TWI702270B - Hardening adhesive for polarizing film, polarizing film, optical film and image display device - Google Patents

Abstract

The curable adhesive for polarizing films of the present invention containing curable components, when the cured product of the curable adhesive for polarizing films is immersed in pure water at 23°C for 24 hours, the overall water absorption is expressed by the following formula Below 10% by weight, that is: overall water absorption (%) = formula: {(M2-M1)/M1}×100(%)

{However, in the foregoing formula, M1 represents the weight of the cured product before immersion, and M2 represents the weight of the cured product after immersion}. The hardening type adhesive for polarizing film is very good in the adhesion of polarizer and transparent protective film, and it can meet the optical durability under severe environment of high temperature and high humidity. At the same time, even when immersed in water for a long time, It also has sufficient adhesion.

Description

Hardening adhesive for polarizing film, polarizing film, optical film and image display device

The present invention relates to a curable adhesive for polarizing films, which is used to form the aforementioned adhesive layer in a polarizing film in which a polarizer and a transparent protective film are laminated via the adhesive. Furthermore, the present invention also relates to a polarizing film using the aforementioned adhesive layer. The polarizing film can be used alone or as an optical film laminated with the polarizing film to form image display devices such as liquid crystal display devices (LCD), organic EL display devices, CRTs, and PDPs.

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 the polarization state using the switching of the liquid crystal, and uses a polarizer according to its display principle. Especially in TV and other applications, high brightness, high contrast, and wide viewing angle are increasingly required, and in polarizing films, high transmittance, high polarization, and high color reproducibility are also increasingly required.

Because of its high transmittance and high degree of polarization, for example, iodine-based polarizers with a structure in which iodine is adsorbed on polyvinyl alcohol (hereinafter referred to as "PVA") and stretched are generally the most widely used as polarizers Pieces. Generally speaking, the polarizing film uses the following polarizing film, that is, by dissolving a polyvinyl alcohol-based material in a so-called water-based adhesive, a transparent protective film is adhered to both sides of the polarizing member (Patent Document 1 and patent below) Literature 2). The transparent protective film uses triacetyl cellulose with high moisture permeability. When using the aforementioned water-based adhesive (so-called wet lamination), after bonding the polarizer and the transparent protective film, a drying step is necessary.

On the other hand, active energy ray-curable adhesives are currently disclosed to replace the aforementioned water-based adhesives. When a polarizing film is produced using an active energy ray hardening adhesive, since a 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 is currently disclosed (Patent Document 3 and Patent Document 4 below). The aforementioned adhesives can exhibit excellent durability in severe environments under high humidity and high temperatures. However, the reality is that adhesives that can improve further adhesiveness and/or water resistance are still required in the market.

In addition, focusing on the SP value (solubility parameter) of the curable component, there is currently disclosed an active energy ray curable adhesive that uses at least three radically polymerizable compounds with different SP values in a predetermined composition ratio, thereby , Can form an adhesive layer that improves durability and water resistance (Patent Document 5 below).

Advanced technical literature Patent literature

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

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

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

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

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

Summary of the invention

According to the active energy ray curable adhesive disclosed in the aforementioned Patent Document 5, durability and water resistance can be satisfied for various transparent protective films used in the production of polarizing films. However, although the polarizing film prepared by using the active energy ray curable adhesive disclosed in Patent Document 5 can meet the water resistance (warm water immersion test) immersed in warm water at 60°C for 6 hours, it is not on the market. It requires further optical durability in harsh environments under high temperature and humidity. Furthermore, the aforementioned polarizing film is required to have sufficient adhesion even when it is immersed in water for a long time.

The object of the present invention is to provide a hardening adhesive for polarizing films, which has excellent adhesion between polarizers and transparent protective films, and can meet the optical durability in severe environments under high temperature and high humidity, and even It also has sufficient adhesion when immersed in water for a long time.

In addition, the object of the present invention is to provide a polarizing film, which is formed by using an adhesive layer formed of a hardening adhesive for polarizing film, and a transparent protective film is provided on a polarizing member, and further, to provide a polarizing film using the aforementioned polarizing film The optical film further provides an image display device using the aforementioned polarizing film or optical film.

In order to solve the above-mentioned problems, the inventors have repeatedly studied and found that the above-mentioned object can be achieved by the following hardening type adhesive for polarizing films, thereby solving the present invention.

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

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

The octanol/water partition coefficient (logPow value) of the curable adhesive for polarizing films is preferably 1 or more.

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

The above-mentioned curable adhesive for polarizing films may further contain an acrylic oligomer (A).

The aforementioned curable adhesive for polarizing films may further contain a photoacid generator (B).

The aforementioned curable adhesive for polarizing films may further contain a compound (C) containing either an alkoxy group or an epoxy group. The aforementioned compound (C) containing either an alkoxy group or an epoxy group is preferably a compound (C1) containing an alkoxy group. Furthermore, the aforementioned alkoxy-containing compound (C1) is preferably an alkoxy-containing melamine compound.

Moreover, the said curable adhesive agent for polarizing films may further contain an isocyanate compound (D).

When the curable component is a thermosetting component, the curable adhesive for polarizing films further contains a thermal polymerization initiator, whereby it can be used as a thermosetting adhesive.

In addition, the present invention relates to a polarizing film in which a transparent protective film is provided on at least one side of a polarizer via an adhesive layer, and the adhesive layer is cured by the hardening type adhesive for the polarizing film Layer formation.

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

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

Furthermore, the present invention relates to an image display device which uses the aforementioned polarizing film or the aforementioned optical film.

The curable adhesive for polarizing films of the present invention has an overall water absorption rate of 10% by weight or less of the cured product obtained by curing the curable adhesive. This overall water absorption rate shows that the water absorption when the adhesive layer is formed from the cured product layer obtained from the curable adhesive for polarizing films of the present invention is very low. Therefore, a polarizing film in which a transparent protective film is provided on the adhesive layer composed of the aforementioned cured layer on the polarizing member is very good in the adhesion between the polarizing member and the transparent protective film layer, and can meet high temperature and high humidity. Optical durability under severe environments.

For example, a polarizing film having a hardened layer (adhesive layer) formed using the curable adhesive for polarizing films of the present invention is optically durable even in a severe humidified environment (85℃×85%RH) Performance (humidification durability test) is also good. Therefore, even when the polarizing film of the present invention is placed in the aforementioned severe humidified environment, the transmittance and polarization of the polarizing film can be reduced (change). In addition, the polarizing film of the present invention can suppress the decrease in adhesion even under severe environments such as being immersed in water, and can provide a polarizing film having sufficient adhesion even when immersed in water for a long time.

The form used to implement the invention

<Overall water absorption>

The curable adhesive for polarizing films of the present invention has an overall 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 environment of high temperature and humidity (85°C/85%RH, etc.), the water that has passed through the transparent protective film and the adhesive layer will penetrate into the polarizer and the cross-linked structure will be hydrolyzed, thereby, The orientation of the dichroic pigments is disordered, and causes the deterioration of optical durability such as increase in transmittance and decrease in polarization. By setting the overall water absorption rate of the adhesive layer to 10% by weight or less, the movement of water toward the polarizer when the polarizing film is placed in a severe high temperature and humidity environment can be suppressed, and the transmittance of the polarizer can be inhibited from increasing and polarizing. Degree decreases. Regarding the adhesive layer of the polarizing film, if the optical durability under the severe environment at high temperature is made better, the overall water absorption rate should be less than 5% by weight, and more preferably less than 3% by weight , And more preferably 1.5% by weight or less, most desirably 1% by weight or less. On the other hand, when bonding the polarizer and the transparent protective film, the polarizer will retain a certain amount of moisture, and when the hardened adhesive comes into contact with the moisture contained in the polarizer, it will cause dents, bubbles and other appearance defects. . In order to prevent poor appearance, the hardened adhesive should absorb a certain amount of water. 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 aforementioned overall water absorption is measured by the water absorption test method disclosed in JIS K 7209.

