet, a metal foil and a laminate thereof may be used as the separator, Or a material obtained by coating with an appropriate releasing agent such as a fluorine-based or molybdenum sulfide, may be used.

The polarizing film or optical film of the present invention can be suitably used for the formation of various devices such as a liquid crystal display device. The formation of the liquid crystal display device can be carried out conventionally. That is, the 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 needed, and integrally forming a driving circuit. In the present invention, Except that a polarizing film or an optical film produced by using a polarizing film or an optical film is used. As for the liquid crystal cell, any type of TN type, STN type, π type, or the like can be used.

A suitable liquid crystal display device such as a liquid crystal display device in which a polarizing film or an optical film is disposed on one side or both sides of the liquid crystal cell and a backlight or a reflector is used in the illumination system can be formed. In this case, the polarizing film or optical film according to the present invention can be provided on one side or both sides of the liquid crystal cell. When polarizing films or optical films are formed on both sides, they may be the same or different. In forming the liquid crystal display device, appropriate parts such as a diffusion plate, an anti-glare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate, a backlight, Or more.

Example

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

(Adjustment of active energy ray-curable adhesive composition)

The components used were as follows.

(1) Radical Polymerizable Compound (A)

HEAA (hydroxyethyl acrylamide), SP value 29.6 (MJ / m 3) ^1/2 , Tg of homopolymer 123 ° C, manufactured by Kyowa Co.,

Light acrylate 1.9 ND-A (1.9-nonanediol diacrylate), SP value 19.2 (MJ / m 3) ^1/2 , Tg of homopolymer 69 ° C, manufactured by Kyowa Chemical Industry Co.,

, The SP value 22.9 (MJ / m &lt; 3 &gt;) ^1/2 , the Tg of the homopolymer 150 DEG C,

(2) radical generator (B)

IRGACURE 907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one)

(3) Light-generating agent (C)

CPI-101A (triarylsulfonium-SbF ₆ salt), manufactured by San A &

(4) Alkoxy group-containing amino compound (D)

Alkoxy group-containing aminosilane coupling agent (D1): KBM603 (N-2 (aminoethyl) -3-aminopropyltrimethoxysilane)

(Example 1)

30 parts by weight of HEAA, 30 parts by weight of light acrylate 1.9 ND-A, and 40 parts by weight of ACMO when the total amount of the radically polymerizable compound (A) is 100 parts by weight, 1 part by weight of the radical generator (B) (IRGACURE 819) as the photoacid generator (C), 1 part by weight of CPI-101A as the photoacid generator (C), 1 part by weight of the alkoxyl group- The adhesive composition added by weight was adjusted. (Cohesive surface) of two untreated acrylic films (transparent protective film, SP value 22.2, water vapor permeability 70 g / m 2/24 h) with a microgravure coater so that the thickness of the final adhesive layer was 0.6 탆, The composition was applied. Next, both surfaces of the polarizer were subjected to corona treatment at a discharge amount of 100 W / min / m &lt; 2 &gt;, and two transparent protective films coated with an adhesive composition on both surfaces of the polarizer were bonded from the application side. Further, ultraviolet rays of 700 mJ / cm 2 were irradiated from the side of the transparent protective film on both sides of the laminated body, respectively, to obtain a polarizing film having a transparent protective film on both sides of the polarizer.

Examples 2 to 3

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

Comparative Examples 1 to 2

A polarizing film was produced in the same manner as in Example 1 except that neither the photo-generating agent (C) nor the alkoxy group-containing amino compound (D) was used.

[evaluation]

The polarizing films obtained in Examples and Comparative Examples were subjected to the following evaluations.

The results are shown in Table 1.

&Lt; Tg: glass transition temperature &gt;

Tg was measured using the TA instrument dynamic viscoelasticity measurement apparatus RSAIII under the following measurement conditions.

Sample size: width 10 mm, length 30 mm,

Clamp distance 20 mm,

Measurement mode: tensile, frequency: 1 Hz, heating rate: 5 ° C / minute

The dynamic viscoelasticity was measured and adopted as the temperature Tg of the peak top of tan delta.

&Lt; Water vapor permeability of transparent protective film &gt;

The measurement of the moisture permeability was carried out in accordance with the moisture permeability test (cup method) of JIS Z0208. A sample cut into a diameter of 60 mm was set in a moisture-permeable cup containing about 15 g of calcium chloride, and a sample was taken at a temperature of 40 DEG C and a humidity of 90% RH. (G / m &lt; 2 &gt; / 24 h) was obtained by measuring the increase in the weight of calcium chloride before and after standing for 24 hours.

