TW201514269A - Curable adhesive for polarizing films, polarizing film, optical film and image display device - Google Patents

Abstract

This curable adhesive for polarizing films, which contains a curable component, has a bulk water absorption of 10% by weight or less in cases where a cured product of this curable adhesive for polarizing films is immersed in pure water at 23 DEG C for 24 hours, said bulk water absorption being represented by the following formula. Bulk water absorption (%) = {(M2 - M1)/M1} x 100 (%) (In this formula, M1 represents the weight of the cured product before immersion, and M2 represents the weight of the cured product after immersion.) This curable adhesive for polarizing films provides excellent adhesion between a polarizer and a transparent protective film, and is able to have satisfactory optical durability in a harsh environment at high temperature and high humidity. In addition, this curable adhesive for polarizing films exhibits sufficient adhesive power even if immersed in water for a long period of time.

Description

Hardened adhesive for polarizing film, polarizing film, optical film and image display device Technical field

The present invention relates to a curing adhesive for a polarizing film which is used for forming the above-mentioned adhesive layer in a polarizing film in which a polarizer and a transparent protective film are laminated via an adhesive. Further, the present invention relates to a polarizing film using the above adhesive layer. The polarizing film may be formed as an image display device such as a liquid crystal display (LCD), an organic EL display device, a CRT or a PDP, either alone or as an optical film in which the polarizing film is laminated.

Background technique

In watches, mobile phones, PDAs, notebook personal computers, personal computer monitors, DVD players, TVs, etc., liquid crystal display devices are rapidly expanding in the market. The liquid crystal display device visualizes a polarization state by switching of liquid crystals, and uses a polarizer according to the display principle thereof. In particular, in applications such as TVs, high brightness, high contrast, and wide viewing angle are required, and in the polarizing film, high transmittance, high degree of polarization, high color reproducibility, and the like are required.

Since it has high transmittance and high degree of polarization, for example, iodine is adsorbed to polyvinyl alcohol (hereinafter, simply referred to as "PVA") and the knot is extended. The iodine-based polarizer is generally most widely used as a polarizer. In general, the polarizing film is a polarizing film in which a transparent protective film is bonded to both sides of a polarizing member by a so-called water-based adhesive in which a polyvinyl alcohol-based material is dissolved in water (Patent Document 1 and Patent Application below) Literature 2). The transparent protective film is made of triacetone cellulose or the like having a high moisture permeability. When the water-based adhesive is used (so-called wet lamination), after the polarizer and the transparent protective film are bonded, a drying step must be performed.

On the other hand, it is currently disclosed that there is an active energy ray hardening type. To replace the aforementioned aqueous binder. When a polarizing film is produced by using an active energy ray-curable adhesive, since the drying step is not required, the productivity of the polarizing film can be improved. For example, a radical polymerization type active energy ray-curable adhesive using an N-substituted amide-based monomer as a curable component has been disclosed (Patent Documents 3 and 4). The above-mentioned adhesive exhibits excellent durability in a severe environment under high humidity and high temperature. However, the fact is that an adhesive which can improve further adhesion and/or water resistance is still required on the market.

Also, focusing on the SP value (solubility parameter) of the curable component, There has been disclosed an active energy ray-curable adhesive which uses at least three kinds of radical polymerizable compounds having different SP values by a predetermined composition ratio, whereby an adhesive layer for improving durability and water resistance can be formed (under Patent Document 5).

Advanced technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2006-220732

Patent Document 2: Japanese Patent Laid-Open Publication No. 2001-296427

Patent Document 3: Japanese Patent Laid-Open Publication No. 2008-287207

Patent Document 4: Japanese Patent Laid-Open Publication No. 2010-078700

Patent Document 5: Japanese Patent Laid-Open Publication No. 2012-144690

Summary of invention

According to the active energy ray-curable adhesive disclosed in Patent Document 5, various transparent protective films used in the production of the polarizing film can satisfy durability and water resistance. However, the polarizing film obtained by using the active energy ray-curable adhesive disclosed in Patent Document 5 can satisfy the water resistance (warm water immersion test) immersed in warm water of 60 ° C for 6 hours, however, on the market. Further requirements for optical durability in harsh environments under high temperature and high humidity are required. Further, the polarizing film is required to have sufficient adhesion even when immersed in water for a long period of time.

An object of the present invention is to provide a hardening type adhesive for a polarizing film which is excellent in adhesion between a polarizing member and a transparent protective film, and which can satisfy optical durability in a severe environment under high temperature and high humidity, and even It is also a sufficient adhesion when immersed in water for a long time.

Moreover, an object of the present invention is to provide a polarizing film which is provided with a transparent protective film on a polarizing member by using an adhesive layer formed of a curing adhesive for a polarizing film, and further, a polarizing film using the foregoing The optical film further provides an image display device using the above polarizing film or optical film.

In order to solve the above problems, the inventors have found that the above object can be attained by the following curing agent for a polarizing film, so as to solve the present invention.

In other words, the present invention relates to a curable adhesive for a polarizing film which contains a curable component, and the cured adhesive for a polarizing film is immersed in a cured product obtained by curing the curable adhesive at 23 ° C. In the case of pure water for 24 hours, the overall water absorption ratio expressed by the following formula is 10% by weight or less, that is, the overall water absorption rate (%) = {(M2-M1) / M1} × 100

{However, in the above formula, M1 represents the weight of the cured product before impregnation, and M2 represents the weight of the cured product after impregnation}.

The octanol/water partition coefficient (logPow value) of the hardening type adhesive for a polarizing film is preferably 1 or more.

The curable adhesive for a polarizing film can be used as an active energy ray-curable adhesive when the curable component is an active energy ray-curable component. The curable component may contain a radical polymerizable compound. The radically polymerizable compound preferably contains a (meth) acrylamide derivative. Moreover, it is preferable that the radically polymerizable compound contains a polyfunctional compound, and the polyfunctional compound has at least two radically polymerizable functional groups. Further, the active energy ray-curable adhesive may further contain a photopolymerization initiator.

The hardening type adhesive for a polarizing film may further contain an acrylic oligomer (A).

The curing adhesive for a polarizing film may further contain a photoacid generator (B).

The hardening type adhesive for a polarizing film may further contain a compound (C) containing any one of an alkoxy group and an epoxy group. The compound (C) containing any one of an alkoxy group and an epoxy group is preferably a compound (C1) containing an alkoxy group. Further, the alkoxy group-containing compound (C1) is preferably a melamine compound containing an alkoxy group.

Further, the hardening type adhesive for a polarizing film may further contain an isocyanate compound (D).

The curable adhesive for a polarizing film further contains a thermal polymerization initiator when the curable component is a thermosetting component, and can be used as a thermosetting adhesive.

Moreover, the present invention relates to a polarizing film in which at least one of the polarizing members is provided with a transparent protective film via an adhesive layer, and the adhesive layer is a cured product of a hardening type adhesive for the polarizing film. The layer is formed.

In the polarizing film, the thickness of the cured layer of the adhesive is preferably 0.1 to 3 μm.

Furthermore, the present invention relates to an optical film which laminates at least one of the aforementioned polarizing films.

Furthermore, the present invention relates to an image display device using the above-described polarizing film or the above optical film.

The hardening type adhesive for polarizing film of the present invention is used for hardening The cured product obtained by curing the type of the adhesive has an overall water absorption of 10% by weight or less. The overall water absorption rate shows that the water absorbing property when the adhesive layer is formed from the cured layer obtained from the hardening type adhesive for a polarizing film of the present invention is extremely low. Therefore, a polarizing film of a transparent protective film is provided on the polarizer on the adhesive layer formed by the cured layer, and the adhesion between the polarizer and the transparent protective film layer is good, and the high temperature and high humidity can be satisfied. Optical durability in harsh environments.

For example, a polarizing film having a cured layer (adhesive layer) formed using a hardening type adhesive for a polarizing film of the present invention is optically durable even in a severe humidifying environment (85 ° C × 85% RH) The properties (humidification durability test) were also good. Therefore, even when the polarizing film of the present invention is placed in the above-mentioned severe humidification environment, the transmittance and the degree of polarization of the polarizing film can be lowered (changed). Further, the polarizing film of the present invention can suppress the decrease in the adhesion force even in a severe environment such as immersion in water, and can provide a polarizing film having sufficient adhesion even when immersed in water for a long period of time.

Form for implementing the invention

<Overall water absorption rate>

The cured water-repellent adhesive for a polarizing film of the present invention has a total water absorption of 10% by weight or less as measured by immersing the cured product obtained by curing the curable adhesive in pure water at 23 ° C for 24 hours. When the polarizing film is placed in a harsh high temperature and high humidity (85 ° C / 85% RH, etc.) environment, it has been thoroughly The moisture in the transparent protective film and the adhesive layer penetrates into the polarizer, and the crosslinked structure is hydrolyzed, whereby the orientation of the dichroic dye is disturbed, and the optical durability such as an increase in transmittance and a decrease in the degree of polarization is deteriorated. By setting the overall water absorption rate of the adhesive layer to 10% by weight or less, it is possible to suppress the movement of water toward the polarizing member when the polarizing film is placed in a severe high-temperature and high-humidity environment, and it is possible to suppress the transmittance of the polarizing member from rising and polarizing. Degree is reduced. The adhesive layer of the polarizing film is preferably 5% by weight or less, and more preferably 3% by weight or less, from the viewpoint of further improving the optical durability in a severe environment at a high temperature. Further, it is preferably 1.5% by weight or less, and most preferably 1% by weight or less. On the other hand, when the polarizing member and the transparent protective film are bonded, the polarizing member retains a certain amount of moisture, and when the hardening type adhesive is in contact with the moisture contained in the polarizing member, there is a possibility of occurrence of collapse or bubbles and appearance defects. . In order to suppress poor appearance, the hardening type adhesive preferably absorbs a certain amount of moisture. More specifically, the overall water absorption rate is preferably 0.01% by weight or more, and more preferably 0.05% by weight or more. Specifically, the overall water absorption rate is measured by a water absorption rate test method disclosed in JIS K 7209.

The hardening type adhesive for polarizing film of the present invention is preferably octanol/water The distribution coefficient (hereinafter referred to as logPow value) is high. The so-called logPow value is an indicator of the lipophilicity of a substance and means the logarithm of the partition coefficient of octanol/water. A high logPow means that it is lipophilic, that is, it means that the water absorption rate is low. The logPow value can be measured (the flask oscillating method disclosed in JIS-Z-7260), but it can also be calculated by the structure of each compound which is a constituent component (hardening component, etc.) of the hardening type adhesive for polarizing film. To calculate. In this manual, use Cambridge by Cambridge Software The logPow value calculated by Draw Ultra.

According to the above calculated value, the logPow value of the hardening type adhesive for a polarizing film in the present invention can be calculated by the following formula.

Hardening type of adhesive logPow = Σ (logPowi × Wi)

logPowi: logPow value of each component of the hardened adhesive

Wi: (the number of moles of the i component) / (the total number of moles of each component of the hardened adhesive)

In the above calculation, among the components of the curable adhesive, the components of the skeleton which does not form a cured product (adhesive layer) such as a polymerization initiator or a photoacid generator are deducted from the components in the above calculation. The logPow value of the curing adhesive for a polarizing film of the present invention is preferably 1 or more, and more preferably 1.5 or more, and most preferably 2 or more. Thereby, the subsequent water resistance or humidification durability can be improved. On the other hand, the logPow value of the curable adhesive for a polarizing film of the present invention is usually 8 or less, and preferably 5 or less, more preferably 4 or less. If the logPow value is too high, as described above, it is less desirable because it is liable to cause appearance defects such as collapse or bubbles.

Further, the method of setting the total water absorption rate in the present invention to 10% by weight or less is not particularly limited. However, when the curing adhesive for a polarizing film is a composition containing a plurality of components, by selecting each component, The overall water absorption can be controlled within the aforementioned range. For example, when the curing adhesive for a polarizing film is an adhesive composition containing a plurality of components, the entire composition can be reduced by reducing the log Pow value of the adhesive composition to a ratio of 1 or less. The water absorption rate is controlled within the aforementioned range. When the overall water absorption rate in the present invention is adjusted to 10% by weight or less, for example, In other words, the polarizing film can be controlled to have a log Pow value of 1 or more.

<hardening shrinkage rate>

Further, since the curable adhesive for a polarizing film of the present invention has a curable component, when the curable adhesive is cured, curing shrinkage usually occurs. The hardening shrinkage ratio is an index showing the ratio of hardening shrinkage when forming an adhesive layer from a hardening type adhesive for a polarizing film. When the curing shrinkage ratio of the adhesive layer is increased, it is preferable that the interface film is formed when the polarizing film is cured with a curing adhesive to form an adhesive layer, and it is preferable to suppress occurrence of adhesion defects. From the above viewpoints, the curing shrinkage ratio of the cured product obtained by curing the polarizing film of the present invention with a curing adhesive is preferably 10% or less. It is preferable that the curing shrinkage ratio is small, and the curing shrinkage ratio is preferably 8% or less, more preferably 5% or less. The hardening shrinkage ratio is measured by the method disclosed in JP-A-2013-104869, and specifically, it is measured by the method of the SENTEC company hardening shrinkage sensor disclosed in the examples.

<hardenable ingredients>

The curable adhesive for a polarizing film of the present invention contains a curable component. The curable component can be appropriately selected so that the cured product satisfies the aforementioned overall water absorption rate.

The curable component can be roughly distinguished from an active energy ray-curing type and a thermosetting type such as an electron beam curing type, an ultraviolet curing type, and a visible light curing type. Further, the ultraviolet curable type and visible light curing type adhesive can be classified into a radical polymerization curing type adhesive and a cationic polymerization type adhesive. Yu Ben In the invention, an active energy ray having a wavelength range of 10 nm to less than 380 nm is denoted as ultraviolet ray, and an active energy ray having a wavelength range of 380 nm to 800 nm is denoted as visible light. The curable component of the radical polymerization-curing adhesive can be used as a curable component of a thermosetting adhesive.

<1: Radical polymerization hardening type adhesive>

For example, the curable component may be, for example, a radical polymerizable compound used in a radical polymerization curing type adhesive. The radical polymerizable compound may, for example, be a compound having a radical polymerizable functional group having a carbon-carbon double bond such as a (meth)acryl fluorenyl group or a vinyl group. As the curable component, any of a monofunctional radical polymerizable compound or a polyfunctional radical polymerizable compound having a difunctional or higher functional group can be used. In addition, these radically polymerizable compounds may be used alone or in combination of two or more. For example, the radically polymerizable compound is suitably a compound having a (meth) acrylonitrile group. In the present invention, the (meth)acryl fluorenyl group means an acryl fluorenyl group and/or a methacryl fluorenyl group, and "(meth)" means the same as the following.

Monofunctional Radical Polymerizable Compound

For example, the monofunctional radically polymerizable compound may, for example, be a (meth) acrylamide derivative having a (meth) acrylamide group. Further, in terms of ensuring adhesion to a polarizing member or various transparent protective films, a (meth)acrylamide derivative is preferable in that the polymerization rate is fast and the productivity is excellent. Specific examples of the (meth) acrylamide derivative may, for example, be N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N. -Diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, etc. -alkyl (Meth) acrylamide derivatives; N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol-N-propane (methyl) propylene a (meth) acrylamide derivative containing an N-hydroxyalkyl group such as a decylamine; an N-aminoalkyl group such as an amine methyl (meth) acrylamide or an amine ethyl (meth) acrylamide; Methyl) acrylamide derivative; (meth) acrylamide derivative containing N-alkoxy group such as N-methoxymethyl propylene decylamine or N-ethoxymethyl acrylamide; A (meth) acrylamide derivative containing an N-fluorenyl group such as a (meth) acrylamide or a decyl (meth) acrylamide. Further, by way of example, the (meth) acrylamide derivative containing a hetero ring containing a hetero ring of a nitrogen atom of a (meth) acrylamide group may, for example, be N-propenylmorpholine or N-propene fluorene. Piperidine, N-methylpropenylpiperidine, N-propenylpyrrolidine, and the like.

In the above (meth) acrylamide derivative, if used with a polarizer Or a viewpoint of the adhesion of various transparent protective films, it is also preferably a (meth) acrylamide derivative containing an N-hydroxyalkyl group, particularly preferably N-hydroxyethyl (meth) acrylamide .

Further, as an example, the monofunctional radically polymerizable compound may, for example, be a variety of (meth)acrylic acid derivatives having a (meth)acryloxy group. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate may be mentioned. , 2-methyl-2-nitropropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate , t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, 2, 2- Methyl butyl (meth) acrylate, n-hexyl (meth) acrylate, hexadecyl (meth) acrylate Ester, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 4-methyl-2-propylpentyl (meth) acrylate, n-octadecyl (A) (meth)acrylic acid (carbon number 1-20) alkyl esters such as acrylate.