The curable adhesive for polarizing films of the present invention preferably has a high octanol/water partition coefficient (hereinafter referred to as logPow value). The so-called logPow value is an indicator of the lipophilicity of a substance and means the logarithmic value of the octanol/water partition coefficient. High logPow means it is lipophilic, that is, it means low water absorption. The logPow value can be measured (flask shaking method disclosed in JIS-Z-7260). However, it can also be calculated based on the structure of each compound that is a component (curable component, etc.) of a curable adhesive for polarizing films To work out. In this manual, the logPow value calculated by Chem Draw Ultra manufactured by CambridgeSoft is used.

Based on the aforementioned calculated value, the logPow value of the curable adhesive for polarizing films of the present invention can be calculated by the following formula.

Hardening adhesive logPow=Σ(logPowi×Wi)

logPowi: The logPow value of each component of the hardening adhesive

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

In the foregoing calculation, among the components of the curing adhesive, the components that do not form the skeleton of the cured product (adhesive layer), such as polymerization initiators or photoacid generators, will be deducted from the foregoing calculations. The logPow value of the curable adhesive for polarizing films of the present invention is preferably 1 or more, more preferably 1.5 or more, and most preferably 2 or more. Thereby, the adhesion resistance to water or humidification durability can be improved. On the other hand, the logPow value of the curable adhesive for polarizing films of the present invention is usually 8 or less, and preferably 5 or less, and more preferably 4 or less. If the logPow value is too high, as described above, it is undesirable because of the appearance defects such as sinking and bubbles.

In addition, there is no particular limitation on the method of making the aforementioned overall water absorption rate of 10% by weight or less in the present invention. However, when the curable adhesive for polarizing films is a composition containing multiple components, by selecting each component, The overall water absorption rate can be controlled within the aforementioned range. For example, when the curable adhesive for polarizing film is an adhesive composition containing a plurality of components, it is possible to reduce the ratio of the components whose logPow value constitutes 1 or less in the adhesive composition. The water absorption rate is controlled within the aforementioned range. When the overall water absorption in the present invention is to be adjusted to 10% by weight or less, for example, it can be done by controlling the logPow value of the curable adhesive for polarizing films to 1 or more.

<hardening shrinkage>

Moreover, since the curable adhesive for polarizing films of the present invention has curable components, curing shrinkage usually occurs when the curable adhesive is cured. The curing shrinkage rate is an index showing the curing shrinkage ratio when the adhesive layer is formed from the curing adhesive for polarizing films. If the curing shrinkage rate of the adhesive layer increases, interface strain will occur when the hardening type adhesive for polarizing films is cured to form the adhesive layer, which is preferable in terms of suppressing the occurrence of poor adhesion. From the foregoing viewpoint, the curing shrinkage rate of the cured product obtained by curing the curing adhesive for polarizing films of the present invention is preferably 10% or less. Preferably, the curing shrinkage rate is small, and the curing shrinkage rate is preferably 8% or less, more preferably 5% or less. The aforementioned curing shrinkage rate is measured by the method disclosed in JP 2013-104869 No., specifically, measured by the method disclosed in the examples using a curing shrinkage sensor manufactured by SENTEC.

<Sclerosing ingredients>

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

The curable component can be roughly divided into an active energy ray curable type such as an electron beam curable type, an ultraviolet curable type, and a visible light curable type, and a thermally curable type. Furthermore, ultraviolet curing type and visible light curing type adhesives can be divided into radical polymerization curing type adhesives and cationic polymerization type adhesives. In the present invention, the active energy lines with a wavelength range of 10 nm to less than 380 nm are labeled as ultraviolet rays, and the active energy lines with a wavelength range of 380 nm to 800 nm are labeled as visible rays. The curable component of the aforementioned radical polymerization curable adhesive can be used as the curable component of the thermosetting adhesive.

<1: Radical polymerization hardening adhesive>

For example, the aforementioned curable component may be a radical polymerizable compound used in a radical polymerization curable adhesive. Examples of the radically polymerizable compound include compounds having a radically polymerizable functional group having carbon-carbon double bonds such as (meth)acrylic groups and vinyl groups. As these curable components, either a monofunctional radical polymerizable compound or a bifunctional or more polyfunctional radical polymerizable compound can be used. Moreover, these radically polymerizable compounds can be used individually by 1 type or in combination of 2 or more types. For example, the radically polymerizable compounds are suitable compounds having a (meth)acryloyl group. In addition, in the present invention, the term “(meth)acryloyl group” means an acryloyl group and/or methacryloyl group, and "(meth)" has the same meaning as follows.

"Monofunctional radical polymerizable compound"

For example, the monofunctional radical polymerizable compound may include (meth)acrylamide derivatives having (meth)acrylamide groups. In terms of ensuring adhesion to polarizers and various transparent protective films, and in terms of high polymerization speed and excellent productivity, (meth)acrylamide derivatives are more desirable. For example, specific examples of (meth)acrylamide derivatives include: 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. contain N -Alkyl (meth)acrylamide derivatives; N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxymethyl-N-propane ( (Meth)acrylamide and other N-hydroxyalkyl-containing (meth)acrylamide derivatives; aminomethyl (meth)acrylamide, aminoethyl (meth)acrylamide, etc., containing N-amine Alkyl (meth)acrylamide derivatives; N-methoxymethacrylamide, N-ethoxymethacrylamide, etc. (meth)acrylamide derivatives containing N-alkoxy Products; mercaptomethyl (meth)acrylamide, mercaptoethyl (meth)acrylamide, and other N-mercaptoalkyl-containing (meth)acrylamide derivatives. Also, for example, the (meth)acrylamide derivatives containing heterocycles in which the nitrogen atom of the (meth)acrylamide group forms a heterocyclic ring include: N-acrylamide morpholine, N-acrylamide Piperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine, etc.

Among the aforementioned (meth)acrylamide derivatives, from the viewpoint of adhesion to polarizers or various transparent protective films, they are also preferably derived from (meth)acrylamide containing N-hydroxyalkyl groups. The substance is particularly preferably N-hydroxyethyl (meth)acrylamide.

Also, for example, the monofunctional radical polymerizable compound includes various (meth)acrylic acid derivatives having a (meth)acryloyloxy group. Specifically, for example, there may be mentioned: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (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-di Methyl butyl (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 and other (meth)acrylic acid (carbon number 1-20) alkyl esters .

Also, for example, the aforementioned (meth)acrylic acid derivatives include cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate and cyclopentyl (meth)acrylate; benzyl ( Aralkyl (meth)acrylates such as meth)acrylate; 2-isobornyl (meth)acrylate, 2-norbornylmethyl (meth)acrylate, 5-norbornene-2- -Methyl (meth)acrylate, 3-methyl-2-norbornylmethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl Polycyclic (meth)acrylates such as methyl (meth)acrylate and dicyclopentyl (meth)acrylate; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl Base (meth)acrylate, 2-methoxymethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate , Phenoxyethyl (meth)acrylate, alkylphenoxy polyethylene glycol (meth)acrylate, etc. (meth)acrylates containing alkoxy or phenoxy.