<Water resistance test>

With respect to the water resistance test, the following three tests were conducted.

[Test (1): 40 ° C, 92% R.H., 500 h]

92% R.H. Under the environment, the polarizing film was cut out in a size of 1.5 cm x 15 cm, left for 500 hours, peeled at a peeling speed of 300 m / min at 90 deg., And the peel force was measured.

[Test (2): 40 ° C hot water, 2 h]

A sample (a sample having the same shape as the test (1)) was immersed in hot water at 40 占 폚 for 2 hours and immediately peeled off at 90 占 peeling speed of 300 m / min.

[Test (3): 40 ° C hot water, 2 h, with aging]

Before the test, the sample (sample having the same shape as the test (1)) was heated (aged) at 50 캜 for 12 hours, immersed in hot water at 40 캜 for 2 hours, 90 DEG peeling was performed, and the peel force was measured.

In the tests (1) to (3), the evaluation criteria of the peel force measured are as follows.

◎: Peel force 1.0 N / 15 mm or more

○: Peel force 0.5 N or more, 1.0 N / 15 mm or less

?: Peel force of 0.2 N or more and less than 0.5 N / 15 mm

X: Peel force less than 0.2 N / 15 mm

Claims (19)

(D) a radically polymerizable compound (A), a radical generator (B), a photoacid generator (C) and an alkoxy group-
Wherein the radically polymerizable compound (A) is at least one member selected from the group consisting of hydroxyethyl acrylamide, N-methylol acrylamide, acryloylmorpholine and N-methoxymethyl acrylamide,
Wherein the alkoxy group-containing amino compound (D) is an alkoxy group-containing amino silane coupling agent (D1). delete The method according to claim 1,
Wherein the content of the alkoxyl group-containing aminosilane coupling agent (D1) is 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of the radically polymerizable compound (A). The method according to claim 1,
Wherein the photoacid generator (C) comprises a photoacid generator having at least one selected from the group consisting of PF ₆ ^- , SbF ₆ ^- and AsF ₆ ^- as counteranions. delete delete The method according to claim 1,
As the radical generator (B), a compound represented by the following general formula (1);
[Chemical 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). 8. The method of claim 7,
A compound represented by the following general formula (2) as the radical generator (B);
(2)

(Wherein, R ^3, R ⁴ and R ⁵ are _{-H, -CH 3, -CH 2 CH} 3, or -iPr represents Cl, R ^3, R ⁴ and R ⁵ are the same or different) a By weight of an active energy ray curable adhesive composition. As a polarizing film having a transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm formed on at least one surface of a polarizer via an adhesive layer,
Wherein the adhesive layer is formed of a cured layer formed by irradiating an active energy ray to the active energy ray curable adhesive composition according to claim 1. 10. The method of claim 9,
Wherein the adhesive layer has a glass transition temperature (Tg) of 20 DEG C or higher. 10. The method of claim 9,
Wherein the transparent protective film has a moisture permeability of 150 g / m 2/24 h or less. 10. The method of claim 9,
Wherein the transparent protective film has an SP value of 29.0 (MJ / m 3) ^1/2 or more and 33.0 (MJ / m 3) ^1/2 . 10. The method of claim 9,
Wherein the transparent protective film has an SP value of 18.0 (MJ / m 3) ^1/2 or more and ^less than 24.0 (MJ / m 3) ^1/2 . A transparent protective film having a light transmittance of less than 5% at a wavelength of 365 nm is formed on at least one surface of a polarizer via an adhesive layer,
An application step of applying the active energy ray-curable adhesive composition according to claim 1 onto at least one surface of the polarizer or the transparent protective film,
An adhesion step of bonding the polarizer and the transparent protective film,
And adhering the polarizer and the transparent protective film via an adhesive layer obtained by irradiating an active energy ray from the side of the polarizer surface or the surface of the transparent protective film and curing the active energy ray curable adhesive composition &Lt; / RTI &gt; 15. The method of claim 14,
Wherein at least one surface of the polarizer or the transparent protective film is subjected to a corona treatment, a plasma treatment, a frame treatment, or an excimer treatment on the side to which the active energy ray curable adhesive composition is applied, &Lt; / RTI &gt; 15. The method of claim 14,
Wherein the polarizer has a water content of less than 15% during the bonding step. 15. The method of claim 14,
Wherein the polarizing film has a heating step during or after irradiation with an active energy ray in the adhering step. An optical film characterized in that at least one polarizing film according to claim 9 is laminated. An image display apparatus characterized by using the polarizing film according to claim 9 and / or the optical film according to claim 18.