Further, by way of example, the aforementioned (meth)acrylic acid derivative can be enumerated For example: cycloalkyl (meth) acrylate, cyclopentyl (meth) acrylate and other cycloalkyl (meth) acrylate; benzyl (meth) acrylate and other aralkyl (meth) acrylate; 2-isodecyl (meth) acrylate, 2-norbornylmethyl (meth) acrylate, 5-northene-2-yl-methyl (meth) acrylate, 3-methyl- 2-norbornylmethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (methyl) Polycyclic (meth) acrylate such as acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxy Ethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxy ethyl (meth) acrylate, alkyl benzene An oxypolyethylene glycol (meth) acrylate or the like containing an alkoxy group or a phenoxy group (meth) acrylate or the like.

Further, the aforementioned (meth)acrylic acid derivative may, for example, be 2-hydroxyethyl Base (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( Methyl) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (methyl) Hydroxyalkyl (meth) acrylate such as acrylate or [4-(hydroxymethyl)cyclohexyl]methacrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxy Hydroxy-containing (meth) acrylate such as propyl (meth) acrylate; (meth) acrylate, epoxy group-containing (meth) acrylate such as 4-hydroxybutyl (meth) acrylate epoxy propyl ether; 2, 2, 2-trifluoroethyl (methyl) Acrylate, 2,2,2-trifluoroethylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl ( a halogen-containing (meth) acrylate such as methyl acrylate, heptafluorodecyl (meth) acrylate or 3-chloro-2-hydroxypropyl (meth) acrylate; dimethylamino group B Alkylaminoalkyl (meth) acrylate such as (meth) acrylate; 3-oxetanylmethyl (meth) acrylate, 3-methyl-oxetanyl (meth) acrylate, 3-ethyl-oxetanylmethyl (meth) acrylate, 3-butyl-oxetanylmethyl (meth) acrylate, 3- (meth) acrylate containing oxetane group, such as hexyl-oxetanylmethyl (meth) acrylate; tetrahydroindenyl (meth) acrylate, butyrolactone (methyl) a heterocyclic (meth) acrylate or a hydroxytrimethyl acetic acid neopentyl glycol (meth) acrylate adduct such as an acrylate or the like P-phenylphenol (meth) acrylate or the like.

Further, the monofunctional radically polymerizable compound may be, for example, a carboxyl group-containing monomer such as acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid or isocrotonic acid.

Also, by way of example, a monofunctional radically polymerizable compound can be listed For example: N-vinylpyrrolidone, N-vinyl-ε-caprolactam, methyl vinylpyrrolidone and other internal guanamine-based vinyl monomers; vinyl pyridine, vinyl piperidone, A vinyl-based monomer having a nitrogen-containing hetero ring such as vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxime or vinylmorpholine.

Further, a monofunctional radically polymerizable compound can be used to have activity A radically polymerizable compound of a methylene group. The radically polymerizable compound having an active methylene group is a compound having an active double bond group such as a (meth)acrylonyl group at the terminal or molecule and having an active methylene group. For example, the active methylene group may, for example, be an ethyl acetonitrile group, an alkoxy propylene group or a cyanoethyl group. The aforementioned active methylene group is preferably an ethyl oxime group. Specific examples of the radically polymerizable compound having an active methylene group include, for example, 2-ethlyoximeoxyethyl (meth) acrylate and 2-ethyl acetoxypropyl propyl ( Ethyl ethoxylated alkyl (meth) acrylate such as methyl acrylate or 2-acetamethylene-1-methylethyl (meth) acrylate; 2-ethoxy propylene Mercaptooxyethyl (meth) acrylate, 2-cyanoethoxy ethoxyethyl (meth) acrylate, N-(2-cyanoethoxy ethoxyethyl) acrylamide, N- (2-propionyl ethoxylated butyl) acrylamide, N-(4-acetamidooxymethylbenzyl) acrylamide, N-(2-acetamidoamine) Base) acrylamide and the like. The radically polymerizable compound having an active methylene group is preferably acetoxyethoxyalkyl (meth) acrylate.

"Polyfunctional Radical Polymerizable Compound"

Further, examples of the polyfunctional or higher-radical polymerizable compound having a difunctional or higher functional group include, for example, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and 1,6-hexanediol. Di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-nonanediol diacrylate, 2-ethyl-2-butylpropanediol di(meth)acrylic acid Ester, bisphenol A di(meth) acrylate, bisphenol A ethylene oxide adduct di(meth) acrylate, bisphenol A propylene oxide adduct di(meth) acrylate, bisphenol A diglycidyl ether di(meth) acrylate, neopentyl glycol di(meth) acrylate, tricyclodecane dimethanol di(methyl) Acrylate, cyclic trimethylolpropane formal (meth) acrylate, dioxol diol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl alcohol Tris(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO denatured diglycerol An ester of (meth)acrylic acid with a polyhydric alcohol such as tetra(meth)acrylate or 9,9-bis[4-(2-(methyl)acryloxyethoxyethoxy)phenyl]anthracene. Specific examples include ARONIX M-220, M-306 (manufactured by Toagosei Co., Ltd.), LIGHT ACRYLATE1, 9ND-A (manufactured by Kyoeisha Chemical Co., Ltd.), LIGHT ACRYLATE DGE-4A (manufactured by Kyoeisha Chemical Co., Ltd.), LIGHT ACRYLATE DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), SR-531 (manufactured by Sartomer Co., Ltd.), CD-536 (manufactured by Sadol Co., Ltd.), and the like. Further, if necessary, various epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, or various (meth) acrylate monomers may be mentioned. .

In controlling the water absorption rate of the hardened material, and in addition, satisfying the polarized light In the optical durability of the film in a severe humidifying environment, the radical polymerizable compound preferably contains the polyfunctional radical polymerizable compound. Among the above polyfunctional radically polymerizable compounds, those having a high log Pow value are also preferred. The logPow value of the radically polymerizable compound is preferably 2 or more, and more preferably 3 or more, and most preferably 4 or more.

For example, a radical polymerizable compound having a high logPow value can be used. For example, an alicyclic (meth) acrylate such as tricyclodecane dimethanol di(meth) acrylate (logPow=3.05) or isodecyl (meth) acrylate (logPow=3.27); 1,9- Decanediol di(meth)acrylate Long chain aliphatic (meth) acrylate such as (logPow=3.68), 1,10-nonanediol diacrylate (logPow=4.10); hydroxytrimethylacetic acid neopentyl glycol (meth)acrylic acid adduct (logPow = 3.35), multi-branched (meth) acrylate such as 2-ethyl-2-butyl propylene glycol di(meth) acrylate (logPow = 3.92); bisphenol A di(meth) acrylate ( logPow=5.46), bisphenol A ethylene oxide 4 molar addition di(meth)acrylate (logPow=5.15), bisphenol A propylene oxide 2 molar addition di(meth)acrylate (logPow=6.10), bisphenol A propylene oxide 4 molar addition di(meth) acrylate (logPow=6.43), 9,9-bis[4-(2-(methyl) propylene oxy group An (meth) acrylate or the like containing an aromatic ring such as ethoxy)phenyl]anthracene (logPow=7.48) or p-phenylphenol (meth)acrylate (logPow=3.98).

If both by the polarizer or various transparent protective films From the viewpoint of optical durability in a severe environment and a harsh environment, a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound are preferably used in combination with the radical polymerizable compound. In general, it is preferable to use 3 to 80% by weight of the monofunctional radically polymerizable compound and 20 to 97% by weight of the polyfunctional radically polymerizable compound in combination with 100% by weight of the radically polymerizable compound.

<The aspect of the radical polymerization hardening type adhesive>

When the curable component is used as an active energy ray-curable component, the curable adhesive for a polarizing film of the present invention can be used as an active energy ray-curable adhesive, and a curable component can be used as a thermosetting component. When used, it can be used as a thermosetting adhesive. When the active energy ray-curable adhesive uses an electron beam or the like on the active energy ray, the activity The performance amount wire hardening type adhesive does not need to contain a photopolymerization initiator. However, when ultraviolet rays or visible rays are used for the active energy ray, a photopolymerization initiator is preferably contained. On the other hand, when the curable component of the above-mentioned adhesive is used as a thermosetting component, the adhesive preferably contains a thermal polymerization initiator.

Photopolymerization Initiator

The photopolymerization initiator in the case of using a radical polymerizable compound can be appropriately selected in accordance with the active energy ray. When it is hardened by ultraviolet rays or visible rays, a photopolymerization initiator which cleaves ultraviolet rays or visible rays is used. For example, the photopolymerization initiator may, for example, be diphenylethylenedione, diphenylketone, benzamidinebenzoic acid or 3,3'-dimethyl-4-methoxydiphenyl ketone. Phenyl ketone compound; 4-(2-hydroxyethoxy)phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α'-dimethylacetophenone, 2-methyl An aromatic ketone compound such as 2-hydroxypropiophenone or α-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-di Acetophenone-based compound such as ethoxyacetophenone or 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinepropane-1; benzoin methyl ether, benzoin a benzoin ether compound such as diethyl ether, benzoin isopropyl ether, benzoin butyl ether, fennel aceton methyl ether; an aromatic ketal compound such as diphenylethylenedione dimethyl ketal; 2-naphthalene Aromatic sulfonium chloride compound such as sulfonium chloride; photoactive lanthanide compound such as 1-benzophenone-1,1-propanedione-2-(o-ethoxycarbonyl)anthracene; 9-oxosulfur (thioxanthone), 2-chloro 9-oxosulfur 2-methyl 9-oxosulfur 2,4-dimethyl 9-oxosulfur Isopropyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-diisopropyl 9-oxosulfur Twelve base 9-oxosulfur 9-oxosulfur a compound; camphorquinone; a halogenated ketone; a fluorenylphosphine oxide; a decylphosphonate. In the photopolymerization initiator, it is also preferred that the logPow value is high. The photopolymerization initiator is not included in the calculation of the log Pow value of the hardening type adhesive for a polarizing film. However, the photopolymerization initiator preferably has a log Pow value of 1 or more, and more preferably 2 or more, and most preferably 3 or more. .

Relative to the hardening component (radical polymerizable compound) The amount of the photopolymerization initiator blended is 20 parts by weight or less based on 100 parts by weight. The blending amount of the photopolymerization initiator is preferably from 0.01 to 20 parts by weight, and more preferably from 0.05 to 10 parts by weight, further preferably from 0.1 to 5 parts by weight.

Further, a radical polymerizable compound is contained as a curable component In the visible light curing type, when the curing adhesive for a polarizing film of the present invention is used, it is particularly preferable to use a photopolymerization initiator which is highly sensitive to light of 380 nm or more. The photopolymerization initiator which is high in sensitivity to light of 380 nm or more is mentioned later.

The above photopolymerization initiator is preferably used alone as a compound represented by the following general formula (1): (wherein R ¹ and R ² represent -H, -CH ₂ CH ₃ , -iPr or Cl, and R ¹ and R ² may be the same or different), or a compound represented by the general formula (1) may be used in combination with A photopolymerization initiator which is highly sensitive to light of 380 nm or more will be described later. When a photopolymerization initiator which is highly sensitive to light of 380 nm or more is used alone, the compound represented by the general formula (1) is excellent in adhesion. Among the compounds represented by the general formula (1), it is also particularly preferred that diethyl 1 - oxysulfide wherein R ¹ and R ² are -CH ₂ CH ₃ . The composition ratio of the compound represented by the general formula (1) in the adhesive is preferably 0.1 to 5 parts by weight, and more preferably 0.5 to 4 parts by weight, and further preferably 0.9, based on 100 parts by weight of the total amount of the curable component. ~3 parts by weight.

Further, a polymerization initiation aid is preferably added as needed. Polymerization The agent may, for example, be triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylamine benzoic acid, methyl 4-dimethylaminebenzoate, ethyl 4-dimethylamine benzoate, Isoamyl 4-dimethylamine benzoate or the like, particularly preferably ethyl 4-dimethylamine benzoate. When the polymerization initiation aid is used, the amount thereof is usually 0 to 5 parts by weight, and preferably 0 to 4 parts by weight, and most preferably 0 to 3 parts by weight, based on 100 parts by weight of the total amount of the curable component.

Further, a known photopolymerization initiator may be used in combination as needed. due to The transparent protective film having a UV absorbing ability does not transmit light of 380 nm or less. Therefore, a photopolymerization initiator is preferably used as a photopolymerization initiator having a high sensitivity to light of 380 nm or more. Specific examples thereof include 2-methyl-1-(4-methylthiophenyl)-2-morpholinepropan-1-one and 2-benzyl-2-dimethylamino-1-( 4-morpholinylphenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)benzene 1-butanone, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine Oxide, bis(η 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium or the like.

In particular, in addition to the photopolymerization initiator of the general formula (1), the photopolymerization initiator is preferably a compound represented by the following general formula (2): (wherein R ³ , R ⁴ and R ⁵ represent -H, -CH ₃ , -CH ₂ CH ₃ , -iPr or Cl, and R ³ , R ⁴ and R ⁵ may be the same or different). 2-methyl-1-(4-methylthiophenyl)-2-morpholinepropan-1-one which is also a commercial product can be suitably used by the compound represented by the general formula (2) (trade name) :IRGACURE907, manufacturer: BASF). In addition, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1 (trade name: IRGACURE 369, manufacturer: BASF), 2-(dimethylamine) Benzyl-2-(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: IRGACURE 379, manufacturer: BASF) due to High sensitivity, so it is ideal.

<The radically polymerizable compound (a1) having an active methylene group and a radical polymerization initiator (a2) having a hydrogen abstracting action>

In the above-mentioned active energy ray-curable adhesive, when a radically polymerizable compound (a1) having an active methylene group is used as the radical polymerizable compound, it is preferably combined with a radical polymerization initiator (a2) having a hydrogen abstracting action. And use. According to the above configuration, even if it is taken out from a high-humidity environment or water in particular (non-dry state), the adhesion of the adhesive layer of the polarizing film can be remarkably improved. This reason is not clear, however, it is generally considered to be the following reason. That is, the radically polymerizable compound (a1) having an active methylene group is polymerized together with other radically polymerizable compounds constituting the adhesive layer, and is taken into the main chain and/or side of the base polymer in the adhesive layer. Chain and form an adhesive layer. In the above polymerization process, if a radical polymerization initiator (a2) having a hydrogen abstracting action is present, a radical polymerizable compound (a2) having an active methylene group which forms a base polymer constituting the adhesive layer is formed. Hydrogen, and produces free radicals at the methylene group. Also, the radicals that have produced free radicals The base reacts with a hydroxyl group of a polarizer such as PVA, and forms a covalent bond between the adhesive layer and the polarizer. As a result, it is generally estimated that the adhesion of the adhesive layer of the polarizing film can be remarkably improved even in a particularly non-dry state.

In the present invention, as an example, the radical polymerization initiator (a2) having a hydrogen abstracting action can be exemplified by 9-oxosulfur A radical polymerization initiator, a diphenyl ketone radical polymerization initiator, or the like. The aforementioned radical polymerization initiator (a2) is preferably 9-oxosulfur A free radical polymerization initiator. For example, 9-oxygen sulfur The radical polymerization initiator may, for example, be a compound represented by the above general formula (1). For example, specific examples of the compound represented by the general formula (1) include, for example, 9-oxosulfur Dimethyl 9-oxosulfur Diethyl 9-oxosulfur Isopropyl 9-oxosulfur Chlorine 9-oxosulfur Wait. Among the compounds represented by the general formula (1), it is also particularly preferred that the diethyl 9-oxosulfuric acid wherein R ¹ and R ² are -CH ₂ CH ₃ .

In the aforementioned active energy ray-curable adhesive, when contained When the radically polymerizable compound (a1) of the active methylene group and the radical polymerization initiator (a2) having a hydrogen abstracting action are used, when the total amount of the curable component is 100% by weight, it is preferred to contain the above-mentioned active methylene group. 1 to 50% by weight of the radical polymerizable compound (a1) and 0.1 to 10 parts by weight of the radical polymerization initiator (a2) per 100 parts by weight of the total amount of the curable component.