In addition, examples of the aforementioned (meth)acrylic acid derivatives include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxy Hydroxyalkyl (meth)acrylates such as decyl (meth)acrylate and 12-hydroxylauryl (meth)acrylate or [4-(hydroxymethyl)cyclohexyl]methacrylate, cyclohexane Dimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate and other hydroxyl-containing (meth)acrylates; Glycidyl(meth)acrylate, 4 -Hydroxybutyl (meth)acrylate glycidyl ether and other epoxy-containing (meth)acrylates; 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2 -Trifluoroethyl ethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, seventeen fluorine Decyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate and other halogen-containing (meth)acrylates; dimethylaminoethyl (meth)acrylate and other alkanes Amino alkyl (meth) acrylate; 3-oxetanyl methyl (meth) acrylate, 3-methyl-oxetanyl methyl (meth) acrylate, 3 -Ethyl-oxetanyl methyl (meth)acrylate, 3-butyl-oxetanyl methyl (meth)acrylate, 3-hexyl-oxetanyl methyl (Meth)acrylates such as oxetanyl groups; tetrahydrofurfuryl (meth)acrylates, butyrolactone (meth)acrylates and other (meth)acrylates with heterocycles Yl)acrylate or hydroxytrimethylacetate neopentyl glycol (meth)acrylic acid adduct, p-phenylphenol (meth)acrylate, etc.

In addition, examples of monofunctional radical polymerizable compounds include (meth)acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, etc. The monomer.

Also, for example, the monofunctional radical polymerizable compound may be exemplified by internal amine-based vinyl such as N-vinylpyrrolidone, N-vinyl-ε-caprolactone, and methyl vinylpyrrolidone. Group monomer; vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl morpholine, etc. have nitrogen-containing hetero Ring vinyl monomers, etc.

In addition, as the monofunctional radical polymerizable compound, a radical polymerizable compound having active methylene groups can be used. The radically polymerizable compound having an active methylene group is a compound having an active double bond group such as a (meth)acryloyl group in the terminal or molecule and having an active methylene group. For example, the active methylene group can be exemplified by acetylacetoxy, alkoxypropanedioxin or cyanoacetoxy. The aforementioned active methylene group is preferably acetyl acetyl group. For example, specific examples of radically polymerizable compounds having active methylene groups include: 2-acetylacetoxyethyl (meth)acrylate, 2-acetylacetoxypropyl ( Acetylacetoxyalkyl (meth)acrylates such as meth)acrylate, 2-acetoxyacetoxy-1-methylethyl (meth)acrylate; 2-ethoxypropane Acetyloxyethyl (meth)acrylate, 2-cyanoacetoxyethyl (meth)acrylate, N-(2-cyanoacetoxyethyl)acrylamide, N- (2-Propylacetoxybutyl)acrylamide, N-(4-acetoxymethylbenzyl)acrylamide, N-(2-acetylacetoxymethylbenzyl) Base) acrylamide and the like. The radically polymerizable compound having a reactive methylene group is preferably acetoxyalkyl (meth)acrylate.

"Multifunctional radical polymerizable compound"

Also, for example, the multifunctional radical polymerizable compound with more than bifunctionality can include tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol Di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol diacrylate, 2-ethyl-2-butylpropanediol di(meth)acrylic acid Esters, bisphenol A di(meth)acrylate, bisphenol A ethylene oxide adduct di(meth)acrylate, bisphenol A propylene oxide adduct di(meth)acrylate, bisphenol A Diglycidyl ether di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, cyclic trimethylolpropane formal (Meth)acrylate, dioxanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, neopentaerythritol Tetra (meth) acrylate, dineopentaerythritol penta (meth) acrylate, dineopentaerythritol hexa (meth) acrylate, EO modified diglycerol tetra (meth) acrylate, etc. (meth) Acrylic acid and polyhydric alcohol ester, 9,9-bis[4-(2-(meth)propenyloxyethoxy)phenyl]茀. Specific examples include: ARONIX M-220, M-306 (manufactured by Toagosei Co., Ltd.), LIGHT ACRYLATE 1,9ND-A (manufactured by Kyoeisha Chemical Co., Ltd.), LIGHT ACRYLATE DGE-4A (manufactured by Kyoeisha Chemical Co., Ltd.), LIGHT ACRYLATE DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), SR-531 (manufactured by Sartomer Corporation), CD-536 (manufactured by Sartomer Corporation), etc. In addition, if necessary, various epoxy (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates, or various (meth)acrylate monomers can be listed. .

In order to control the water absorption of the cured product, and to satisfy the optical durability of the polarizing film in a severe humidified environment, it is preferable that the radical polymerizable compound contains the aforementioned polyfunctional radical polymerizable compound. Among the aforementioned polyfunctional radical polymerizable compounds, those with a high logPow value are also preferable. The logPow value of the radical polymerizable compound is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more.

For example, radically polymerizable compounds with high logPow values include: tricyclodecane dimethanol di(meth)acrylate (logPow=3.05), isobornyl (meth)acrylate (logPow=3.27) Alicyclic (meth)acrylates; 1,9-nonanediol di(meth)acrylate (logPow=3.68), 1,10-decanediol diacrylate (logPow=4.10), long-chain aliphatic (Meth) acrylate; hydroxytrimethyl acetate neopentyl glycol (meth) acrylic acid adduct (logPow=3.35), 2-ethyl-2-butylpropanediol di(meth)acrylate (logPow= 3.92) and other multi-branched (meth)acrylates; bisphenol A di(meth)acrylate (logPow=5.46), bisphenol A ethylene oxide 4 mol adduct di(meth)acrylate ( logPow=5.15), bisphenol A propylene oxide 2 mol adduct di(meth)acrylate (logPow=6.10), bisphenol A propylene oxide 4 mol adduct di(meth)acrylate ( logPow=6.43), 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]Pow (logPow=7.48), p-phenylphenol (meth)acrylate ( logPow=3.98) and other (meth)acrylates containing aromatic rings.

From the viewpoint of compatibility with polarizers or various transparent protective films and optical durability in harsh environments, the radical polymerizable compound should be used in combination with a monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound. Compound. Generally speaking, it is preferable to use a combination of 3 to 80% by weight of the monofunctional radical polymerizable compound and 20 to 97% by weight of the polyfunctional radical polymerizable compound relative to 100% by weight of the radical polymerizable compound.

<The state of radical polymerization hardening adhesive>

The curable adhesive for polarizing films of the present invention can be used as an active energy ray curable adhesive when the curable component is used as an active energy ray curable component. In addition, when the curable component is used as a thermosetting component When used, it can be used as a thermosetting adhesive. The active energy ray-curable adhesive does not need to contain a photopolymerization initiator when the active energy rays use electron beams or the like. However, when the active energy rays use ultraviolet or visible rays, they preferably contain photopolymerization. Initiator. On the other hand, when using the curable component of the aforementioned adhesive as a thermosetting component, the adhesive preferably contains a thermal polymerization initiator.

"Photoinitiator"

(thioxanthone)、2-氯9-氧硫

、2-甲基9-氧硫

、2,4-二甲基9-氧硫

、異丙基9-氧硫

、2,4-二氯9-氧硫

、2,4-二乙基9-氧硫

、2,4-二異丙基9-氧硫

、十二基9-氧硫

等9-氧硫

系化合物；樟腦醌；鹵化酮；醯基氧化膦；醯基膦酸酯等。於光聚合引發劑中，亦宜為logPow值高者。光聚合引發劑並未包含於偏光薄膜用硬化型接著劑之logPow值之計算中之成分，然而，光聚合引發劑之logPow值宜為1以上，且更宜為2以上，最宜為3以上。 The photopolymerization initiator when using a radical polymerizable compound can be appropriately selected in accordance with active energy rays. When curing by ultraviolet or visible light, a photopolymerization initiator split by ultraviolet or visible light is used. For example, the aforementioned photopolymerization initiator can be exemplified by diacetophenone, benzophenone, benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, etc. Phenyl ketone compounds; 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, α-hydroxy-α,α'-dimethylacetophenone, 2-methyl Aromatic ketone compounds such as -2-hydroxypropiophenone and α-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-di Acetophenone compounds such as ethoxyacetophenone, 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinepropane-1; benzoin methyl ether, benzoin Benzoin ether compounds such as diethyl ether, benzoin isopropyl ether, benzoin butyl ether, and anisin methyl ether; aromatic ketal compounds such as benzoin dimethyl ketal; 2-naphthalene Aromatic sulfonyl chloride compounds such as sulfonyl chloride; photoactive oxime compounds such as 1-phenone-1,1-propanedione-2-(o-ethoxycarbonyl)oxime; 9-oxysulfur

(thioxanthone), 2-chloro-9-oxysulfur

, 2-Methyl 9-oxysulfur

, 2,4-Dimethyl 9-oxysulfur

, Isopropyl 9-oxysulfur

, 2,4-Dichloro 9-oxysulfur

, 2,4-Diethyl 9-oxysulfur

, 2,4-Diisopropyl 9-oxysulfur

, Dodecyl 9-oxysulfur

9-oxysulfur

Series of compounds; camphorquinone; halogenated ketones; acyl phosphine oxide; acyl phosphonate, etc. Among the photopolymerization initiators, it is also preferable to have a high logPow value. The photopolymerization initiator is not included in the calculation of the logPow value of the curable adhesive for polarizing films. However, the logPow value of the photopolymerization initiator is preferably 1 or more, more preferably 2 or more, and most preferably 3 or more .

The blending amount of the aforementioned photopolymerization initiator is 20 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component (radical polymerizable compound). The blending amount of the photopolymerization initiator is preferably 0.01-20 parts by weight, more preferably 0.05-10 parts by weight, and further 0.1-5 parts by weight.

Moreover, when using the curable adhesive for polarizing films of the present invention with a visible light curable type containing a radical polymerizable compound as a curable component, it is particularly suitable to use a photopolymerization initiator that is highly sensitive to light of 380 nm or more. The photopolymerization initiator with high sensitivity to light of 380 nm or more will be described later.

The aforementioned photopolymerization initiator is preferably used alone as a compound represented by the following general formula (1):

。相對於硬化性成分之全量100重量份，接著劑中藉由一般式(1)所表示之化合物之組成比率宜為0.1~5重量份，且更宜為0.5~4重量份，進而宜為0.9~3重量份。 (In the formula, 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 use the compound represented by general formula (1) in combination with The photopolymerization initiator with high sensitivity to light of 380 nm or more is described later. Compared to when a photopolymerization initiator with high sensitivity to light of 380 nm or more is used alone, the adhesiveness is superior when the compound represented by the general formula (1) is used. Among the compounds represented by the general formula (1), it is also particularly preferable that R ¹ and R ² are -CH ₂ CH ₃ diethyl 9-oxysulfur

. The composition ratio of the compound represented by the general formula (1) in the adhesive is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 4 parts by weight, and more preferably 0.9 parts by weight relative to 100 parts by weight of the total amount of curable ingredients ~3 parts by weight.

In addition, it is advisable to add a polymerization initiation assistant as required. Examples of polymerization initiators include: triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylamine benzoic acid, methyl 4-dimethylamine benzoate, 4-dimethylamine benzoic acid Ethyl ester, isoamyl 4-dimethylamine benzoate, etc., especially ethyl 4-dimethylamine benzoate. When the polymerization initiation aid is used, the added amount is usually 0 to 5 parts by weight, preferably 0 to 4 parts by weight, and most preferably 0 to 3 parts by weight relative to 100 parts by weight of the total amount of the curable component.

Furthermore, if necessary, a known photopolymerization initiator can be used in combination. Since the transparent protective film with UV absorption ability does not transmit light below 380nm, it is better to use a photopolymerization initiator with high sensitivity to light above 380nm. Specifically, examples include: 2-methyl-1-(4-methylthiophenyl)-2-morpholin-1-one, 2-benzyl-2-dimethylamino-1-( 4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)benzene Yl)-1-butanone, 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine Oxide, bis(η 5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium and the like.

In particular, in addition to the photopolymerization initiator of the general formula (1), the photopolymerization initiator is more preferably a compound represented by the following general formula (2):

(In the formula, 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). As the compound represented by the general formula (2), 2-methyl-1-(4-methylthiophenyl)-2-morpholin-1-one (trade name : IRGACURE907, Manufacturer: BASF). In addition, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (trade name: IRGACURE369, manufacturer: BASF), 2-(dimethylamine Group)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: IRGACURE379, manufacturer: BASF) The sensitivity is high, so it is ideal.

<The radical polymerizable compound (a1) with active methylene group and the radical polymerization initiator (a2) with hydrogen abstraction>

In the aforementioned active energy ray-curable adhesive, when the radical polymerizable compound is used as the radical polymerizable compound (a1) with active methylene, it is suitable to be combined with the radical polymerization initiator (a2) with hydrogen abstraction And use. With the aforementioned structure, even if it is taken out from a high-humidity environment or water (non-dry state), the adhesiveness of the adhesive layer of the polarizing film can be significantly improved. The reason is not clear, however, it is generally considered to be the following reason. That is, the radical polymerizable compound (a1) having a living methylene group is polymerized together with other radical polymerizable compounds constituting the adhesive layer and taken into the main chain and/or side of the base polymer in the adhesive layer Chain and form an adhesive layer. In the foregoing polymerization process, if a radical polymerization initiator (a2) with hydrogen abstraction is present, it will form a radical polymerizable compound (a2) with a living methylene group as the base polymer constituting the adhesive layer. Hydrogen, and generate free radicals in methylene. In addition, the methylene group that has generated free radicals reacts with the hydroxyl group of the 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 adhesiveness of the adhesive layer of the polarizing film can be significantly improved even in a non-dried state.

系自由基聚合引發劑、二苯基酮系自由基聚合引發劑等。前述自由基聚合引發劑(a2)宜為9-氧硫

系自由基聚合引發劑。舉例言之，9-氧硫

系自由基聚合引發劑可列舉如：藉由前述一般式(1)所表示之化合物。舉例言之，藉由一般式(1)所表示之化合物之具體例可列舉如：9-氧硫

、二甲基9-氧硫

、二乙基9-氧硫

、異丙基9-氧硫

、氯9-氧硫

等。於藉由一般式(1)所表示之化合物中，亦特別宜為R¹及R²為-CH₂CH₃之二乙基9-氧硫

。 In the present invention, for example, the radical polymerization initiator (a2) with hydrogen abstraction can be exemplified as: 9-oxysulfur

-Based radical polymerization initiator, benzophenone-based radical polymerization initiator, etc. The aforementioned radical polymerization initiator (a2) is preferably 9-oxysulfur

Department of free radical polymerization initiator. For example, 9-oxysulfur

Examples of the radical polymerization initiator include compounds represented by the aforementioned general formula (1). For example, specific examples of the compound represented by the general formula (1) include: 9-oxysulfur

, Dimethyl 9-oxysulfur

, Diethyl 9-oxysulfur

, Isopropyl 9-oxysulfur

, Chlorine 9-oxysulfur

Wait. Among the compounds represented by the general formula (1), it is also particularly preferable that R ¹ and R ² are -CH ₂ CH ₃ diethyl 9-oxysulfur

.