As described above, in the present invention, a radical having a hydrogen abstracting action In the presence of the polymerization initiator (a2), a methylene group of the radically polymerizable compound (a1) having an active methylene group generates a radical, and the methylene group reacts with a hydroxyl group of a polarizing member such as PVA to form a total of Price key. Therefore, in order to generate a radical in the methylene group of the radically polymerizable compound (a1) having an active methylene group, When the total amount of the curable component is 100% by weight, the radical polymerizable compound (a1) having an active methylene group preferably contains 1 to 50% by weight, and more preferably 3 ~30% by weight. When the water resistance is sufficiently improved to improve the adhesion in a non-dry state, the radically polymerizable compound (a1) having an active methylene group is preferably made 1% by weight or more. On the other hand, when it is more than 50% by weight, there is a case where hardening failure of the adhesive layer occurs. In addition, the radical polymerization initiator (a2) having a hydrogen abstracting action is preferably contained in an amount of 0.1 to 10 parts by weight, more preferably 0.3 to 9 parts by weight, based on 100 parts by weight of the total amount of the curable component. In order to sufficiently carry out the hydrogen abstraction reaction, it is preferred to use 0.1 part by weight or more of the radical polymerization initiator (a2). On the other hand, if it is more than 10 parts by weight, there is a case where it is not completely dissolved in the adhesive.

Thermal Polymerization Initiator

The thermal polymerization initiator is preferably one which does not initiate polymerization by thermal splitting at the time of formation of the adhesive layer. For example, the thermal polymerization initiator is preferably a 10-hour half-life temperature of 65 ° C or higher, and further 75 to 90 ° C. Further, the half-life is an index indicating the decomposition rate of the polymerization initiator, and means a time until the residual amount of the polymerization initiator is half. The decomposition temperature for obtaining the half-life at any time or the half-life time at any temperature is disclosed in the manufacturer's catalog, etc., for example, disclosed in the "Organic Peroxide Catalogue" of the Japan Oils and Fats Co., Ltd. (2003) May)) and so on.

For example, a thermal polymerization initiator may be exemplified by: a peroxidized laurel Sulfhydryl (10-hour half-life temperature: 64 ° C), benzammonium peroxide (10-hour half-life temperature: 73 ° C), 1,1-bis(t-butoxy)-3,3,5-trimethyl Cyclohexane (10 hour half-life temperature: 90 ° C), di(2-ethylhexyl) peroxydicarbonate (10-hour half-life temperature: 49 ° C), bis(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butyl peroxydicarbonate (10-hour half-life temperature: 51 ° C), t-butyl Peroxy neodecanoate (10 hour half-life temperature: 48 ° C), t-hexylperoxytrimethyl acetate, t-butyl peroxytrimethyl acetate, dilauroyl peroxide (10 hours) Half-life temperature: 64 ° C), di-n-octyl peroxy peroxide, 1,1,3,3-tetramethylbutoxy-2-ethylhexanoate (10-hour half-life temperature: 66 ° C), two ( 4-methylbenzhydryl)peroxide, benzhydryl peroxide (10-hour half-life temperature: 73 ° C), t-butyl peroxyisobutyrate (10-hour half-life temperature: 81 ° C), An organic peroxide such as 1,1-di(t-hexylperoxy)cyclohexane.

Further, as an example, the thermal polymerization initiator may, for example, be 2,2'-azobisisobutyronitrile (10-hour half-life temperature: 67 ° C), 2,2'-azobis(2-methylbutyronitrile). (A 10-hour half-life temperature: 67 ° C), an azo compound such as 1,1-azobis-cyclohexane-1-carbonitrile (10-hour half-life temperature: 87 ° C).

The blending amount of the thermal polymerization initiator is 0.01 to 20 parts by weight based on 100 parts by weight of the total amount of the curable component (radical polymerizable compound). The blending amount of the thermal polymerization initiator is more preferably 0.05 to 10 parts by weight, and further 0.1 to 3 parts by weight.

<2: Cationic polymerization hardening type adhesive>

The hardening component of the cationic polymerization hardening type adhesive may, for example, be a compound having an epoxy group or an oxetane group. The compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in the molecule, and various generally known curable epoxy compounds can be used. The preferred epoxy compound is exemplified by a compound having at least two epoxy groups and at least one aromatic ring in the molecule (aromatic epoxy compound), or having intramolecular At least two epoxy groups and at least one of them is a compound (alicyclic epoxy compound) formed between two adjacent carbon atoms constituting the alicyclic ring.

<Photocationic polymerization initiator>

Since the cationically polymerizable adhesive contains the epoxy compound and the oxetane compound described above as a curable component, and these are all cured by cationic polymerization, the photocationic polymerization initiator is blended. The photocationic polymerization initiator generates a cationic species or a Lewis acid by irradiation with an active energy ray such as visible light, ultraviolet rays, X-rays, or electron beams, and starts polymerization of an epoxy group or an oxetane group.

<Other ingredients>

The hardening type adhesive of the present invention preferably contains the following components.

<Acrylic oligomer (A)>

In addition to the curable component of the radical polymerizable compound, the active energy ray-curable adhesive of the present invention may contain an acrylic oligomer (A) composed of a polymerized (meth)acrylic monomer. By including the acrylic oligomer (A) in the active energy ray-curable adhesive, the curing shrinkage when the active energy ray is irradiated to the adhesive and hardened can be reduced, and the adhesive, the polarizer, the transparent protective film, and the like can be reduced. The interface stress of the adherend. As a result, the decrease in the adhesion between the adhesive layer and the adherend can be suppressed. In order to sufficiently suppress the curing shrinkage of the cured layer (adhesive layer), the content of the acrylic oligomer (A) is preferably 20 parts by weight or less, and more preferably 15 parts by weight based on 100 parts by weight of the total amount of the curable component. The following. When the content of the acrylic oligomer (A) in the adhesive is too large, the decrease in the reaction rate when the active energy ray is irradiated to the adhesive is severe, and the curing failure may be caused. another On the other hand, the acrylic oligomer (A) is preferably contained in an amount of 3 parts by weight or more, and more preferably 5 parts by weight or more, based on 100 parts by weight of the total amount of the curable component.

Active energy ray when considering workability or uniformity during coating The hardening type adhesive is preferably low in viscosity, and therefore, the acrylic oligomer (A) composed of the polymerized (meth)acrylic monomer is also preferably low in viscosity. The acrylic oligomer which is low in viscosity and can prevent hardening shrinkage of the adhesive layer preferably has a weight average molecular weight (Mw) of 15,000 or less, more preferably 10,000 or less, and particularly preferably 5,000 or less. On the other hand, in order to sufficiently suppress the hardening shrinkage of the cured layer (adhesive layer), the weight average molecular weight (Mw) of the acrylic oligomer (A) is preferably 500 or more, and more preferably 1,000 or more, particularly preferably It is 1500 or more. Specifically, examples of the (meth)acrylic monomer constituting the acrylic oligomer (A) include methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl. Base (meth) acrylate, isopropyl (meth) acrylate, 2-methyl-2-nitropropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (Meth) acrylate, S-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, t-pentyl (meth) acrylate , 3-pentyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, n-hexyl (meth) acrylate, hexadecyl (meth) acrylate, n- Octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 4-methyl-2-propylpentyl (meth) acrylate, N-octadecyl (meth) acrylate (meth)acrylic acid (carbon number 1-20) alkyl esters, further, by way of example, cycloalkyl (meth) acrylate (eg cyclohexyl (meth) acrylate, cyclopentyl (A) Acrylate (such as acrylate), aralkyl (meth) acrylate (such as benzyl (meth) acrylate, etc.), polycyclic (meth) propyl Ethyl ester (eg 2-isodecyl (meth) acrylate Ester, 2-norbornylmethyl (meth) acrylate, 5-northene-2-yl-methyl (meth) acrylate, 3-methyl-2-norbornylmethyl (methyl) ) acrylates, etc., hydroxyl-containing (meth) acrylates (eg hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl methyl) -butyl (meth) methacrylate, etc.), alkoxy or phenoxy-containing (meth) acrylates (2-methoxyethyl (meth) acrylate, 2-ethoxyl Ethyl (meth) acrylate, 2-methoxymethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate Ester, phenoxyethyl (meth) acrylate, etc.), epoxy group-containing (meth) acrylates (for example, epoxy propyl (meth) acrylate, etc.), halogen-containing (methyl) Acrylates (eg 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trifluoroethylethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate Ester, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptafluorodecyl (meth) acrylate, etc.), alkylamine Alkyl (meth) acrylate (e.g., dimethylaminoethyl (meth) acrylate, etc.) and the like. These (meth) acrylates may be used alone or in combination of two or more. Specific examples of the acrylic oligomer (A) include "ARUFON" manufactured by Toagosei Co., Ltd., "ACTFLOW" manufactured by Amika Chemical Co., Ltd., and "JONCRYL" manufactured by BASF Corporation of Japan. In the acrylic oligomer (A) composed of a polymerized (meth)acrylic monomer, it is also preferred that the logPow value is high. The acrylic oligomer (A) is a component contained in the calculation of the log Pow value of the curing adhesive for a polarizing film. In the calculation of the logPow value, the molar number of the component of the acrylic oligomer (A) is the number of moles of the (meth)acrylic monomer which has been converted into the acrylic oligomer (A). Acrylic oligomer (A) composed of a polymerized (meth)acrylic monomer The logPow value is preferably 2 or more, and more preferably 3 or more, and most preferably 4 or more.

<Photoacid generator (B)>

The photoactive acid generator (B) may be contained in the active energy ray-curable adhesive. When the photo-acid generator is contained in the active energy ray-curable adhesive, the water resistance and durability of the adhesive layer can be gradually increased as compared with the case where the photo-acid generator is not contained. The photoacid generator (B) can be represented by the following general formula (3).

General formula (3) [Chemical Formula 3] L ⁺ X ^-

(However, L ⁺ represents an arbitrary ruthenium cation. Further, X ^- represents a selected from PF6 ₆ ^- , SbF ₆ ^- , AsF ₆ ^- , SbCl ₆ ^- , BiCl ₅ ^- , SnCl ₆ ^- , ClO ₄ ^- , disulfide a relative anion in the group of carbamate anions and SCN-.)

Should constituting a general structure (3) L ⁺ of the cation of the cation include such as: cation selected from the general formula (4) to the general formula (12) of the following.

General formula (4)

General formula (5) [Chemical Formula 5]

General formula (6)

General formula (7)

General formula (8)

General formula (9) [Chemical Formula 9]

General formula (10)

General formula (11)

General formula (12)

(However, in the above general formulae (4) to (12), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and a substitution. Or unsubstituted aryl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted hydrazine a group of a substituted, unsubstituted carbonyloxy group, a substituted or unsubstituted oxycarbonyl group or a halogen atom. R ⁴ represents the same group as the group disclosed by R ¹ , R ² and R ³ . R ⁵ represents a substitution or not Substituted alkyl, substituted or unsubstituted alkylthio. R ⁶ and R ⁷ each independently represent a substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy group. R represents a halogen atom, a hydroxyl group, a carboxyl group, a fluorenyl group. , cyano, nitro, substituted or unsubstituted amine mercapto, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic, Substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic oxy, substituted or Substituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted heterocyclic thio, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbonyloxy, substituted or unsubstituted oxycarbonyl Any one of Ar ⁴ and Ar ⁵ represents a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, X represents an oxygen or sulfur atom, and i represents an integer of 0 to 5. An integer from 0 to 4. k represents an integer from 0 to 3. Further, 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.

The cation (anthracene cation) corresponding to the general formula (4): for example, dimethylphenyl hydrazine, dimethyl (o-fluorophenyl) fluorene, dimethyl (m-chlorophenyl) fluorene, Dimethyl (p-bromophenyl)fluorene, dimethyl (p-cyanophenyl) anthracene, dimethyl (m-nitrophenyl) anthracene, dimethyl (2,4,6-tribromo) Phenyl) hydrazine, dimethyl (pentafluorophenyl) fluorene, dimethyl (p-(trifluoromethyl)phenyl) fluorene, dimethyl (p-hydroxyphenyl) fluorene, dimethyl (p-fluorenylphenyl) fluorene, dimethyl (p-methylsulfinylphenyl) fluorene, dimethyl (p-methylsulfonyl phenyl) ) 鋶, dimethyl (o-ethyl phenyl) fluorene, dimethyl (o-benzylphenyl) fluorene, dimethyl (p-methylphenyl) fluorene, dimethyl (p -isopropylphenyl)anthracene, dimethyl (p-octadecylphenyl) fluorene, dimethyl (p-cyclohexylphenyl) fluorene, dimethyl (p-methoxyphenyl) fluorene, Dimethyl (o-methoxycarbonylphenyl) hydrazine, dimethyl (p-phenylsulfonylphenyl) fluorene, (7-methoxy-2-oxo-2H-chromen-4-yl) Dimethyl hydrazine, (4-methoxynaphthalen-1-yl) dimethyl hydrazine, dimethyl (p-isopropoxycarbonylphenyl) fluorene, dimethyl (2-naphthyl) anthracene, two Methyl (9-fluorenyl) fluorene, diethyl phenyl hydrazine, methyl ethyl phenyl hydrazine, methyl diphenyl hydrazine, triphenyl fluorene, diisopropyl phenyl hydrazine, diphenyl (4 -phenylsulfonyl-phenyl)-indole, 4,4'-bis(diphenylfluorene)diphenyl sulfide, 4,4'-bis[bis[(4-(2-hydroxy-ethoxy) Base)-phenyl)]鋶]]diphenyl sulfide, 4,4'-bis(diphenylfluorene) extended biphenyl, diphenyl (o-fluorophenyl)fluorene, diphenyl (m- Chlorophenyl)anthracene, diphenyl(p-bromophenyl)anthracene Diphenyl (p-cyanophenyl) fluorene, diphenyl (m-nitrophenyl) fluorene, diphenyl (2,4,6-tribromophenyl) fluorene, diphenyl (pentafluorobenzene) , hydrazine, diphenyl (p-(trifluoromethyl)phenyl) fluorene, diphenyl (p-hydroxyphenyl) fluorene, diphenyl (p-fluorenylphenyl) fluorene, diphenyl (p - sulfinylphenyl) fluorene, diphenyl (p-methylsulfonylphenyl) fluorene, diphenyl (o-ethyl phenyl) fluorene, diphenyl (o-benzyl fluorenyl) Phenyl) fluorene, diphenyl (p-methylphenyl) fluorene, diphenyl (p-isopropylphenyl) fluorene, diphenyl (p-octadecylphenyl) fluorene, diphenyl ( P-cyclohexylphenyl)anthracene, diphenyl(p-methoxyphenyl)anthracene, diphenyl(o-methoxycarbonylphenyl)anthracene, diphenyl (p-phenylsulfonylphenyl)鋶, (7-methoxy-2-oxo-2H-chromen-4-yl)diphenylanthracene, (4-methoxynaphthalen-1-yl)diphenylanthracene, diphenyl ( P-isopropyloxycarbonylphenyl)anthracene, diphenyl(2-naphthyl)anthracene, diphenyl (9-fluorenyl) hydrazine, ethyl diphenyl hydrazine, methyl ethyl (o-methylphenyl) fluorene, methyl bis(p-methylphenyl) fluorene, tris(p-methylphenyl) fluorene, diisopropyl (4-phenylsulfonylphenyl) fluorene, diphenyl (2-thienyl) fluorene, diphenyl (2-furyl) fluorene, diphenyl (9-ethyl-9H carbazole-3) -Base), etc., however, is not limited to these.

Corresponding to the general cation (yttrium oxide cation) of formula (5): For example, dimethyl phenyl ruthenium oxide, dimethyl (o-fluorophenyl) ruthenium oxide, dimethyl (m-chlorophenyl) ruthenium oxide, dimethyl (p-bromophenyl) ruthenium oxide , dimethyl (p-cyanophenyl) ruthenium oxide, dimethyl (m-nitrophenyl) ruthenium oxide, dimethyl (2,4,6-tribromophenyl) ruthenium oxide, dimethyl (pentafluorophenyl)phosphonium oxide, dimethyl (p-(trifluoromethyl)phenyl)phosphonium oxide, dimethyl (p-hydroxyphenyl)phosphonium oxide, dimethyl (p-fluorenylphenyl) Cerium oxide, dimethyl (p-methylsulfinylphenyl) ruthenium oxide, dimethyl (p-methylsulfonylphenyl) ruthenium oxide, dimethyl (o-ethyl phenyl) ruthenium oxide , dimethyl (o-benzylidene phenyl) ruthenium oxide, dimethyl (p-methylphenyl) ruthenium oxide, dimethyl (p-isopropylphenyl) ruthenium oxide, dimethyl ( P-octadecylphenyl)phosphonium oxide, dimethyl (p-cyclohexylphenyl)phosphonium oxide, dimethyl (p-methoxyphenyl)phosphonium oxide, dimethyl (o-methoxycarbonylbenzene) Base, ruthenium oxide, dimethyl (p-phenylsulfonylphenyl) ruthenium oxide, (7-methoxy-2-oxo-2H-chromen-4-yl) dimethyl ruthenium oxide, 4-methoxynaphthalen-1-yl)dimethyl ruthenium oxide, dimethyl (p-isopropoxycarbonylphenyl) ) cerium oxide, dimethyl (2-naphthyl) cerium oxide, dimethyl (9-fluorenyl) cerium oxide, diethyl phenyl cerium oxide, methyl ethyl phenyl cerium oxide, methyl diphenyl Cerium oxide, triphenylsulfoxide, diisopropylphenylphosphonium oxide, diphenyl(4-phenylsulfonyl-phenyl)-ruthenium oxide, 4,4'-bis(diphenylphosphonium oxide) Diphenyl sulfide, 4,4'-bis[bis[(4-(2-hydroxy-ethoxy)-phenyl)]phosphonium]diphenyl sulfide, 4,4'-bis(diphenyl) Base oxygen 鋶) biphenyl, diphenyl (o-fluorophenyl) ruthenium oxide, diphenyl (m-chlorophenyl) ruthenium oxide, diphenyl (p-bromophenyl) ruthenium oxide, diphenyl ( P-cyanophenyl)phosphonium oxide, diphenyl (m-nitrophenyl)phosphonium oxide, diphenyl (2,4,6-tribromophenyl)phosphonium oxide, diphenyl (pentafluorophenyl) ) cerium oxide, diphenyl (p-(trifluoromethyl)phenyl) ruthenium oxide, diphenyl (p-hydroxyphenyl) ruthenium oxide, diphenyl (p-fluorenylphenyl) ruthenium oxide, diphenyl (p-methylsulfinylphenyl) ruthenium oxide, diphenyl (p-methylsulfonylphenyl) ruthenium oxide, diphenyl (o-ethyl phenyl) ruthenium oxide, diphenyl ( O-benzylidene phenyl) ruthenium oxide, diphenyl (p-methylphenyl) ruthenium oxide, diphenyl (p-isopropylphenyl) ruthenium oxide, diphenyl (p-octadecyl) Phenyl) ruthenium oxide, diphenyl (p-cyclohexylphenyl) ruthenium oxide, diphenyl (p-methoxyphenyl) ruthenium oxide, diphenyl (o-methoxycarbonylphenyl) ruthenium oxide, Diphenyl (p-phenylsulfonylphenyl) ruthenium oxide, (7-methoxy-2-oxo-2H-chromen-4-yl)diphenylphosphonium oxide, (4-methoxyl) Naphthalen-1-yl)diphenylphosphonium oxide, diphenyl(p-isopropoxycarbonylphenyl)phosphonium oxide, diphenyl ( 2-naphthyl)phosphorus oxide, diphenyl(9-fluorenyl)phosphonium oxide, ethyldiphenylphosphonium oxide, methylethyl(o-methylphenyl)phosphonium oxide, methyldi(p-methylphenyl) Cerium oxide, tris(p-tolyl)phosphonium oxide, diisopropyl(4-phenylsulfonylphenyl)phosphonium oxide, diphenyl(2-thienyl)phosphonium oxide, diphenyl(2-furan) Base) cerium oxide, diphenyl (9-ethyl-9H oxazol-3-yl) ruthenium oxide, etc., however, it is not limited to these.

An example of a phosphonium cation (anthracene cation) of the general formula (6): a phosphonium cation: for example, trimethylphenylphosphonium, triethylphenylphosphonium, tetraphenylphosphonium, triphenyl (p-fluorine) Phenyl) fluorene, triphenyl (o-chlorophenyl) fluorene, triphenyl (m-bromophenyl) fluorene, triphenyl (p-cyanophenyl) fluorene, triphenyl (m-nitro Phenyl) 鏻, three Phenyl (p-phenylsulfonylphenyl) fluorene, (7-methoxy-2-oxo-2H-chromen-4-yl)triphenylphosphonium, triphenyl (o-hydroxyphenyl)鏻, triphenyl (o-ethyl phenyl) fluorene, triphenyl (m-benzyl phenyl) fluorene, triphenyl (p-methylphenyl) fluorene, triphenyl (p -isopropoxyphenyl)anthracene, triphenyl(o-methoxycarbonylphenyl)anthracene, triphenyl(1-naphthyl)anthracene, triphenyl(9-fluorenyl)anthracene, triphenyl ( 2-Thienyl) fluorene, triphenyl (2-furyl) fluorene, triphenyl (9-ethyl-9H oxazol-3-yl) hydrazine, etc., however, it is not limited to these.

An example of a ruthenium cation (pyridinium cation) of the general formula (7): a pyridinium cation: for example, N-phenylpyridinium, N-(o-chlorophenyl)pyridinium, N-(m- Chlorophenyl)pyridinium, N-(p-cyanophenyl)pyridinium, N-(o-nitrophenyl)pyridinium, N-(p-ethylphenyl)pyridinium, N-( P-isopropylphenyl)pyridinium, N-(p-octadecyloxyphenyl)pyridinium, N-(p-methoxycarbonylphenyl)pyridinium, N-(9-fluorenyl)pyridine Bismuth, 2-chloro-1-phenylpyridinium, 2-cyano-1-phenylpyridinium, 2-methyl-1-phenylpyridinium, 2-vinyl-1-phenylpyridinium, 2 -Phenyl-1-phenylpyridinium, 1,2-diphenylpyridinium, 2-methoxy-1-phenylpyridinium, 2-phenoxy-1-phenylpyridinium, 2-B Mercapto-1-(p-methylphenyl)pyridinium, 2-methoxycarbonyl-1-(p-methylphenyl)pyridinium, 3-fluoro-1-naphthylpyridinium, 4-methyl-1-( 2-furyl pyridinium, N-methylpyridinium, N-ethylpyridinium or the like, however, it is not limited thereto.

An example of a ruthenium cation (quinolinium cation) of the general formula (8): a quinolinium cation: for example, N-methylquinolinium, N-ethylquinolinium, N-phenylquinoline鎓, N-naphthylquinolinium, N-(o-chlorophenyl)quinolinium, N-(m-chlorophenyl) Quinolinium, N-(p-cyanophenyl)quinolinium, N-(o-nitrophenyl)quinolinium, N-(p-ethylphenylphenyl)quinolinium, N-( P-isopropylphenyl)quinolinium, N-(p-octadecyloxyphenyl)quinolinium, N-(p-methoxycarbonylphenyl)quinolinium, N-(9-fluorene Quinolinium, 2-chloro-1-phenylquinolinium, 2-cyano-1-phenylquinolinium, 2-methyl-1-phenylquinolinium, 2-vinyl-1 -Phenylquinolinium, 2-phenyl-1-phenylquinolinium, 1,2-diphenylquinolinium, 2-methoxy-1-phenylquinolinium, 2-phenoxy 1-phenylquinolinium, 2-ethenyl-1-phenylquinolinium, 2-methoxycarbonyl-1-phenylquinolinium, 3-fluoro-1-phenylquinolinium, 4 -methyl-1-phenylquinolinium, 2-methoxy-1-(p-methylphenyl)quinolinium, 2-phenoxy-1-(2-furyl)quinolinium, 2- Ethyl-1-(2-thienyl)quinolinium, 2-methoxycarbonyl-1-methylquinolinium, 3-fluoro-1-ethylquinolinium, 4-methyl-1-iso Propylquinolinium or the like, however, is not limited to these.

An example of a ruthenium cation (isoquinolinium cation) of the general formula (9): an isoquinolinium cation: for example, N-phenylisoquinolinium, N-methylisoquinolinium, N- Ethyl isoquinolinium, N-(o-chlorophenyl)isoquinolinium, N-(m-chlorophenyl)isoquinolinium, N-(p-cyanophenyl)isoquinolinium, N-(o-nitrophenyl)isoquinolinium, N-(p-ethylphenyl)isoquinolinium, N-(p-isopropylphenyl)isoquinolinium, N-( P-octadecyloxyphenyl)isoquinolinium, N-(p-methoxycarbonylphenyl)isoquinolinium, N-(9-fluorenyl)isoquinolinium, 1,2-diphenyl Isoquinoline quinone, N-(2-furyl)isoquinolinium, N-(2-thienyl)isoquinolinium, N-naphthylisoquinolinium, etc., however, it is not limited to these.

Equivalent to the cation of the general formula (10) (benzoxazole cation, benzothiazolium cation): Examples of benzoxazole cations include, for example, N-methylbenzoxazole oxime, N-ethylbenzoxazoloxime, N-naphthylbenzoxazoloxime, N-phenylbenzoxime Azathioprine, N-(p-fluorophenyl)benzoxazolidine, N-(p-chlorophenyl)benzoxazolidine, N-(p-cyanophenyl)benzoxazolidine, N -(o-methoxycarbonylphenyl)benzoxazolidine, N-(2-furyl)benzoxazolidine, N-(o-fluorophenyl)benzoxazoloxime, N-(p- Cyanophenyl)benzoxazolidine, N-(m-nitrophenyl)benzoxazolidine, N-(p-isopropoxycarbonylphenyl)benzoxazolidine, N-(2- Thienyl)benzoxazolidine, N-(m-carboxyphenyl)benzoxazolidine, 2-mercapto-3-phenylbenzoxazolidine, 2-methyl-3-phenylbenzoxan Azathioprine, 2-methylthio-3-(4-phenylsulfonylphenyl)benzoxazolidine, 6-hydroxy-3-(p-methylphenyl)benzoxazolidine, 7-fluorenyl- 3-phenylbenzoxazolium, 4,5-difluoro-3-ethylbenzoxazoloxime, etc., however, it is not limited to these.

Examples of the benzothiazolium cation: exemplified by N-methylbenzothiazolium, N-ethylbenzothiazolium, N-phenylbenzothiazolium, N-(1-naphthyl)benzothiazole Anthracene, N-(p-fluorophenyl)benzothiazolium, N-(p-chlorophenyl)benzothiazolium, N-(p-cyanophenyl)benzothiazolium, N-(o- Methoxycarbonylphenyl)benzothiazolium, N-(p-tolyl)benzothiazolium, N-(o-fluorophenyl)benzothiazolium, N-(m-nitrophenyl)benzo Thiazolium, N-(p-isopropoxycarbonylphenyl)benzothiazolium, N-(2-furyl)benzothiazolium, N-(4-methylthiophenyl)benzothiazolium, N -(4-phenylsulfonylphenyl)benzothiazolium, N-(2-naphthyl)benzothiazolium, N-(m-carboxyphenyl)benzothiazolium, 2-mercapto-3- Phenylbenzothiazolium, 2-methyl-3-phenylbenzothiazolium, 2-methylthio-3-phenylbenzothiazolium, 6-hydroxy-3-phenylbenzothiazole, 7 -mercapto-3-phenylbenzothiazolium, 4,5-difluoro-3- Phenylbenzothiazolium or the like, however, is not limited to these.

The ruthenium cation (furanyl or thienyl sulfonium cation) corresponding to the general formula (11): for example, difuryl hydrazine, dithienyl hydrazine, bis(4,5-dimethyl-2-furan) , bis (5-chloro-2-thienyl) fluorene, bis(5-cyano-2-furyl) fluorene, bis(5-nitro-2-thienyl) fluorene, double (5-Ethyl-2-furanyl)anthracene, bis(5-carboxy-2-thienyl)anthracene, bis(5-methoxycarbonyl-2-furyl)anthracene, bis(5-benzene) Ethyl-2-furyl)anthracene, bis(5-(p-methoxyphenyl)-2-thienyl)anthracene, bis(5-vinyl-2-furyl)anthracene, bis (5 -ethynyl-2-thienyl)anthracene, bis(5-cyclohexyl-2-furanyl)anthracene, bis(5-hydroxy-2-thienyl)anthracene, bis(5-phenoxy-2) -furanyl)anthracene, bis(5-fluorenyl-2-thienyl)anthracene, bis(5-butylthio-2-thienyl)anthracene, bis(5-phenylthio-2-thienyl)錪鎓, etc., however, is not limited to these.

The cation (diaryl sulfonium cation) corresponding to the general formula (12): for example, diphenyl hydrazine, bis(p-methylphenyl) fluorene, bis(p-octylphenyl) fluorene , bis(p-octadecylphenyl)fluorene, bis(p-octyloxyphenyl)fluorene, bis(p-octadecyloxyphenyl)fluorene, phenyl (p-octadecane) Oxyphenyl)anthracene, 4-isopropyl-4'-methyldiphenylanthracene, (4-isobutylphenyl)-p-tolylguanidine, bis(1-naphthyl)anthracene Anthracene, bis(4-phenylsulfonylphenyl)anthracene, phenyl (6-benzylidenyl-9-ethyl-9H-indazol-3-yl)anthracene, (7-methoxyl) -2-oxo-2H-chromen-3-yl)-4'-isopropylphenylhydrazine or the like, however, it is not limited thereto.

Next, the relative anion X ^- in the general formula (3) will be explained.

Counter anion in the general formula (3) X ^- no particular limitation on the principle, however, should be non-nucleophilic anion. When the relative anion X ^{- is a} non-nucleophilic anion, the nucleophilic reaction in various materials coexisting in the molecule or in various materials used in combination is not easily caused, so that the photoacid generated by the general formula (2) can be improved as a result. The stability of the agent itself or the use of its adhesive. The term "non-nucleophilic anion" as used herein refers to an anion having a low ability to cause a nucleophilic reaction. Examples of such an anion include PF ₆ ^- , SbF ₆ ^- , AsF ₆ ^- , SbCl ₆ ^- , BiCl ₅ ^- , SnCl ₆ ^- , ClO ₄ ^- , dithiocarbamate anion, SCN ^- and the like.

In the illustrated embodiment of the anion, particularly suitable as a general formula opposing anions (3) X ^- as exemplified by: PF ₆ ^-, SbF ₆ ^- and AsF ₆ ^-, particularly preferably include such as: PF ₆ ^-, SbF ₆ ^- .

Therefore, a specific example of the ideal onium salt constituting the photoacid generator (B) is an onium salt composed of the above-described exemplified general formula (3) to general formula (12). Specific examples of the structure are anions selected from the group consisting of PF ₆ ^- , SbF ₆ ^- , AsF ₆ ^- , SbCl ₆ ^- , BiCl ₅ ^- , SnCl ₆ ^- , ClO ₄ ^- , dithiocarbamate anions, and SCN ^- .

Specifically, preferred examples of the photoacid generator (B) are: "CYRACURE UVI-6992" and "CYRACURE UVI-6974" (above, manufactured by Dow Chemical Co., Ltd., Japan) "ADEKA OPTOMER SP150", "ADEKA OPTOMER SP152", "ADEKA OPTOMER SP170", "ADEKA OPTOMER SP172" (above, made by ADEKA Co., Ltd.), "IRGACURE250" (Ciba Specialty) Chemicals) System), "CI-5102", "CI-2855" (above is made by Japan's Soda Corporation), "SAN-AID SI-60L", "SAN-AID SI-80L", "SAN-AID SI-100L" , "SAN-AID SI-110L", "SAN-AID SI-180L" (above is Sanxin Chemical Co., Ltd.), "CPI-100P", "CPI-100A" (above is Sanya Pro (SAN-APRO) shares Limited), "WPI-069", "WPI-113", "WPI-116", "WPI-041", "WPI-044", "WPI-054", "WPI-055", "WPAG- 281", "WPAG-567", "WPAG-596" (above is made by Wako Pure Chemical Co., Ltd.).

The content of the photoacid generator (B) is 10 parts by weight or less, and preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, particularly preferably 0.1%, based on 100 parts by weight of the total amount of the curable component. 3 parts by weight.

<Compound (C) containing either an alkoxy group or an epoxy group>

The active energy ray-curable adhesive may contain a compound (C) containing any one of an alkoxy group and an epoxy group. For example, in the relationship with the hydroxyl group of the PVA-based polarizer, the alkoxy group-containing compound (C1) undergoes a condensation reaction of an alkoxy group with a hydroxyl group, and the epoxy group-containing compound (C2) undergoes an epoxy group. It reacts with the addition of a hydroxyl group and imparts a stronger adhesion to the active energy ray-curable adhesive. When the compound (C2) containing an epoxy group is used, a secondary hydroxyl group is formed after the reaction by an addition reaction of an epoxy group and a hydroxyl group, and the overall water absorption rate of the present invention may be increased, and therefore, it is more preferable to have Alkoxy compound (C1). That is, an active energy ray-curable adhesive containing a photoacid generator (B) and a compound (C1) having an alkoxy group is laminated, and a polarizing member and a transparent protective film are laminated and produced by active energy ray irradiation. An acid derived from a photoacid generator (B), a compound having an alkoxy group (C1) The alkoxy group and the hydroxyl group of the polarizing member undergo a condensation reaction, and a good adhesion between the polarizing member and the transparent protective film is exhibited. Further, by the condensation reaction of the alkoxy group-containing compound (C1), an adhesive layer having a lower water absorption rate is formed, and the optical durability in a severe environment under high temperature and high humidity can be satisfied.