In the aforementioned active energy ray curable adhesive, when the radical polymerizable compound (a1) with active methylene group and the radical polymerization initiator (a2) with hydrogen abstraction action are contained, the total amount of the curable component is reduced When it is made 100% by weight, it is preferable to contain 1-50% by weight of the radical polymerizable compound (a1) with active methylene group, and 100 parts by weight relative to the total amount of the curable component, and contain a radical polymerization initiator (a2) 0.1-10 parts by weight.

As mentioned above, in the present invention, in the presence of the radical polymerization initiator (a2) having a hydrogen abstraction effect, the methylene group of the radical polymerizable compound (a1) having a living methylene group is caused to generate free radicals, and The aforementioned methylene group reacts with the hydroxyl group of the polarizer such as PVA to form a covalent bond. Therefore, in order to generate free radicals from the methylene group of the radical polymerizable compound (a1) having active methylene groups and fully form the aforementioned covalent bond, when the total amount of the curable component is 100% by weight, it is preferable to contain The radical polymerizable compound (a1) having active methylene groups is 1-50% by weight, and more preferably 3-30% by weight. When it is desired to sufficiently improve the water resistance and the adhesiveness in a non-dry state, the radical polymerizable compound (a1) having active methylene groups is preferably made 1% by weight or more. On the other hand, if it is more than 50% by weight, poor curing of the adhesive layer may occur. Furthermore, the radical polymerization initiator (a2) having a hydrogen abstraction effect is preferably contained in 0.1 to 10 parts by weight, and more preferably 0.3 to 9 parts by weight relative to 100 parts by weight of the total amount of the curable component. When the hydrogen abstraction reaction is desired to proceed sufficiently, it is preferable to use 0.1 parts by weight or more of the radical polymerization initiator (a2). On the other hand, if it is more than 10 parts by weight, it may not be completely dissolved in the adhesive.

"Thermal polymerization initiator"

The thermal polymerization initiator is preferably one that does not start polymerization by thermal splitting during the formation of the adhesive layer. For example, the thermal polymerization initiator is preferably one with a 10-hour half-life temperature of 65°C or higher, and further 75 to 90°C. In addition, the so-called half-life is an index indicating the decomposition rate of the polymerization initiator, and refers to the time until the remaining amount of the polymerization initiator becomes half. The decomposition temperature used to obtain the half-life at any time or the half-life time at any temperature is disclosed in the manufacturer’s catalog, for example, in the "Organic Peroxide Catalog 9th Edition (2003) May)" etc.

For example, the thermal polymerization initiator can include: lauryl peroxide (10-hour half-life temperature: 64°C), benzyl peroxide (10-hour half-life temperature: 73°C), 1,1-bis(t -Butylperoxy)-3,3,5-trimethylcyclohexane (10-hour half-life temperature: 90℃), bis(2-ethylhexyl) peroxydicarbonate (10-hour half-life temperature: 49℃) , Bis(4-t-butylcyclohexyl)peroxydicarbonate, bis-sec-butaneperoxydicarbonate (10 hours half-life temperature: 51℃), t-butaneperoxyneodecanoate (10 hours Half-life temperature: 48℃), t-hexylperoxy trimethyl acetate, t-butaneperoxy trimethyl acetate, dilaurinyl peroxide (10-hour half-life temperature: 64℃), di- n-octanoyl peroxide, 1,1,3,3-tetramethylbutaneperoxy-2-ethylhexanoate (10-hour half-life temperature: 66℃), bis(4-methylbenzyl) Peroxide, dibenzoyl peroxide (10-hour half-life temperature: 73°C), t-butyperoxyisobutyrate (10-hour half-life temperature: 81°C), 1,1-bis(t-hexane) Peroxo) organic peroxides such as cyclohexane.

Also, for example, the thermal polymerization initiator can include 2,2'-azobisisobutyronitrile (10-hour half-life temperature: 67°C), 2,2'-azobis(2-methylbutyronitrile) ) (10-hour half-life temperature: 67°C), 1,1-azobis-cyclohexane-1-carbonitrile (10-hour half-life temperature: 87°C) and other azo compounds.

The blending amount of the thermal polymerization initiator is 0.01-20 parts by weight relative to 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 adhesive>

Examples of the curable component of the cationic polymerization curable adhesive include compounds having epoxy groups or oxetanyl groups. 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. As an ideal epoxy compound, for example, a compound having at least two epoxy groups and at least one aromatic ring in the molecule (aromatic epoxy compound), or at least two epoxy groups in the molecule 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 cationic polymerization curable adhesive contains the epoxy compound and oxetane compound described above as curable components, and these are cured by cationic polymerization, a photocationic polymerization initiator is blended. The photocationic polymerization initiator is irradiated with active energy rays such as visible rays, ultraviolet rays, X-rays, electron rays, etc. to generate cationic species or Lewis acids, and start the polymerization reaction of epoxy groups or oxetanyl groups.

<Other ingredients>

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

<Acrylic Oligomer (A)>

In addition to the curable component related to the aforementioned radical polymerizable compound, the active energy ray curable adhesive related to the present invention may contain an acrylic oligomer (A) composed of polymerized (meth)acrylic monomers. Since the active energy ray-curable adhesive contains acrylic oligomer (A), the curing shrinkage when the active energy ray is irradiated to the adhesive and hardened can be reduced, and the adhesive, polarizer, transparent protective film, etc. can be reduced The interface stress of the adhered body. As a result, the deterioration of the adhesiveness between the adhesive layer and the adherend can be suppressed. In order to sufficiently suppress the curing shrinkage of the cured product 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 relative to 100 parts by weight of the total amount of the curable component The following. If the content of the acrylic oligomer (A) in the adhesive is too much, the reaction rate when the active energy ray is irradiated to the adhesive is drastically reduced, and the curing may be poor. On the other hand, the acrylic oligomer (A) is preferably 3 parts by weight or more, and more preferably 5 parts by weight or more with respect to 100 parts by weight of the total amount of the curable component.