In the foregoing active energy ray-curable adhesive, comprising an alkoxy The compound (C) of any one of the group and the epoxy group may be used singly or in combination of plural kinds. Further, the compound (C) containing any one of an alkoxy group and an epoxy group may be used in combination with a compound (C1) containing an alkoxy group and a compound (C2) containing an epoxy group. Further, the compound (C) containing any one of an alkoxy group and an epoxy group may be used together with or without a photoacid generator (B), however, if the hydroxyl group and the alkoxy group of the PVA-based polarizer are promoted. In view of the reaction of the epoxy group, the compound (C) containing either an alkoxy group or an epoxy group is preferably used in combination with the photoacid generator (B).

(Alkoxy group-containing compound (C1))

The compound (C1) having an alkoxy group in the molecule is not particularly limited as long as it has one or more alkoxy groups in the molecule, and a known one can be used. For example, it can be exemplified by having the general formula: -(CH ₂ ) _n -OR (wherein n is an integer of 1 to 3, and R is an alkyl group having 1 to 4 carbon atoms or H. In the above formula R is preferably a compound in which alkoxy groups represented by a methyl group are used as a substituent. Specifically, for example, an alkoxy group-containing radical polymerizable compound such as an alkoxyalkyl (meth) acrylate or an alkoxyalkyl (meth) acrylamide or a hydroxyl group is exemplified. A melamine compound such as melamine or alkoxymethylated melamine, an amine resin, and a decane coupling agent. Specific examples of the alkoxy group-containing radical polymerizable compound include WASMER 2MA, WASMER 3MA, WASMER IBM, N-isobutoxymethacrylamide, WASMER EMA, and N-MAM manufactured by Takino Industrial Co., Ltd. - PC, MM90, WASMER A, etc. Specific examples of the melamine compound can be exemplified by M-3, MK, M-6, M-100, MC, etc. of the SUMITEX RESIN series manufactured by Sumitomo Chemical Co., Ltd. or NIKALAC MW-30, MW-100LM manufactured by Sanwa Chemical Co., Ltd. , MX-750LM, MX-280, MX-270, etc. Among these, WASMER 2MA, N-MAM-PC, MX-750LM, etc. are used from a viewpoint of reactivity. Further, when the glass transition temperature Tg of the adhesive layer was calculated, the compound having no alkoxy group and the polymer (C1) were not included in the calculation.

(A compound having an epoxy group (C2))

As the compound (C2) having an epoxy group, a compound having one or more epoxy groups in the molecule or a polymer (epoxy resin) having two or more epoxy groups in the molecule can be used. When a polymer (epoxy resin) is used, a compound having two or more functional groups having reactivity with an epoxy group in the molecule may be used in combination. Here, the functional group having reactivity with an epoxy group is exemplified by a carboxyl group, a phenolic hydroxyl group, a mercapto group, a primary or secondary aromatic amine group, and the like. In view of the three-dimensional hardenability, it is particularly preferable that the functional groups have two or more in one molecule.

For example, a polymer having one or more epoxy groups in the molecule may, for example, be an epoxy resin, and includes: a bisphenol A type epoxy resin derived from bisphenol A and epichlorohydrin, derived from a double Bisphenol F epoxy resin of phenol F and epichlorohydrin, bisphenol S epoxy resin, phenol novolak epoxy resin, cresol novolac epoxy resin, bisphenol A phenolic epoxy resin, bisphenol F phenolic Epoxy resin, alicyclic epoxy resin, diphenyl ether epoxy resin, hydroquinone epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, fluorene epoxy resin, trifunctional A polyfunctional epoxy resin such as an epoxy resin or a tetrafunctional epoxy resin, a glycidyl ester epoxy resin, a glycidylamine epoxy resin, an allantoin epoxy resin, or a trimeric isocyanate epoxy resin. An aliphatic chain epoxy resin or the like, and the epoxy resins may be halogenated or hydrogenated. For example, commercially available epoxy resin products can be exemplified by JER Coatings 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000, manufactured by Japan Epoxy Resin Co., Ltd. EPICLON830, EXA835LV, HP4032D, HP820 made by DIC Co., Ltd., EP4100 series, EP4000 series, EPU series made by AIDCO Co., Ltd., CELLOXIDE series (2021, 2021P, 2083) manufactured by DAICEL Chemical Co., Ltd. , 2085, 3000, etc.), EPOLEAD series, EHPE series, YD series, YDF series, YDCN series, YDB series, phenoxy resin (polyhydroxyl synthesized from bisphenols and epichlorohydrin) The polyether has an epoxy group at both ends, a YP series or the like, a DENACOL series manufactured by Nagase Chemtex Co., Ltd., an EPOLIGHT series manufactured by Kyoritsu Chemical Co., Ltd., and the like, but is not limited thereto. These epoxy resins may be used in combination of two or more kinds. Further, when the glass transition temperature Tg of the adhesive layer was calculated, the compound (C2) having an epoxy group was not included in the calculation.

Containing alkoxygen with respect to 100 parts by weight of the total amount of the curable component The blending amount of the compound (C) of any one of the group and the epoxy group is usually 30 parts by weight or less, and the content of the aforementioned compound (C) in the active energy ray-curable adhesive is contained. If the amount is too large, the adhesion is lowered, and the impact resistance to the drop test is deteriorated. The content of the aforementioned compound (C) in the active energy ray-curable adhesive is more preferably 20 parts by weight or less. On the other hand, the active energy ray-curable adhesive preferably contains the compound (C) in an amount of 2 parts by weight or more, more preferably 5 parts by weight or more, from the viewpoint of water resistance.

<isocyanate compound (D)>

The active energy ray-curable adhesive of the present invention may contain an isocyanate compound (D). The isocyanate compound (D) is a compound having at least one isocyanate group in the molecule. When the active energy ray-curable adhesive contains the isocyanate compound (D), the hydroxy group on the surface of the polarizer interacts with the isocyanate group to impart stronger adhesion and water resistance to the polarizing film. Further, when the active energy ray-curable adhesive contains a N-hydroxyalkyl group-containing (meth) acrylamide derivative as a radical polymerizable compound, if it contains an N-hydroxyalkyl group (meth) propylene oxime When the content of the amine derivative is increased, since the hydroxyl group is contained in the adhesive layer, the overall water absorption rate tends to increase, and as a result, the optical durability in a severe humidifying environment tends to decrease. By using a combination of a (meth) acrylamide derivative containing an N-hydroxyalkyl group and a compound having an isocyanate group, it does not contribute to the formation of a urethane bond with the hydroxyl group and the isocyanate group of the polarizer. It can reduce the overall water absorption while maintaining the adhesion.

The isocyanate compound (D) may, for example, be a polyfunctional isocyanate A compound, an active energy ray-hardening isocyanate compound, or the like. For example, the polyfunctional isocyanate compound may, for example, be a lower aliphatic ester such as 1,2-ethylidene diisocyanate, 1,4-butylene diisocyanate or 1,6-hexamethylene diisocyanate. Aliphatic polyisocyanates; cyclopentadienyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated methyl phenyl diisocyanate, hydrogenated xylene diisocyanate and other alicyclic polyisocyanates; An aromatic polyisocyanate such as 4-methylphenyl diisocyanate, 2,6-methylphenylene diisocyanate, 4,4'-diphenylmethane diisocyanate or decyl diisocyanate. For example, the isocyanate compound (D) may, for example, be a trimethylolpropane/methylphenylene diisocyanate adduct (manufactured by Nippon Polyurethane Co., Ltd., trade name "CORONATE L"). ], trimethylolpropane / hexamethylene diisocyanate adduct [manufactured by Japan Polyurethane Co., Ltd., trade name "CORONATE HL"], trade name "CORONATE HX" (Japanese polyamine base) A commercially available product such as a formate (Indole Chemical Co., Ltd.), a trimethylolpropane/extension-based diisocyanate adduct (manufactured by Mitsui Chemicals, Inc., trade name "TAKENATE110N"). The active energy ray-curable isocyanate compound (D) is, for example, an isocyanate having a (meth) acrylonitrile group, and, for example, KARENZ AOI (manufactured by Showa Denko Co., Ltd.) and KARENZ BEI (Showa Denko) Commercial products such as Co., Ltd., and Laromer LR9000 (manufactured by BASF Corporation).

Isocyanate relative to 100 parts by weight of the total amount of the curable component The blending amount of the compound (D) is usually 30 parts by weight or less, and if the content of the compound (D) in the active energy ray-curable adhesive is too large, the adhesion is lowered and the impact resistance against the drop test is obtained. The situation of deterioration. The content of the aforementioned compound (D) in the active energy ray-curable adhesive is more preferably 20 parts by weight or less. On the other hand, from the viewpoint of water resistance, the active energy ray-curable adhesive preferably contains 0.1 parts by weight or more of the above compound (D), and more preferably It is preferred to contain 1 part by weight or more.

<Chane coupling agent (E)>

When the curable adhesive for a polarizing film of the present invention is an active energy ray-curable curing type, the active energy ray-curable compound is preferably used as the decane coupling agent (E). However, the active energy ray-curable compound may be used in the same manner. Water resistance.

As a specific example of the decane coupling agent (E), active energy ray hardening The compound may, for example, be vinyl trichloromethane, vinyl trimethoxy decane, vinyl triethoxy decane, 2-(3,4 epoxycyclohexyl)ethyltrimethoxy decane, 3-epoxy propyl Oxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, p-styryltrimethoxydecane , 3-methacryloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxy Decane, 3-methacryloxypropyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, and the like.

More preferred are 3-methacryloxypropyltrimethoxydecane and 3-propenyloxypropyltrimethoxydecane.

A specific example of the decane coupling agent which is not an active energy ray-hardening property is preferably a decane coupling agent (E1) having an amine group. Specific examples of the decane coupling agent (E1) having an amine group include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, and γ-aminopropyltriisopropoxydecane. Γ-aminopropylmethyldimethoxydecane, γ-aminopropylmethyldiethoxydecane, γ-(2-aminoethyl)aminepropyltrimethoxydecane, γ-(2-amine B Aminopropylmethyldimethoxydecane, γ-(2-aminoethyl)aminepropyltriethoxydecane, γ-(2-amine B Aminopropylmethyldiethoxydecane, γ-(2-aminoethyl)aminepropyltriisopropoxydecane, γ-(2-(2-aminoethyl)amineethyl)amine C Trimethoxy decane, γ-(6-aminohexyl)aminopropyltrimethoxydecane, 3-(N-ethylamino)-2-methylpropyltrimethoxydecane, γ-ureidopropyltrimethoxy Baseline, γ-ureidopropyltriethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, N-benzyl-γ-aminopropyltrimethoxydecane, N-vinylbenzyl - γ-aminopropyltriethoxydecane, N-cyclohexylaminomethyltriethoxydecane, N-cyclohexylaminomethyldiethoxymethyldecane, N-phenylaminomethyl An amino group-containing decane such as trimethoxy decane, (2-aminoethyl)amine methyltrimethoxynonane or N,N'-bis[3-(trimethoxyindolyl)propyl]ethylenediamine; a ketimine-type decane such as N-(1,3-dimethylbutylidene)-3-(triethoxyindolyl)-1-propanamine.

The decane coupling agent (E1) having an amine group may also be used alone, and A plurality of types can also be used in combination. In these, in order to ensure good adhesion, it is preferably γ-aminopropyltrimethoxydecane, γ-(2-aminoethyl)aminepropyltrimethoxydecane, γ-(2-aminoethyl). Aminopropylmethyldimethoxydecane, γ-(2-aminoethyl)aminepropyltriethoxydecane, γ-(2-aminoethyl)aminepropylmethyldiethoxydecane, N -(1,3-Dimethylbutylene)-3-(triethoxyindolyl)-1-propanamine.

Decane coupling relative to 100 parts by weight of the total amount of the hardenable component The blending amount of the agent (E) is preferably in the range of 0.01 to 20 parts by weight, and is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight. This is because when the blending amount is more than 20 parts by weight, the storage stability of the adhesive is deteriorated, and when it is less than 0.1 part by weight, the effect of water resistance resistance cannot be sufficiently exhibited. In addition, when calculating the glass transition temperature Tg of the adhesive layer, the decane coupling agent is not formed. (E) included in the calculation.

a non-active energy ray-curable decane coupling agent other than the above Specific examples thereof include 3-ureidopropyltriethoxydecane, 3-chloropropyltrimethoxydecane, 3-mercaptopropylmethyldimethoxydecane, and 3-mercaptopropyltrimethoxydecane. , bis(triethoxydecylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxydecane, imidazolium, and the like.

For the aforementioned photoacid generator (B), comprising an alkoxy group, an epoxy group The compound (C), the isocyanate compound (D), and the decane coupling agent (E) of any of them is preferably a log Pow value of 1 or more, and more preferably 2 or more. Further, the photoacid generator (B) and the decane coupling agent (E) are not included in the calculation of the log Pow value of the curable adhesive for polarizing film. On the other hand, the compound (C) containing any one of an alkoxy group and an epoxy group, and the isocyanate compound (D) are contained in the calculation of the logPow value of the hardening type adhesive for polarizing film.

<Additives other than the aforementioned>

Further, in the curable adhesive for a polarizing film of the present invention, various additives may be blended as other optional components insofar as the object and effect of the present invention are not impaired. The foregoing additives may, for example, be polyamine, polyamidoximine, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymerization. a polymer or oligomer such as a substance, a petroleum resin, a xylene resin, a ketone resin, a cellulose resin, a fluorine-based oligomer, a polyoxynene oligomer, or a polysulfide oligomer; phenothiazine, 2, a polymerization inhibitor such as 6-di-t-butyl-4-methylphenol; a polymerization initiator; a leveling agent; a wettability improver; a surfactant; a plasticizer; a UV absorber; an inorganic filler; Dyes, etc. Among various additives, it is also preferred that the logPow value is high. The logPow value of each of the additives is preferably 2 or more, and more preferably 3 or more, and most preferably 4 or more. Further, the additives are not included in the calculation of the log Pow value of the hardening type adhesive for polarizing film.

The aforementioned addition with respect to 100 parts by weight of the total amount of the curable component The agent is usually 0 to 10 parts by weight, and preferably 0 to 5 parts by weight, most preferably 0 to 3 parts by weight.

<Adhesive viscosity>

The curable adhesive for a polarizing film of the present invention contains the curable component. However, from the viewpoint of coatability, the adhesive has a viscosity of preferably 100 cp or less at 25 °C. On the other hand, when the curable adhesive for a polarizing film of the present invention is at most 100 cp at 25 ° C, it can be used by controlling the temperature of the adhesive at the time of coating and adjusting it to 100 cp or less. The more ideal range of viscosity is 1~80cp, and the most ideal is 10~50cp. The viscosity can be measured using an E-type viscometer TVE22LT manufactured by Toki Sangyo Co., Ltd.

Moreover, if viewed from the viewpoint of safety, the polarizing thin of the present invention As the curable adhesive for film, a material having low skin irritation is preferably used as the curable component. Skin irritation can be judged by the index of the so-called P.I.I. P.I.I is widely used to show the degree of skin disorder and is determined by the Cui method. The measured value is expressed in the range of 0 to 8. The smaller the value, the lower the irritancy is determined. However, since the error of the measured value is large, it can be grasped as a reference value. P.I.I is preferably 4 or less, and more preferably 3 or less, and most preferably 2 or less.

<Polarized film>

The polarizing film of the present invention is separated from at least one side of the polarizing member by the aforementioned partial A thin protective film is adhered to the adhesive layer formed of the cured layer of the cured adhesive for the light film. As described above, the adhesive layer belonging to the above-mentioned cured layer has an overall water absorption of 10% by weight or less.

<Binder layer>

The thickness of the adhesive layer formed by the above-mentioned hardening type adhesive is preferably controlled to be 0.1 to 3 μm. The thickness of the layer of the agent is preferably from 0.3 to 2 μm, and more preferably from 0.5 to 1.5 μm. It is preferable that the thickness of the adhesive layer is 0.1 μm or more in suppressing the occurrence of defects or the formation of defects (bubbles) by the cohesive force of the adhesive layer. On the other hand, if the adhesive layer is thicker than 3 μm, the polarizing film may not satisfy the durability.

Further, the hardening type adhesive is preferably selected as the adhesive formed thereby The Tg of the layer will be 60 ° C or higher, and more preferably 70 ° C or higher, and more preferably 75 ° C or higher, further 100 ° C or higher, or even 120 ° C or higher. On the other hand, if the Tg of the adhesive layer is too high, the flexibility of the polarizing film is lowered. Therefore, the Tg of the adhesive layer is preferably 300 ° C or lower, further 240 ° C or lower, or even 180 ° C or lower. Tg <glass transition temperature> was measured using a dynamic viscoelasticity measuring apparatus RSAIII manufactured by TA Instruments, and was measured by the following measurement conditions.