When considering workability or uniformity during coating, the active energy ray-curable adhesive should have a low viscosity. Therefore, the acrylic oligomer (A) composed of polymerized (meth)acrylic monomers should also be low Viscosity. The acrylic oligomer with low viscosity and capable of preventing the curing shrinkage of the adhesive layer preferably has a weight average molecular weight (Mw) of 15,000 or less, and more preferably 10,000 or less, especially preferably 5,000 or less. On the other hand, in order to sufficiently suppress the curing shrinkage of the cured product layer (adhesive layer), the weight average molecular weight (Mw) of the acrylic oligomer (A) is preferably 500 or more, and more preferably 1000 or more, especially Is above 1500. Specifically, for example, the (meth)acrylic monomers constituting the acrylic oligomer (A) include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propylene 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, and for example, cycloalkyl (meth) acrylate (e.g. cyclohexyl (meth) acrylate, cyclopentyl (methyl) (Base) acrylate, etc.), aralkyl (meth)acrylate (e.g. benzyl (meth)acrylate, etc.), polycyclic (meth)acrylate (e.g. 2-isobornyl (meth)acrylic acid) Ester, 2-norbornylmethyl (meth)acrylate, 5-norbornen-2-yl-methyl (meth)acrylate, 3-methyl-2-norbornylmethyl (methyl) ) Acrylate, etc.), hydroxyl-containing (meth)acrylates (e.g. hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropylmethyl -Butyl (meth)methacrylate, etc.), (meth)acrylates containing alkoxy or phenoxy (2-methoxyethyl (meth)acrylate, 2-ethoxy Ethyl (meth)acrylate, 2-methoxymethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate Ester, phenoxyethyl (meth)acrylate, etc.), epoxy-containing (meth)acrylates (such as glycidyl (meth)acrylate, etc.), halogen-containing (meth) Acrylic esters (e.g. 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trifluoroethylethyl (meth)acrylate, tetrafluoropropyl (meth)acrylic acid Ester, hexafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptafluorodecyl (meth)acrylate, etc.), alkylaminoalkyl (meth)acrylate (For example, dimethylaminoethyl (meth)acrylate, etc.) and the like. These (meth)acrylates can be used individually or in combination of 2 or more types. Specific examples of the acrylic oligomer (A) include "ARUFON" manufactured by Toagosei Co., Ltd., "ACTFLOW" manufactured by Soken Chemical Co., Ltd., and "JONCRYL" manufactured by BASF Corporation in Japan. In the acrylic oligomer (A) composed of polymerized (meth)acrylic monomer, it is also preferable to have a high logPow value. The acrylic oligomer (A) is a component included in the calculation of the logPow value of the curable adhesive for polarizing films. In the calculation of the logPow value, the molar number of the components of the acrylic oligomer (A) is the molar number of the (meth)acrylic monomer that has been converted into the acrylic oligomer (A). The logPow value of the acrylic oligomer (A) composed of polymerized (meth)acrylic monomers is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more.

<Photo Acid Generator (B)>

The active energy ray-curable adhesive may contain a photoacid generator (B). When the photoacid generator is contained in the active energy ray-curable adhesive, the water resistance and durability of the adhesive layer can be improved drastically compared to when the photoacid 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 a cation and any of, X ^-. Selected from the group consisting represents _{^{PF6 6 -, SbF 6 -,}} AsF 6 -, SbCl 6 -, BiCl 5 -, SnCl 6 -, ClO 4 -, disulfide The relative anion in the group consisting of urethane anion and SCN-.)

Suitable structures for the onium cation constituting the onium cation L ⁺ of the general formula (3) include onium cations selected from the following general formulas (4) to (12).

General formula (4)

General formula (5)

General formula (6)

General formula (7)

General formula (8)

General formula (9)

General formula (10)

[Chemical formula 10]

General formula (11)

General formula (12)

[Chemical formula 12] Ar ⁴ -I ⁺ -Ar ⁵

(However, in the aforementioned general formulas (4)-(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, a substituted Or unsubstituted aryl, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic oxy, substituted or unsubstituted acyl Group, substituted or unsubstituted carbonyloxy group, substituted or unsubstituted oxycarbonyl group or halogen atom group. R ⁴ represents the same group as disclosed in R ¹ , R ² and R ^3. R ⁵ represents substituted or unsubstituted A substituted alkyl group, a substituted or unsubstituted alkylthio group. R ⁶ and R ⁷ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group. R represents a halogen atom, a hydroxyl group, a carboxyl group, a mercapto group , Cyano, nitro, substituted or unsubstituted aminemethanyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic group, Substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted heterocyclic oxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio, substituted or unsubstituted Any one of the heterocyclic thio group, substituted or unsubstituted acyl group, substituted or unsubstituted carbonyloxy group, substituted or unsubstituted oxycarbonyl group. Ar ⁴ , Ar ⁵ represent substituted or unsubstituted aryl groups, Any one of a substituted or unsubstituted heterocyclic group. X represents an oxygen or sulfur atom. i represents an integer from 0 to 5. j represents an integer from 0 to 4. k represents an integer from 0 to 3. In addition, adjacent R To each other, 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 also be cyclic structures bonded to each other.)

Onium cations (a cations) corresponding to general formula (4): Examples include: dimethyl phenyl sulfonium, dimethyl (o-fluorophenyl) sulfonium, dimethyl (m-chlorophenyl) sulfonium, Dimethyl (p-bromophenyl) arunium, dimethyl (p-cyanophenyl) arunium, dimethyl (m-nitrophenyl) arunium, dimethyl (2,4,6-tribromo Phenyl) amenium, dimethyl (pentafluorophenyl) amenium, dimethyl (p-(trifluoromethyl) phenyl) amenium, dimethyl (p-hydroxyphenyl) amenium, dimethyl (p -Mercaptophenyl) sulfonium, dimethyl (p-methanesulfinyl phenyl) sulfonium, dimethyl (p-methanesulfonyl phenyl) sulfonium, dimethyl (o-acetylphenyl) Arunium, dimethyl (o-benzylphenyl) arunnium, dimethyl (p-methylphenyl) arunnium, dimethyl (p-isopropylphenyl) arunnium, dimethyl (p- Octadecylphenyl) arunnium, dimethyl (p-cyclohexylphenyl) arunnium, dimethyl (p-methoxyphenyl) arunnium, dimethyl (o-methoxycarbonylphenyl) arunnium, two Methyl (p-phenylsulfonylphenyl) sulfonium, (7-methoxy-2-oxo-2H-chromen-4-yl) dimethyl sulfonium, (4-methoxynaphthalene-1 -Base) dimethyl arunnium, dimethyl (p-isopropoxycarbonylphenyl) arunnium, dimethyl (2-naphthyl) arunnium, dimethyl (9-anthryl) arunnium, diethyl phenyl Arunnium, methyl ethyl phenyl arunnium, methyl diphenyl arunnium, triphenyl arunnium, diisopropyl phenyl arunnium, diphenyl (4-phenylsulfonyl-phenyl)-arunnium, 4, 4'-bis(diphenyl sulfide) diphenyl sulfide, 4,4'-bis[bis[(4-(2-hydroxy-ethoxy)-phenyl)] sulfide]] diphenyl sulfide , 4,4'-Bis (diphenyl sulfonium) biphenyl, diphenyl (o-fluorophenyl) sulfonium, diphenyl (m-chlorophenyl) sulfonium, diphenyl (p-bromophenyl) ) Amenium, diphenyl (p-cyanophenyl) amenium, diphenyl (m-nitrophenyl) amenium, diphenyl (2,4,6-tribromophenyl) amenium, diphenyl ( Pentafluorophenyl) arunnium, diphenyl (p-(trifluoromethyl)phenyl) arunnium, diphenyl (p-hydroxyphenyl) arunnium, diphenyl (p-mercaptophenyl) arunnium, diphenyl Group (p-methanesulfinylphenyl) sulfonium, diphenyl (p-methanesulfonylphenyl) sulfonium, diphenyl (o-acetylphenyl) sulfonium, diphenyl (o-benzene) Methylphenyl) sulfonium, diphenyl (p-methylphenyl) sulfonium, diphenyl (p-isopropylphenyl) sulfonium, diphenyl (p-octadecylphenyl) sulfonium, two Phenyl (p-cyclohexylphenyl) sulfonium, diphenyl (p-methoxyphenyl) sulfonium, diphenyl (o-methoxycarbonylphenyl) sulfonium, diphenyl (p-phenylsulfonyl) Phenyl) arunnium, (7-methoxy-2-oxo-2H-chromen-4-yl) diphenyl arunnium, (4-methoxynaphthalene-1-yl) diphenyl arunnium, two Phenyl (p-isopropyloxycarbonylphenyl) amenium, diphenyl (2-naphthyl) amenium, diphenyl (9-anthryl) amenium, ethyl diphenyl amenium, methyl ethyl (o- Tolyl) sulfonium, methyl bis (p-tolyl) sulfonium, tris (p-tolyl) sulfonium, diisopropyl (4-phenylsulfonyl phenyl) sulfonium, diphenyl (2-thienyl) ) Arunium, diphenyl (2-furyl) arunium, diphenyl (9-ethyl-9H carbazole- 3-base) 鋶, etc. However, it is not limited to these.

Corresponding to the general formula (5) onium cation (sulfurium oxide cation): for example: dimethyl phenyl sulfonium oxide, dimethyl (o-fluorophenyl) sulfonium oxide, dimethyl (m-chlorophenyl) ) Sulfonium oxide, dimethyl (p-bromophenyl) sulfonium oxide, dimethyl (p-cyanophenyl) sulfonium oxide, dimethyl (m-nitrophenyl) sulfonium oxide, dimethyl (2 ,4,6-Tribromophenyl) sulfonium oxide, dimethyl (pentafluorophenyl) sulfonium oxide, dimethyl (p-(trifluoromethyl)phenyl) sulfonium oxide, dimethyl (p-hydroxyl) Phenyl) sulfonium oxide, dimethyl (p-mercaptophenyl) sulfonium oxide, dimethyl (p-methanesulfinyl phenyl) sulfonium oxide, dimethyl (p-methanesulfonyl phenyl) oxidation Phosphorus, dimethyl (o-acetylphenyl) sulfonium oxide, dimethyl (o-benzylphenyl) sulfonium oxide, dimethyl (p-methylphenyl) sulfonium oxide, dimethyl (p-isopropylphenyl) sulfonium oxide, dimethyl (p-octadecylphenyl) sulfonium oxide, dimethyl (p-cyclohexylphenyl) sulfonium oxide, dimethyl (p-methoxy) Phenyl) sulfonium oxide, dimethyl (o-methoxycarbonylphenyl) sulfonium oxide, dimethyl (p-phenylsulfonylphenyl) sulfonium oxide, (7-methoxy-2-oxo- 2H-chromen-4-yl) dimethyl sulfonium oxide, (4-methoxynaphthalene-1-yl) dimethyl sulfonium oxide, dimethyl (p-isopropoxycarbonylphenyl) sulfonium oxide, two Methyl (2-naphthyl) sulfonium oxide, dimethyl (9-anthryl) sulfonium oxide, diethyl phenyl sulfonium oxide, methyl ethyl phenyl sulfonium oxide, methyl diphenyl sulfonium oxide, triphenyl Sulfonium oxide, diisopropylphenyl sulfonium oxide, diphenyl (4-phenylsulfonyl-phenyl)-sulfonium oxide, 4,4'-bis(diphenyl sulfonium oxide) diphenyl sulfide , 4,4'-bis[bis[(4-(2-hydroxy-ethoxy)-phenyl)] sulfonium oxide] diphenyl sulfide, 4,4'-bis(diphenyl sulfonium oxide) Biphenyl, diphenyl (o-fluorophenyl) sulfonium oxide, diphenyl (m-chlorophenyl) sulfonium oxide, diphenyl (p-bromophenyl) sulfonium oxide, diphenyl (p-cyano) Phenyl) sulfonium oxide, diphenyl (m-nitrophenyl) sulfonium oxide, diphenyl (2,4,6-tribromophenyl) sulfonium oxide, diphenyl (pentafluorophenyl) sulfonium oxide, Diphenyl (p-(trifluoromethyl)phenyl) sulfonium oxide, diphenyl (p-hydroxyphenyl) sulfonium oxide, diphenyl (p-mercaptophenyl) sulfonium oxide, diphenyl (p- Methylsulfinyl phenyl) sulfonium oxide, diphenyl (p-methylsulfonyl phenyl) sulfonium oxide, diphenyl (o-acetylphenyl) sulfonium oxide, diphenyl (o-benzyl) Oxidation of sulfonium oxide, diphenyl (p-methylphenyl) sulfonium oxide, diphenyl (p-isopropylphenyl) sulfonium oxide, diphenyl (p-octadecylphenyl) oxide Aluminium, diphenyl (p-cyclohexylphenyl) sulfonium oxide, diphenyl (p-methoxyphenyl) sulfonium oxide, diphenyl (o-methoxycarbonylphenyl) sulfonium oxide, diphenyl ( p-Phenylsulfonylphenyl) sulfonium oxide, (7-methoxy-2-oxo-2H-chromen-4-yl)diphenyl sulfonium oxide, (4-methoxynaphthalene-1- Group) diphenyl sulfonium oxide, diphenyl (p-isopropoxycarbonyl phenyl) oxygen Aluminium oxide, diphenyl(2-naphthyl) oxonium oxide, diphenyl(9-anthryl) oxonium oxide, ethyldiphenyl oxonium oxide, methyl ethyl (o-tolyl) oxonium oxide, methyl Two (p-tolyl) sulfonium oxide, three (p-tolyl) sulfonium oxide, diisopropyl (4-phenylsulfonyl phenyl) sulfonium oxide, diphenyl (2-thienyl) sulfonium oxide, Diphenyl (2-furyl) sulfonium oxide, diphenyl (9-ethyl-9H carbazol-3-yl) sulfonium oxide, etc., however, it is not limited to these.

Onium cation (phosphonium cation) equivalent to general formula (6): Examples of phosphonium cations: Examples include: trimethylphenylphosphonium, triethylphenylphosphonium, tetraphenylphosphonium, triphenyl(p-fluoro Phenyl) phosphonium, triphenyl (o-chlorophenyl) phosphonium, triphenyl (m-bromophenyl) phosphonium, triphenyl (p-cyanophenyl) phosphonium, triphenyl (m-nitro Phenyl) phosphonium, triphenyl (p-phenylsulfonylphenyl) phosphonium, (7-methoxy-2-oxo-2H-chromen-4-yl) triphenyl phosphonium, triphenyl (o-hydroxyphenyl) phosphonium, triphenyl (o-acetylphenyl) phosphonium, triphenyl (m-benzyl phenyl) phosphonium, triphenyl (p-methylphenyl) phosphonium , Triphenyl (p-isopropoxyphenyl) phosphonium, triphenyl (o-methoxycarbonylphenyl) phosphonium, triphenyl (1-naphthyl) phosphonium, triphenyl (9-anthryl) Phosphonium, triphenyl(2-thienyl)phosphonium, triphenyl(2-furyl)phosphonium, triphenyl(9-ethyl-9Hcarbazol-3-yl)phosphonium, etc., however, it is not limited to this Wait.