Specimen size: width 10mm, length 30mm, clamp distance 20mm, measurement mode: stretching, frequency: 1 Hz, heating rate: 5 ° C / min

The dynamic viscoelasticity was measured and used as the temperature Tg of the peak of tan δ.

Further, the hardening type adhesive is preferably 1.0 × 10 ⁶ Pa or more in a field in which the storage modulus of the adhesive layer formed is 70 ° C or less. Further, it is more preferably 1.0 × 10 ⁷ Pa or more. The storage modulus of the subsequent layer affects the polarizer crack when the polarizing film is subjected to thermal cycling (-40 ° C to 80 ° C, etc.), and when the storage modulus is low, the problem of cracking of the polarizer is liable to occur. The temperature field having a high storage modulus is preferably 80 ° C or less, and most preferably 90 ° C or less. The storage modulus was measured simultaneously with Tg <glass transition temperature> using a dynamic viscoelasticity measuring apparatus RSAIII manufactured by TA Instruments, and was measured by the same measurement conditions. The dynamic viscoelasticity was measured and the value of the storage modulus (Eˊ') was used.

The polarizing film according to the present invention has a step of bonding a polarizing member and a transparent protective film after the surface of the polarizing member forming the adhesive layer and/or the surface of the transparent protective film forming the adhesive layer is coated with a curing adhesive; A step of hardening the hardening type adhesive to form an adhesive layer.

The polarizing member and the transparent protective film may be subjected to surface modification treatment before the application of the hardening type adhesive. Specific treatments include, for example, treatment by corona treatment, plasma treatment, saponification treatment, and the like.

The coating method of the hardening type adhesive can be appropriately selected depending on the viscosity of the hardening type adhesive or the target thickness. For example, examples of the coating method include, for example, a reverse coater, a gravure coater (direct, reverse or indirect), a bar reverse coater, a roll coater, and a die-casting die coating. Machine, bar coater, rod coater, etc. In addition to this, the coating may suitably be carried out by means of a dipping method or the like.

The polarizing member and the transparent protective film are bonded to each other via a hardening type adhesive which has been coated as described above. The bonding of the polarizing member and the transparent protective film can be performed by a roll laminator or the like.

<hardening of adhesive>

The curable adhesive for a polarizing film of the present invention can be used as an active energy ray-curable adhesive or a thermosetting adhesive. In the active energy ray-curable adhesive, it can be used in an electron beam curing type, an ultraviolet curing type, or a visible light curing type. From the viewpoint of productivity, the aspect of the hardening type adhesive is that the active energy ray-curable adhesive is superior to the heat-curing adhesive, and further, from the viewpoint of productivity, the active energy ray The hardening type adhesive is preferably a visible light curing type adhesive.

Active Light Wire Hardening

In the active energy ray-curable adhesive, after bonding the polarizer and the transparent protective film, the active energy ray (electron ray, ultraviolet ray, visible light, etc.) is irradiated, and the active energy ray-curable adhesive is hardened to form an adhesive layer. . The irradiation direction of the active energy ray (electron ray, ultraviolet ray, visible ray, etc.) can be irradiated from any appropriate direction. It is desirable to irradiate from the side of the transparent protective film. When the light is irradiated from the side of the polarizer, the polarizer is deteriorated by the active energy rays (electron rays, ultraviolet rays, visible rays, etc.).

"Electronic ray hardening type"

In the electron beam curing type, the irradiation conditions of the electron beam may be any suitable conditions as long as the active energy ray-curable adhesive can be cured. For example, the electron beam irradiation is preferably an acceleration voltage of 5 kV to 300 kV, and more preferably 10 kV to 250 kV. When the accelerating voltage is less than 5 kV, the electron beam cannot reach the adhesive and there is insufficient hardening. If the accelerating voltage is greater than 300 kV, the penetration of the sample is too strong to cause damage to the transparent protective film or the polarizing member. The amount of illumination line is 5 to 100 kGy, and more preferably 10 to 75 kGy. When the amount of illumination is less than 5kGy, the adhesive will harden. If it is more than 100 kGy, the transparent protective film or the polarizing member may be damaged, and the mechanical strength may be lowered or yellowed, and predetermined optical characteristics may not be obtained.

Electron beam irradiation is usually carried out in an inert gas, However, if necessary, it can also be carried out in the atmosphere or with a small amount of oxygen introduced. Although it differs depending on the material of the transparent protective film, by appropriately introducing oxygen, the surface of the transparent protective film on which the electron beam is initially irradiated is intentionally caused to suppress oxygen, and damage to the transparent protective film can be prevented, and the film can be effectively and effectively The electron beam is irradiated only to the adhesive.

"Ultraviolet hardening type, visible light curing type"

In the method for producing a polarizing film according to the present invention, it is preferable to use an active energy ray including a visible light having a wavelength range of 380 nm to 450 nm, particularly a visible light having a wavelength range of 380 nm to 450 nm. In the ultraviolet curing type or the visible light curing type, when a transparent protective film (ultraviolet-opaque transparent protective film) which has been provided with ultraviolet absorbing ability is used, since light having a wavelength shorter than 380 nm is substantially absorbed, light having a wavelength shorter than 380 nm is used. The active energy ray-curable adhesive does not reach the polymerization reaction. Further, light having a wavelength shorter than 380 nm absorbed by the transparent protective film is converted into heat, and the transparent protective film itself generates heat, which causes defects such as curling and wrinkles of the polarizing film. Therefore, when the ultraviolet curable type or the visible light curing type is used in the present invention, the active energy ray generating means should preferably use a device that does not emit light having a wavelength shorter than 380 nm, and more specifically, the cumulative illuminance in the wavelength range of 380 to 440 nm. The ratio of the cumulative illumination of the wavelength range of 250 to 370 nm is preferably 100:0 to 100:50, and is more suitable. It is 100:0~100:40. The active energy ray of the present invention is preferably a metal halide lamp enclosed in gallium and an LED light source having an emission wavelength range of 380 to 440 nm. Alternatively, 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, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, a gallium lamp, an excimer laser or Sunlight and the like include a source of ultraviolet light and visible light, and a band pass filter can also be used to block ultraviolet rays having a wavelength shorter than 380 nm. In order to improve the adhesion properties of the adhesive layer between the polarizer and the transparent protective film, and to prevent the curling of the polarizing film, it is preferable to use the following active energy ray, that is, using a metal halide lamp sealed with gallium and transmitting a wavelength shorter than 380 nm. The active energy line obtained by the band pass filter of the light, or the active energy line having a wavelength of 405 nm obtained by using the LED light source.

Suitable for irradiation in ultraviolet curing or visible light curing The active energy ray-curable adhesive is heated before the ultraviolet ray or visible light (warming before irradiation). In this case, the temperature is preferably 40 ° C or higher, and more preferably 50 ° C or higher. Further, it is also preferable to heat the active energy ray-curable adhesive after irradiation with ultraviolet rays or visible rays (heating after irradiation). In this case, it is preferable to increase the temperature to 40 ° C or higher, and more preferably to 50 ° C or higher.

The active energy ray-curable adhesive of the present invention can be suitably used, in particular, for forming an adhesive layer of a transparent protective film which is followed by a polarizing member and a light transmittance of less than 5% at a wavelength of 365 nm. Here, the active energy ray-curable adhesive of the present invention contains the photopolymerization initiator of the above general formula (1), whereby the transparent protective film having UV absorbing ability can be irradiated with ultraviolet rays to be hardened to form an adhesive layer. . Accordingly, even a transparent protective film having UV absorbing ability has been laminated on the partial In the polarizing film on both sides of the light member, the adhesive layer can also be hardened. However, it is a matter of course that the adhesive layer can be hardened in a polarizing film which has been laminated with a transparent protective film having no UV absorbing ability. Further, the transparent protective film having a UV absorbing ability means a transparent protective film having a transmittance of light of 380 nm of less than 10%.

The method of imparting UV absorbing ability to the transparent protective film may be, for example, a method of including a UV absorber in the transparent protective film, or a method of laminating a surface treatment layer containing the ultraviolet absorber on the surface of the transparent protective film.

For example, specific examples of the ultraviolet absorber may be, for example, A well-known oxydiphenyl ketone type compound, a benzotriazole type compound, a salicylate type compound, a diphenyl ketone type compound, a cyanoacrylate type compound, a nickel-salt salt type compound, a triazine type compound, etc. .

After bonding the polarizer and the transparent protective film, an active energy ray (electron ray, ultraviolet ray, visible light, or the like) is irradiated, and the active energy ray-curable adhesive is cured to form an adhesive layer. The irradiation direction of the active energy ray (electron ray, ultraviolet ray, visible ray, etc.) can be irradiated from any appropriate direction. It is desirable to irradiate from the side of the transparent protective film. When the light is irradiated from the side of the polarizer, the polarizer is deteriorated by the active energy rays (electron rays, ultraviolet rays, visible rays, etc.).

"thermosetting type"

On the other hand, in the thermosetting type adhesive, after the polarizing member and the transparent protective film are bonded, polymerization is started by the thermal polymerization initiator by heating, and a cured layer is formed. Heating temperature can be set according to thermal polymerization initiator Set, but 60~200 °C, and preferably 80~150 °C.

When manufacturing a polarizing film according to the present invention by a continuous wire, the wire Although the speed varies depending on the hardening time of the adhesive, it is preferably from 1 to 500 m/min, and more preferably from 5 to 300 m/min, and further preferably from 10 to 100 m/min. When the linear velocity is too small, the productivity is lacking, or the damage to the transparent protective film is too large to produce a polarizing film which can withstand durability tests and the like. When the linear velocity is too large, the hardening of the adhesive is insufficient, and there is a case where the target is not obtained.

In addition, the polarizing film of the present invention is hard across the active energy ray The adhesive layer formed by the cured layer of the chemical adhesive adheres to the polarizer and the transparent protective film. However, an easy adhesion layer may be disposed between the transparent protective film and the adhesive layer. For example, the easy-adhesive layer may have a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a polyoxyl system, a polyamine skeleton, a polyimine skeleton, and a polyethylene. It is formed by various resins such as an alcohol skeleton. These polymer resins may be used alone or in combination of two or more. Further, other additives may be added to the formation of the easy adhesion layer. Specifically, a stabilizer such as an adhesion-imparting agent, an ultraviolet absorber, an antioxidant, or a heat-resistant stabilizer can be further used.

The easy-adhesive layer is usually disposed in advance on the transparent protective film, and the easy-contact layer side of the transparent protective film and the polarizing member are bonded by the adhesive layer. The formation of the easy-adhesion layer is carried out by coating and drying the formation of the easily-adhesive layer by a known technique on the transparent protective film. The formation of the easy-adhesion layer is usually adjusted to a solution which has been diluted to a suitable concentration in consideration of the thickness after drying, the smoothness of coating, and the like. The thickness of the easy-to-layer layer after drying is preferably 0.01~5μm, and more preferably 0.02~2μm, and further preferably 0.05~1μm. Further, the easy-adhesion layer may be provided with a plurality of layers, however, in this case, the total thickness of the easy-adhesion layer is also preferably made into the aforementioned range.

<polarizer>

The polarizer is not particularly limited, and various polarizers can be used. For example, the polarizing member may be, for example, a dichroic material such as iodine or a dichroic dye adsorbed on a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or ethylene. The vinyl acetate copolymer is a hydrophilic polymer film such as a partially saponified film, and a polyaxial oriented film such as a uniaxially stretched product, a dehydrated product of polyvinyl alcohol, or a dechlorinated product of polyvinyl chloride. Among these, it is also suitable as a polarizer composed of a polyvinyl alcohol-based film and a dichroic substance such as iodine. The thickness of the polarizing members is not particularly limited, however, it is generally 80 μm or less.

For example, a polarizing member which dyes a uniaxially stretched polyvinyl alcohol film by iodine can be produced by immersing polyvinyl alcohol in an aqueous solution of iodine, and extending it to an original length. 3 to 7 times. If necessary, it may be immersed in an aqueous solution of boric acid or potassium iodide. Further, if necessary, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, the surface of the polyvinyl alcohol-based film can be washed with dirt or an anti-caking agent. In addition, by swelling the polyvinyl alcohol-based film, it is possible to prevent uneven dyeing. Uniform effect. The extension can be carried out by dyeing with iodine, or by stretching on one side, or by iodine after stretching. It can also be extended in an aqueous solution of boric acid or potassium iodide or in a water bath.

Further, the hardening type adhesive of the present invention has a thickness of 10 μm. When the following thin polarizing member is used as a polarizing member, the effect can be clearly exhibited (to satisfy the optical durability in a severe environment under high temperature and high humidity). Compared with a polarizing member having a thickness of more than 10 μm, the polarizing member having a thickness of 10 μm or less has a relatively large influence on moisture, and has insufficient optical durability under an environment of high temperature and high humidity, and is liable to cause an increase in transmittance or a decrease in polarization. . In other words, when the polarizer of 10 μm or less is laminated by the adhesive having an overall water absorption of 10% by weight or less according to the present invention, it is possible to prevent the movement of the water toward the polarizer under the environment of severe high temperature and high humidity. The deterioration of the optical durability such as the increase in the transmittance of the polarizing film and the decrease in the degree of polarization is suppressed. From the viewpoint of thinning, the thickness of the polarizer is preferably 1 to 7 μm. Such a thin polarizer has a small thickness unevenness, is excellent in visibility, and has little dimensional change. Further, it is preferable that the thickness of the polarizing film is reduced in thickness.

For the sake of representative, thin polarizers can be listed, for example, as disclosed in Japan. Japanese Patent Publication No. Sho. No. Sho. No. No. 2010-269 Thin polarizing film. The thin polarizing film can be obtained by a method comprising the steps of: extending a layer of a polyvinyl alcohol resin (hereinafter also referred to as a PVA resin) and a resin substrate for stretching in a state of a laminate; And the step of dyeing. According to this production method, even if the PVA-based resin layer is thin, by supporting the resin substrate for stretching, it is not stretchable due to problems such as cracking due to stretching.

In the method of including the step of extending in the state of the laminated body and the step of dyeing, if the polarizing property is improved by extending to a high magnification In view of the above, the thin polarizing film is also preferably included in the specification as disclosed in the specification of WO2010/100917, the specification of PCT/JP2010/001460, or the specification of Japanese Patent Application No. 2010-269002 or the specification of Japanese Patent Application No. 2010-263692. The step of the step of extending the aqueous solution of the boric acid is carried out, in particular, the step of assisting in the air extension in the aqueous solution of boric acid, as disclosed in the specification of Japanese Patent Application No. 2010-269002 or the specification of Japanese Patent Application No. 2010-263692. The method of production.

Thin as disclosed in the aforementioned specification of PCT/JP2010/001460 The high-performance polarizing film is integrally formed on a resin substrate, and is composed of a PVA-based resin which has been oriented with a dichroic substance, and has a thickness of 7 μm or less and a single transmittance of 42.0% or more and a degree of polarization. It is an optical characteristic of 99.95% or more.

The aforementioned thin high-performance polarizing film can be manufactured as follows: By applying and drying a PVA-based resin, a PVA-based resin layer is formed on a resin substrate having a thickness of at least 20 μm, and the formed PVA-based resin layer is immersed in a dyeing liquid of a dichroic substance, and two colors are obtained. The PVA-based resin layer which has adsorbed the dichroic substance and the resin base material are integrally formed in the boric acid aqueous solution, and the total stretching ratio is 5 times or more of the original length.

Moreover, a manufacturing consists of a thin film that has been oriented to direct the dichroic material. A method for forming a laminate film of a high-performance polarizing film, comprising the steps of: forming a laminate film comprising a resin substrate and a PVA-based resin layer, wherein the resin substrate has at least 20 μm The thickness of the PVA-based resin layer is due to the inclusion of PVA on one side of the resin substrate. The aqueous solution of the resin is applied and dried, and the adsorption step is performed by immersing the laminated film including the resin substrate and the PVA-based resin layer formed on one surface of the resin substrate in a dye containing a dichroic substance. In the liquid, the PVA-based resin layer contained in the laminated film is adsorbed to the dichroic material; and the stretching step is carried out in an aqueous solution of boric acid to form the laminated film including the PVA-based resin layer to which the dichroic substance has been adsorbed. The stretching is performed in such a manner that the stretching is 5 times or more of the original length; and the step of producing the laminated film is carried out by integrally extending the PVA-based resin layer which has adsorbed the dichroic substance and the resin substrate The thin high-performance polarizing film is formed on one side of the material, and the thin high-performance polarizing film is composed of a PVA-based resin layer which has been oriented with a dichroic substance, has a thickness of 7 μm or less, and has a single transmittance of 42.0%. The optical characteristics of the above and the degree of polarization are 99.95% or more; whereby the thin high-performance polarizing film can be manufactured.

The thin polarizing film of the above-mentioned Japanese Patent Application No. 2010-269002 or the specification of Japanese Patent Application No. 2010-263692 is a polarizing film of a continuous base material composed of a PVA-based resin which has been oriented with a dichroic substance, and includes a film which has been formed into a film. The laminate of the PVA-based resin layer of the amorphous ester-based thermoplastic resin substrate is stretched by a two-stage stretching step, thereby forming a thickness of 10 μm or less, and the two-stage extension step is extended by air and boric acid. It consists of an extension of water. When the monomer transmittance is T and the degree of polarization is made to P, the thin polarizing film is preferably formed to have a P>-(10 ^{0.929T-42.4-1} )×100 (however, T<42.3) and P≧99.9. (However, T≧42.3) the optical properties of the conditions.

Specifically, the aforementioned thin polarizing film can include the following steps A method for producing a thin-type polarizing film, that is, a step of generating a high-temperature extension of a PVA-based resin layer of a non-crystalline ester-based thermoplastic resin substrate which has been formed into a continuous base material, An extended intermediate product composed of a PVA-based resin layer which has been oriented; in one step, by the adsorption of a dichroic substance which extends the intermediate product, a dichroic substance (preferably iodine or iodine and organic) is formed. a mixture of dyes; a colored intermediate product composed of an oriented PVA-based resin layer; and a step of forming a PVA-based resin layer having a dichroic substance oriented by stretching the boric acid water of the colored intermediate product A polarizing film having a thickness of 10 μm or less is formed.

In the manufacturing method, using high temperature extension in the air and boric acid water The total stretching ratio of the PVA-based resin layer which has been formed into a film of the amorphous ester-based thermoplastic resin substrate is preferably 5 times or more. The liquid temperature of the boric acid aqueous solution for extending the boric acid water can be made 60 ° C or higher. Before the colored intermediate product is extended in the aqueous boric acid solution, the colored intermediate product is preferably subjected to insolubilization treatment. In this case, it is preferred to immerse the colored intermediate product in a boric acid aqueous solution having a liquid temperature of not more than 40 °C. The amorphous ester-based thermoplastic resin substrate can be formed as a copolymerized polyethylene terephthalate containing copolymerized polyethylene terephthalate copolymerized with isononanoic acid and copolymerized with cyclohexanedimethanol. Or other amorphous polyethylene terephthalate copolymerized with polyethylene terephthalate, and preferably composed of a transparent resin, the thickness of which may be more than 7 times the thickness of the formed PVA resin layer. . Further, the stretching ratio of the high-temperature extension in the air is preferably 3.5 times or less, and the extension temperature of the high-temperature extension in the air is preferably a glass transition temperature of the PVA-based resin or more, specifically, a range of 95 ° C to 150 ° C. When the high temperature extension in the air is carried out by the uniaxial extension of the free end, the film has been formed into an amorphous state. The total stretching ratio of the PVA-based resin layer of the ester-based thermoplastic resin substrate is preferably 5 times or more and 7.5 times or less. In addition, when the high-temperature extension in the air is performed by the uniaxial stretching at the fixed end, the total stretch ratio of the PVA-based resin layer which has been formed on the amorphous ester-based thermoplastic resin substrate 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 in which a continuous binder of polyethylene terephthalate (amorphous PET) is copolymerized with isonononic acid copolymerized with 6 mol% of isononanoic acid. The glass transition temperature of the amorphous PET was 75 °C. A laminate comprising a continuous PET base material and a polyvinyl alcohol (PVA) layer was produced as follows. Incidentally, the glass transition temperature of PVA is 80 °C.

A 200 μm thick amorphous PET substrate was prepared, and a PVA aqueous solution having a polymerization degree of 1,000 or more and a saponification degree of 99% or more was dissolved in water at a concentration of 4 to 5% in PVA. Next, the PVA aqueous solution was applied to a 200 μm thick amorphous PET substrate, and dried at a temperature of 50 to 60 ° C to obtain a laminate of a PVA layer having a thickness of 7 μm formed on the amorphous PET substrate.

The laminate including the PVA layer having a thickness of 7 μm was subjected to the following steps including a two-stage extension step of air-assisted extension and extension of boric acid water, and a thin high-performance polarizing film of 3 μm thick was produced. The laminate including the PVA layer having a thickness of 7 μm was integrally extended with the amorphous PET substrate by the air assisted extension step of the first stage, and an extended laminate including a PVA layer having a thickness of 5 μm was formed. Specifically, the extended laminated body is an extension device provided by placing a laminate body including a PVA layer having a thickness of 7 μm in an oven, and is uniaxially stretched at a free end to have a stretching ratio of 1.8 times, and the oven is set to 130. °C extended temperature environment. By the extension processing, the PVA included in the extended laminated body is made The layer was changed to a 5 μm thick PVA layer that the PVA molecule had oriented.

Secondly, by the dyeing step, the iodine is adsorbed to the PVA. A colored layer of a 5 μm thick PVA layer that has been oriented by the molecule. Specifically, the colored laminated body is obtained by immersing the extended laminated body in a dyeing liquid containing iodine and potassium iodide at a liquid temperature of 30 ° C for any time so as to constitute a single transmittance of the PVA layer constituting the finally formed high functional polarizing film. The composition is 40 to 44%, whereby iodine is adsorbed to the PVA layer contained in the extended laminate. In this step, the dyeing solution uses water as a solvent, and the iodine concentration is in the range of 0.12 to 0.30% by weight, and the potassium iodide concentration is made in the range of 0.7 to 2.1% by weight. The concentration ratio of iodine to potassium iodide is 1 to 7. Incidentally, when iodine is dissolved in water, potassium iodide must be used. More specifically, by immersing the extended laminate in a dyeing liquid having an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.1% by weight for 60 seconds, a PVA layer having a thickness of 5 μm which has been oriented by the PVA molecule has been formed. Coloring the laminate.

Furthermore, the coloring process is carried out by the step of extending the boric acid water in the second stage. The laminate was further extended integrally with the amorphous PET substrate, and an optical film laminate including a PVA layer constituting a high functional polarizing film of 3 μm thick was produced. Specifically, the optical film laminate is an extension device provided in the processing device, and is uniaxially stretched at a free end to have a stretching ratio of 3.3 times, and the processing device is set to contain boric acid and potassium iodide. A boric acid aqueous solution having a liquid temperature range of 60 to 85 °C. More specifically, the liquid temperature of the aqueous boric acid solution was 65 °C. Further, the boric acid content was made to 4 parts by weight based on 100 parts by weight of water, and the potassium iodide content was made to 5 parts by weight based on 100 parts by weight of water. In this step, the colored layer body which has been adjusted for the iodine adsorption amount is firstly immersed. Sprinkle in boric acid solution for 5 to 10 seconds. Then, the colored layered body is directly passed between the rolls having different circumferential speeds of the multiple arrays belonging to the stretching device provided in the processing apparatus, and takes 30 to 90 seconds, and is uniaxially extended at the free end to have a stretching ratio of 3.3 times. By this stretching treatment, the PVA layer contained in the colored layered body was changed to the adsorbed iodine to form a polyiodide complex, and the PVA layer having a thickness of 3 μm in one direction was repeatedly guided. The PVA layer constitutes a high-performance polarizing film of an optical film laminate.

Although not a necessary step in the manufacture of optical film laminates However, it is preferable to take out the optical film laminate from the aqueous boric acid solution by the washing step, and to wash the boric acid adhering to the surface of the 3 μm-thick PVA layer which has been formed on the amorphous PET substrate by the potassium iodide aqueous solution. Then, the washed optical film laminate was dried by a drying step using a warm air of 60 °C. Further, the washing step is a step for solving the appearance defect such as boric acid precipitation.

Although it is not necessary for the manufacture of optical film laminates However, it is also possible to apply an adhesive to the surface of a 3 μm-thick PVA layer which has been formed on a non-crystalline PET substrate by a bonding and/or transfer step, and bond 80 μm thick triethylene sulfonate on one surface. After the cellulose film, the amorphous PET substrate was peeled off, and a 3 μm thick PVA layer was transferred to a 80 μm thick triethylene cellulose film.

[other steps]

In addition to the foregoing steps, the method of manufacturing the aforementioned thin polarizing film may include other steps. For example, other steps may be exemplified by an insolubilization step, a crosslinking step, a drying (adjustment of water content) step, and the like. Other steps can be arbitrarily At the right time.

Representatively, the insolubilization step is carried out by immersing the PVA-based resin layer in an aqueous boric acid solution. By performing the insolubilization treatment, the PVA-based resin layer can be imparted with water resistance. The concentration of the aqueous boric acid solution is preferably from 1 part by weight to 4 parts by weight based on 100 parts by weight of water. The liquid temperature of the insolubilizing bath (aqueous boric acid solution) is preferably from 20 ° C to 50 ° C. Preferably, the insolubilization step is carried out after the production of the laminate, before the dyeing step or the water stretching step.

Representatively, the crosslinking step is carried out by immersing the PVA-based resin layer in an aqueous boric acid solution. By performing the crosslinking treatment, the PVA-based resin layer can be imparted with water resistance. The concentration of the aqueous boric acid solution is preferably from 1 part by weight to 4 parts by weight based on 100 parts by weight of water. Further, when the crosslinking step is carried out after the dyeing step, it is more preferable to blend the iodide. By doping the iodide, the elution of iodine which has been adsorbed to the PVA-based resin layer can be suppressed. The amount of the iodide blended is preferably from 1 part by weight to 5 parts by weight per 100 parts by weight of the water. Specific examples of the iodide are as described above. The liquid temperature of the crosslinking bath (aqueous boric acid solution) is preferably from 20 ° C to 50 ° C. Preferably, the crosslinking step is carried out before the step of extending the second boric acid water. In a preferred embodiment, the dyeing step, the crosslinking step, and the second boric acid water extending step are carried out in this order.

<Transparent protective film>

The material for forming the transparent protective film provided on one surface or both surfaces of the polarizing member is preferably a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, and isotropic property. For example, a polyester polymer such as polyethylene terephthalate or polyethylene naphthalate, a cellulose polymer such as diethyl cellulose or triacetyl cellulose, and polymethyl Methyl methacrylate Acrylic polymer, polystyrene or acrylonitrile. A styrene-based polymer such as a styrene copolymer (AS resin) or a polycarbonate-based polymer. Further, examples of the polymer forming the transparent protective film may be exemplified by polyethylene, polypropylene, polyolefin having a ring system or a norbornene structure, and ethylene. a polyolefin polymer such as a propylene copolymer, a vinyl chloride polymer, a guanamine polymer such as nylon or an aromatic polyamine, a quinone imine polymer, a fluorene polymer, a polyether fluorene polymer, Polyetheretherketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, ethylene butyral polymer, aryl ester polymer, polyoxymethylene polymer, epoxy A polymer or a blend of the foregoing polymers, and the like. One or more optional additives may be contained in the transparent protective film. For example, the additives may, for example, be ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, color preventive agents, flame retardants, nucleating agents, antistatic agents, pigments, colorants, and the like. The content of the thermoplastic resin in the transparent protective film is preferably from 50 to 100% by weight, and more preferably from 50 to 99% by weight, further preferably from 60 to 98% by weight, particularly preferably from 70 to 97% by weight. When the content of the thermoplastic resin in the transparent protective film is 50% by weight or less, the high transparency and the like which the thermoplastic resin originally has may not be sufficiently exhibited.

Moreover, the transparent protective film can be exemplified by: The polymer film disclosed in JP-A-2001-343529 (WO01/37007), for example, contains (A) a thermoplastic resin having a substituted and/or unsubstituted imine group in the side chain and (B) a side chain having a substitution and/or A resin composition of a non-substituted phenyl group and a nitrile group-based thermoplastic resin. Specific examples include, for example, an alternating copolymer composed of isobutylene and N-methylmaleimide and acrylonitrile. Phenylene A film of a resin composition of an olefin copolymer. As the film, a film composed of a mixed product of a resin composition or the like can be used. Since these films have a small phase difference and a small photoelastic coefficient, the problem of unevenness caused by the strain of the polarizing film can be solved, and since the moisture permeability is small, the humidifying durability is excellent.

In the polarizing film, the transparent protective film preferably has a moisture permeability of 150 g/m ² /24 h or less. According to the above configuration, it is difficult for moisture in the air to enter the polarizing film, and the change in the water content of the polarizing film itself can be suppressed. As a result, it is possible to suppress the curling or dimensional change of the polarizing film caused by the storage environment.

The material for forming the transparent protective film provided on one or both sides of the polarizing member is preferably a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropic property, and the like, and particularly preferably has a moisture permeability. It is 150 g/m ² /24 h or less, and particularly preferably 140 g/m ² /24 h or less, more preferably 120 g/m ² /24 h or less. The moisture permeability can be obtained by the method disclosed in the examples.

For example, the transparent protective film that satisfies the aforementioned low moisture permeability The forming material may be: a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; a polycarbonate resin; an aryl ester resin; a guanamine resin such as nylon or an aromatic polyamide; Polyethylene, polypropylene, ethylene. A polyolefin-based polymer of a propylene copolymer, a cyclic olefin-based resin having a ring-based or norbornene structure, a (meth)acrylic resin, or a mixture thereof. Among the above resins, a polycarbonate resin, a cyclic polyolefin resin, and a (meth)acrylic resin are preferable, and a cyclic polyolefin resin or a (meth)acrylic resin is preferable.

The thickness of the transparent protective film can be appropriately determined, in general, It is 1 to 100 μm from the viewpoints of workability such as strength and handling properties, and thin layer properties. In particular, it is preferably 1 to 80 μm, and more preferably 3 to 60 μm.

Further, when a transparent protective film is provided on both surfaces of the polarizing member, a transparent protective film made of the same polymer material as the surface may be used, or a transparent protective film composed of a different polymer material or the like may be used.

A functional layer such as a hard coat layer, an antireflection layer, an anti-adhesion layer, a diffusion layer or an anti-glare layer may be disposed on the surface of the transparent protective film that is not attached to the polarizer. In addition, the functional layer such as the hard coat layer, the antireflection layer, the anti-adhesion layer, the diffusion layer or the anti-glare layer may be additionally provided separately from the transparent protective film in addition to the transparent protective film itself.

<Optical film>

The polarizing film of the present invention can be used as an optical film which is practically laminated with other optical layers. The optical layer is not particularly limited. For example, one or two or more reflective plates, semi-transmissive plates, phase difference plates (including 1/2 or 1/4 wavelength plates) or viewing angle compensation may be used. A film or the like is used for an optical layer formed by a liquid crystal display device or the like. Particularly preferred is a reflective polarizing film or a semi-transmissive polarizing film which is a laminated film or a semi-transmissive reflector of the polarizing film of the present invention, and an elliptically polarizing film or a circularly polarized film which is formed by laminating a retardation film on a polarizing film. The film is a polarizing film which is formed by a wide viewing angle polarizing film which is a multilayer viewing angle compensation film in a polarizing film or a brightness increasing film which is laminated on the polarizing film.

The optical film which has been laminated on the optical layer in the polarizing film can also be sequentially laminated in the manufacturing process of the liquid crystal display device or the like. In the case of forming an optical film in advance, it is advantageous in that the optical film is excellent in quality stability and assembly work, and the manufacturing steps of the liquid crystal display device or the like can be improved. An appropriate bonding mechanism such as an adhesive layer can be used for the laminate. When the polarizing film or other optical film is followed, the optical axes can be appropriately arranged according to the target phase difference characteristics or the like.

The polarizing film or the optical film in which at least one polarizing film is laminated may be provided with an adhesive layer for subsequent bonding with other members such as a liquid crystal cell. The adhesive for forming the adhesive layer is not particularly limited, and, for example, an acrylic polymer, a polyoxymethylene polymer, a polyester, a polyurethane, a polyamide, a poly A polymer such as an ether, a fluorine or a rubber is used as an adhesive for the base polymer. In particular, it is preferable to use an adhesive which is excellent in optical transparency such as an acrylic adhesive and exhibits excellent wettability, cohesiveness and adhesion properties, and weather resistance or heat resistance.

The adhesive layer may be formed as a superposed layer of different compositions or types, and may be provided on one or both sides of the polarizing film or the optical film. Further, when it is provided on both sides, an adhesive layer of a different composition, type or thickness may be formed in the surface of the polarizing film or the optical film. The thickness of the adhesive layer can be appropriately determined depending on the purpose of use or the adhesion, etc., however, it is usually 1 to 500 μm, and preferably 1 to 200 μm, particularly preferably 1 to 100 μm.

During the period until the application is practical, the exposed surface of the adhesive layer is temporarily adhered to and covered with the separator for the purpose of preventing contamination or the like. Thereby, it is possible to prevent contact with the adhesive layer in a conventional treatment state. In addition to the aforementioned thickness conditions, the separator may be, for example, a plastic film, a rubber sheet, or a suitable release agent such as a polyfluorinated or long-chain alkyl group, a fluorine-based or a molybdenum sulfide. A suitable sheet such as paper, cloth, non-woven fabric, mesh, foamed sheet or metal foil, or a laminate thereof is subjected to a coating treatment or the like according to a conventional standard.

<Image display device>

The polarizing film or the optical film of the present invention can be preferably used for formation of various devices such as a liquid crystal display device. The formation of the liquid crystal display device can be carried out in accordance with the conventional standards. In other words, the liquid crystal display device is generally formed by appropriately assembling a liquid crystal cell, a polarizing film, an optical film, and a lighting system such as an illumination system, and the like, and is incorporated in a driving circuit or the like. However, in the present invention, There is no particular limitation on the use of the polarizing film or the optical film according to the present invention, and the conventional standard can be complied with. For example, the liquid crystal cell can also be of any type such as TN type, STN type or π type.

A liquid crystal display device in which a polarizing film or an optical film is disposed on one side or both sides of a liquid crystal cell, or a liquid crystal display device such as a backlight or a reflector in an illumination system can be formed. At this time, the polarizing film or the optical film according to the present invention may be disposed on one side or both sides of the liquid crystal cell. When the polarizing film or the optical film is provided on both sides, the materials may be the same or different. Furthermore, in the formation of the liquid crystal display device, for example, appropriate components such as a diffusion plate, an anti-glare layer, an anti-reflection film, a protective plate, a ruthenium array, a lens array sheet, a light diffusion plate, and a backlight can be used. One or two or more layers are arranged at appropriate positions.

Example

The embodiments of the present invention are disclosed below, however, the embodiments of the present invention are not limited thereto.

<Production of polarizer>

A polyvinyl alcohol film having an average polymerization degree of 2400 and a saponification degree of 99.9 mol% and a thickness of 75 μm was immersed in warm water of 30 ° C for 60 seconds, and swelled. Subsequently, the film was immersed in an aqueous solution of 0.3% by weight of iodine/potassium iodide (weight ratio = 0.5/8), and the film was dyed while extending to 3.5 times. Then, the stretching was carried out in an aqueous solution of borate at 65 ° C to make the total stretching ratio 6 times. After stretching, it was dried by an oven at 40 ° C for 3 minutes, and a PVA-based polarizing member X (thickness: 23 μm) was obtained.

<Transparent protective film>

Transparent protective film 1: A triacetonitrile cellulose film (water vapor permeability: 530 g/m ² /24 h) having a thickness of 60 μm (labeled as TAC in Table 1) was used without saponification, corona treatment or the like.

Transparent protective film 2: (meth)acrylic resin having a lactone ring structure (transparent humidity: 96 g/m ² /24 h) having a thickness of 40 μm was subjected to corona treatment (labeled as acrylic acid in Table 1).

Transparent protective film 3: a circular polyolefin film (manufactured by Zeon Co., Ltd.: ZEONOR, moisture permeability: 11 g/m ² /24 h) having a thickness of 55 μm is used for corona treatment (labeled as COP in Table 1). .

<Transparency of transparent protective film>

The measurement of the moisture permeability is measured in accordance with the moisture permeability test (the moisture permeable cup method) of JIS Z0208. The sample which has been cut into a diameter of 60 mm is placed in a moisture-permeable cup which has been placed in a calcium chloride of about 15 g, and placed in a thermostat having a temperature of 40 ° C and a humidity of 90% RH, and the chlorine is placed for 24 hours before and after being placed. The weight of the calcium is increased, whereby the moisture permeability (g/m ² /24h) is obtained.

<active energy line>

The active energy ray is a visible light ray (a metal halide lamp enclosed in gallium), an irradiation device: Light HAMMER 10 manufactured by Fusion UV Systems, Inc., a valve: a V valve, a peak illuminance: 1600 mW/cm ² , and a cumulative irradiation amount of 1000 mJ/cm ² ( Wavelength 380~440nm). In addition, the illuminance of visible light was measured using a Sola-Check system manufactured by Solatell.

Examples 1 to 4 and Comparative Examples 1 to 5

(modulation of active energy ray-curable adhesive)

According to the blending table disclosed in Table 1, the components were mixed and stirred at 50 ° C for 1 hour, and the active energy ray-curable adhesives of Example 1 and Comparative Example 1 were obtained. Further, the viscosity of the active energy ray-curable adhesive of Example 1 was 95 cp (25 ° C), and the viscosity of the active energy ray-curable adhesive of Comparative Example 1 was 45 cp (25 ° C).

(production of polarizing film)

Using the MCD coater (manufactured by Fuji Machinery Co., Ltd.) (single cell shape: honeycomb shape, number of gravure roll lines: 1000 pieces/inch, rotation speed 140%/pairwise line speed), the above-mentioned implementation will be described on the above transparent protective film. The active energy ray-curable adhesive of the example or the comparative example was applied to a thickness of 0.7 μm, and bonded to both faces of the polarizing member X by a roll machine. Then, using an IR heater, the self-adhesive transparent protective film side (both sides) is heated to 50 ° C, and the visible light rays are irradiated to both sides to make the active energy ray-curable adhesive of the foregoing embodiment or the comparative example. After hardening, it was dried by hot air at 70 ° C for 3 minutes, and a polarizing film having a transparent protective film on both sides of the polarizing member was obtained. The line speed of bonding is performed by 25 m/min.

The production of the polarizing film was carried out separately for the above-mentioned transparent protective films 1 to 3.

The following evaluations were performed on the polarizing films obtained by the foregoing Examples and Comparative Examples. Table 1 shows the results of the evaluation. Further, in the evaluation of the humidifying durability and the subsequent water resistance, the same polarizing film was separately produced.

<Overall water absorption rate>

The cured adhesive for a polarizing film used in each of the examples was used, and sandwiched by two sheets of glass provided with a separator of 100 μm, and hardened by the same active energy conditions as in the examples to prepare a thickness of 100 μm. Agent layer (hardened). This was taken as a sample. The weight of the sample was made into M1g. The sample M1g was immersed in pure water at 23 ° C for 24 hours. Then, after taking out from pure water and wiping with a dry cloth, the weight (M2g) of the sample was measured again within 1 minute. The overall water absorption rate was calculated from the results by the following formula: that is: {(M2-M1)/M1}×100 (%).

<hardening shrinkage rate>

It was measured by a "hardening shrinkage stress measuring device EU201C" which is a hardening shrinkage sensor manufactured by the company. Specifically, the curing shrinkage ratio is calculated by the method disclosed in JP-A-2013-104869. Further, the cured shrinkage ratio of the cured product formed from the active energy ray-curable adhesive of Example 1 was 8.9%, and the hardening shrinkage ratio of the cured product formed from the active energy ray-curable adhesive of Comparative Example 1 was obtained. It is 11.9%.

<Continue force>

The polarizing film obtained in each example was cut out to be 200 mm parallel to the extending direction of the polarizing member, and the straight direction was 20 mm, and by a cutting blade, A slit is added between the transparent protective film and the polarizing member, and the polarizing film is bonded to the glass plate. The transparent protective film and the polarizing member were peeled off at a peeling speed of 500 mm/min in a 90-degree direction by a universal testing machine (TENSILON), and the peeling strength was measured. Further, the infrared absorption spectrum of the peeled surface after peeling was measured by the ATR method, and the peeling interface was evaluated based on the following criteria.

A: agglomeration damage of transparent protective film

B: Interfacial peeling between the transparent protective film/adhesive layer

C: interface peeling between the adhesive layer/polarizer

D: condensed damage of polarizer

In the above-mentioned criteria, A and D mean that the bonding force is equal to or higher than the cohesive force of the film, and therefore, the bonding force is extremely excellent. On the other hand, B and C mean that the adhesion of the interface of the transparent protective film/adhesive layer (adhesive layer/polarizer) is insufficient (and then the force difference). Considering these and the subsequent force belonging to A or D is made into ○, which will belong to A. B (At the same time, "cohesive failure of the transparent protective film" and "interfacial peeling between the transparent protective film/adhesive layer") or A. C (At the same time, the adhesion force at the time of "cohesive failure of the transparent protective film" and "interfacial layer peeling between the adhesive layer/polarizer") is Δ, and the adhesion force at the time of B or C is ×.

<Humidification durability: measurement of single transmittance and polarization change>

A polarizing film in which each of the transparent protective films 2 and 3 was laminated on both surfaces of the polarizing member as a transparent protective film was prepared into a sample by the same method as in the examples and the comparative examples. The polarizing film (sample) was placed in a constant temperature and humidity machine at 85 ° C / 85% RH for 500 hours. Using a spectroscopic transmittance measuring instrument with an integrating sphere (Dot-3c of Murakami Color Technology Research Institute), The transmittance and polarization of the polarizing film after the input, and the amount of change in the transmittance of the monomer (ΔT:%) = (the transmittance of the monomer after the input (%)) - (the single before the input) Volume transmittance (%)); amount of change in polarization (ΔP: %) = (polarization (%) after input) - (polarization (%) before input).

In addition, the degree of polarization P is obtained by combining the transmission axes of two identical polarizing films into a transmission axis (parallel transmittance: Tp) and the transmission axes of the two are orthogonal. The transmittance (orthogonal transmittance: Tc) was obtained by applying the following formula.

Polarization P(%)={(Tp-Tc)/(Tp+Tc)} ^1/2 ×100

Each of the transmittances is represented by the Y value obtained by the luminosity correction by the 2 degree field of view (C light source) of JIS Z8701, which is 100% of the total polarization obtained by the Glan Taylor 稜鏡 polarizer.

<The water resistance (warm water immersion test)>

A polarizing film in which each of the transparent protective films 1 and 3 was laminated on both sides of the polarizing member as a transparent protective film was prepared into a sample by the same method as in the examples and the comparative examples. The polarizing film (sample) was cut into a rectangular shape in which the polarizing member was extended in a direction of 50 mm and a vertical direction was 25 mm. After the polarizing film was immersed in warm water of 60 ° C for 6 hours, the length of peeling was visually determined by a magnifying glass. The measurement is the maximum value (mm) of the vertical distance from the cross section of the portion from which the peeling is caused.

<The water resistance (water peeling resistance)>

By using the same method as in the embodiment and the comparative example, each of the transparent protective films 1 and 3 which have been laminated on both sides of the polarizing member is used as a transparent protective film. The polarizing film of the film was prepared into a sample. The polarizing film (sample) was cut into a size parallel to the extending direction of the polarizing member of 200 mm and a straight direction of 20 mm. The polarizing film was immersed in pure water at 23 ° C for 24 hours, and then taken out from the pure water, and after being wiped by a dry cloth, a slit was placed between the transparent protective film and the polarizing member by a cutting blade, and the polarizing film was added. Adhesive to the glass plate. It was carried out within 1 minute from the time of taking out from pure water until the evaluation. Thereafter, the same evaluation as the aforementioned <adjacent force> was performed.

<calculation of logPow>

The log Pow value of each compound obtained by Chem Draw Ultra (manufactured by Cambridge Software Co., Ltd.) was used and calculated by the following formula. In addition, the polymerization initiator and the photoacid generator are deducted from the calculation.

Hardening type of adhesive logPow = Σ (logPowi × Wi)

logPowi: logPow value of each component of the hardened adhesive

Wi: (the number of moles of the i component) / (the total number of moles of each component of the hardened adhesive)

In Table 1, the radical polymerizable compound is: HEAA: hydroxyethyl acrylamide, logPow = -0.56, Tg of the homopolymer = 123 ° C, manufactured by Xingren Co., Ltd.; ACMO: acryloyl morpholine, logPow = -0.20, homopolymer Tg = 150 ° C, manufactured by Xingren Co., Ltd.; FA-THFM: tetrahydroindenyl (meth) acrylate, log Pow = 1.13, homopolymer Tg = 45 ° C, manufactured by Hitachi Chemical Co., Ltd.; LIGHT ACRYLATE DCP-A: tricyclodecane dimethanol diacrylate, logPow=3.05, homopolymer Tg=134°C, manufactured by Kyoeisha Chemical Co., Ltd.; LIGHT ACRYLATE1, 9ND-A: 1,9-nonanediol Diacrylate, logPow=3.68, homopolymer Tg=68°C, manufactured by Kyoeisha Chemical Co., Ltd.; ARONIX M-220: tripropylene glycol diacrylate, logPow=1.68, homopolymer Tg69°C, manufactured by Toagosei Co., Ltd. ARONIX M-306: pentaerythritol tri/tetraacrylate, logPow=1.04, Tg of homopolymer = 250 ° C or higher, manufactured by Toagosei Co., Ltd. Acrylic oligomer: ARUFON UP-1190, logPow=1.95 is a product of East Asia Synthetic Co., Ltd.; alkoxy group-containing compound: NIKALAC MX-750LM, logPow=0.8 is a product of Japan Carbo Industries Co., Ltd.; Compound: JER828, logPow = 4.76 is a product of Nippon Epoxy Resin Co., Ltd.; isocyanate compound: KARENZ AOI, and logPow = 1.6 is a display of Showa Denko Co., Ltd. The photopolymerization initiator is: IRGACURE 907 (2-methyl-1-(4-methylthiophenyl)-2-morpholinepropan-1-one), logPow=2.09, manufactured by BASF Corporation; KAYACURE DETX-s ( Diethyl 9-oxosulfur ), logPow = 5.12, manufactured by Nippon Kayaku Co., Ltd.

The photoacid generator is a propylene carbonate solution which exhibits CPI-100P (50% of an active ingredient of triarylphosphonium hexafluoride as a main component), manufactured by Sanya Pro.

Claims (18)

A hardening type adhesive for a polarizing film, which contains a curable component, and the cured film obtained by curing the curable adhesive is immersed in pure water of 23 ° C for 24 hours. The total water absorption ratio expressed by the following formula is 10% by weight or less, that is, the overall water absorption ratio (%) = {(M2 - M1) / M1} × 100 {however, in the above formula, M1 represents a cured product before impregnation. Weight, M2 represents the weight of the cured product after impregnation}. A hardening type adhesive for a polarizing film according to claim 1, wherein the octanol/water partition coefficient (logPow value) is 1 or more. A hardening type adhesive for a polarizing film according to claim 1 or 2, wherein the curable component is an active energy ray-curable component. A hardening type adhesive for a polarizing film according to claim 3, wherein the active energy ray-curable component contains a radical polymerizable compound. A hardening type adhesive for a polarizing film according to claim 4, wherein the radically polymerizable compound contains a (meth) acrylamide derivative. A hardening type adhesive for a polarizing film according to claim 4 or 5, wherein the radical polymerizable compound contains a polyfunctional compound, and the polyfunctional compound has at least two radically polymerizable functional groups. A hardening type adhesive for a polarizing film according to any one of claims 3 to 6, which further contains a photopolymerization initiator. A hardening type adhesive for a polarizing film according to any one of claims 3 to 7, which further comprises an acrylic oligomer (A). A hardening type adhesive for a polarizing film according to any one of claims 3 to 8, which further comprises a photoacid generator (B). A hardening type adhesive for a polarizing film according to any one of claims 3 to 9, which further comprises a compound (C) comprising any one of an alkoxy group and an epoxy group. A hardening type adhesive for a polarizing film according to claim 10, wherein the compound (C) containing any one of an alkoxy group and an epoxy group is a compound (C1) containing an alkoxy group. The hardening type adhesive for a polarizing film according to claim 11, wherein the alkoxy group-containing compound (C1) is a melamine compound containing an alkoxy group. A hardening type adhesive for a polarizing film according to any one of claims 3 to 12, which further contains an isocyanate compound (D). A hardening type adhesive for a polarizing film according to claim 1 or 2, wherein the curable component is a thermosetting component and further contains a thermal polymerization initiator. A polarizing film which is provided with a transparent protective film on at least one of the polarizing members via an adhesive layer, and the adhesive layer is a hardened adhesive for a polarizing film according to any one of claims 1 to 14. The hardened layer is formed. The polarizing film of claim 15, wherein the thickness of the adhesive layer of the adhesive is 0.1 to 3 μm. An optical film laminated with at least one polarizing film of claim 15 or 16. An image display device using a polarizing film as claimed in claim 15 or 16, or an optical film as in claim 17.