Onium cation (pyridinium cation) corresponding to general formula (7): Examples of pyridinium cation: Examples include: N-phenylpyridinium, N-(o-chlorophenyl)pyridinium, N-(m- Chlorophenyl)pyridinium, N-(p-cyanophenyl)pyridinium, N-(o-nitrophenyl)pyridinium, N-(p-acetylphenyl)pyridinium, N-( p-isopropylphenyl)pyridinium, N-(p-octadecyloxyphenyl)pyridinium, N-(p-methoxycarbonylphenyl)pyridinium, N-(9-anthryl)pyridine Onium, 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-ethyl Pyridine-1-(p-methylphenyl)pyridinium, 2-methoxycarbonyl-1-(p-methylphenyl)pyridinium, 3-fluoro-1-naphthylpyridinium, 4-methyl-1-( 2-furyl)pyridinium, N-methylpyridinium, N-ethylpyridinium, etc., however, it is not limited to these.

Onium cations (quinolinium cations) equivalent to general formula (8): Examples of quinolinium cations: Examples include: N-methylquinolinium, N-ethylquinolinium, and N-phenylquinolinium Onium, N-naphthylquinolinium, N-(o-chlorophenyl)quinolinium, N-(m-chlorophenyl)quinolinium, N-(p-cyanophenyl)quinolinium, N-(o-nitrophenyl)quinolinium, N-(p-acetylphenyl)quinolinium, N-(p-isopropylphenyl)quinolinium, N-(p-ten Octaalkoxyphenyl)quinolinium, N-(p-methoxycarbonylphenyl)quinolinium, N-(9-anthryl)quinolinium, 2-chloro-1-phenylquinolinium, 2-cyano-1-phenylquinolinium, 2-methyl-1-phenylquinolinium, 2-vinyl-1-phenylquinolinium, 2-phenyl-1-phenylquinolinium Onium, 1,2-diphenylquinolinium, 2-methoxy-1-phenylquinolinium, 2-phenoxy-1-phenylquinolinium, 2-acetyl-1-benzene Quinolinium, 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-acetinyl-1-(2-thienyl)quinolinium, 2- Methoxycarbonyl-1-methylquinolinium, 3-fluoro-1-ethylquinolinium, 4-methyl-1-isopropylquinolinium, etc., however, it is not limited to these.

Onium cation (isoquinolinium cation) corresponding to general formula (9): Examples of isoquinolinium cations: Examples include: 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-acetylphenyl)isoquinolinium, N-(p-isopropylphenyl)isoquinolinium, N-( p-octadecyloxyphenyl)isoquinolinium, N-(p-methoxycarbonylphenyl)isoquinolinium, N-(9-anthryl)isoquinolinium, 1,2-diphenyl Butyl isoquinolinium, N-(2-furyl) isoquinolinium, N-(2-thienyl) isoquinolinium, N-naphthyl isoquinolinium, etc. However, it is not limited to these.

Onium cations (benzoxazolium cations, benzothiazolium cations) equivalent to general formula (10): Examples of benzoxazolium cations: Examples include: N-methylbenzoxazolium, N- Ethylbenzoxazolium, N-naphthylbenzoxazolium, N-phenylbenzoxazolium, N-(p-fluorophenyl)benzoxazolium, N-(p-chlorobenzene Yl)benzoxazolium, N-(p-cyanophenyl)benzoxazolium, N-(o-methoxycarbonylphenyl)benzoxazolium, N-(2-furyl)benzene Oxazolium, N-(o-fluorophenyl)benzoxazolium, N-(p-cyanophenyl)benzoxazolium, N-(m-nitrophenyl)benzoxazole Onium, N-(p-isopropoxycarbonylphenyl)benzoxazolium, N-(2-thienyl)benzoxazolium, N-(m-carboxyphenyl)benzoxazolium, 2 -Mercapto-3-phenylbenzoxazolium, 2-methyl-3-phenylbenzoxazolium, 2-methylthio-3-(4-phenylsulfonylphenyl)benzoxazone Azolium, 6-hydroxy-3-(p-tolyl)benzoxazolium, 7-mercapto-3-phenylbenzoxazolium, 4,5-difluoro-3-ethylbenzoxazole Onium etc., however, are not limited to these.

Examples of benzothiazolium cations: for example: N-methylbenzothiazolium, N-ethylbenzothiazolium, N-phenylbenzothiazolium, N-(1-naphthyl)benzothiazole Onium, 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-phenylbenzothiazolium, 7 -Mercapto-3-phenylbenzothiazolium, 4,5-difluoro-3-phenylbenzothiazolium, etc. However, it is not limited to these.

Onium cations (furyl or thienyl ionium cations) equivalent to general formula (11): Examples include: difuryl ionium, dithienyl ionium, bis(4,5-dimethyl-2-furan) Yl) phosphonium, bis(5-chloro-2-thienyl) phosphonium, bis(5-cyano-2-furyl) phosphonium, bis(5-nitro-2-thienyl) phosphonium, double (5-Acetyl-2-furyl)iconium, bis(5-carboxy-2-thienyl)iconium, bis(5-methoxycarbonyl-2-furyl)iconium, bis(5-benzene 2-furanyl) phosphonium, bis(5-(p-methoxyphenyl)-2-thienyl) phosphonium, bis(5-vinyl-2-furyl) phosphonium, bis(5 -Ethynyl-2-thienyl) phosphonium, bis(5-cyclohexyl-2-furyl) phosphonium, bis(5-hydroxy-2-thienyl) phosphonium, bis(5-phenoxy-2) -Furyl) phosphonium, bis(5-mercapto-2-thienyl) phosphonium, bis(5-butylthio-2-thienyl) phosphonium, bis(5-phenylthio-2-thienyl) However, it is not limited to these.

Onium cations (diaryl phosphonium cations) equivalent to general formula (12): Examples include: diphenyl phosphonium, bis(p-tolyl) phosphonium, and bis(p-octylphenyl) phosphonium , Bis(p-octadecylphenyl) phosphonium, bis(p-octyloxyphenyl) phosphonium, bis(p-octadecyloxyphenyl) phosphonium, phenyl (p-octadecane) (Oxyphenyl) phosphonium, 4-isopropyl-4'-methyldiphenyl phosphonium, (4-isobutylphenyl)-p-tolyl phosphonium, bis(1-naphthyl) phosphonium Onium, bis(4-phenylsulfonylphenyl) iodonium, phenyl(6-benzyl-9-ethyl-9H-carbazol-3-yl) iodonium, (7-methoxy -2-oxo-2H-chromen-3-yl)-4'-isopropylphenylinium etc. However, it is not limited to these.

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

The relative anion X ^- in the general formula (3) is not particularly limited in principle, however, it is preferably a non-nucleophilic anion. When the relative anion X ^{-is a} non-nucleophilic anion, it is not easy to cause a nucleophilic reaction in the cations coexisting in the molecule or in various materials used in combination. Therefore, the result can improve the photoacid production indicated by the general formula (2) The stability of the agent itself or the adhesive that uses it. The so-called non-nucleophilic anion here refers to an anion with a low ability to cause a nucleophilic reaction. Such anions include such _{^{as: PF 6 -, SbF 6 -}} , AsF 6 -, SbCl 6 -, BiCl 5 -, SnCl 6 -, ClO 4 -, urethane disulfide 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 following onium cations represented by the general formula (3) to the general formula (12) exemplified above specific examples of the structures selected from _{^{PF 6 -, SbF 6 -,}} AsF 6 -, SbCl 6 -, BiCl 5 -, SnCl 6 -, ClO 4 -, urethane disulfide anion, SCN ^- anion of.

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

The content of the photoacid generator (B) is 10 parts by weight or less, preferably 0.01-10 parts by weight, more preferably 0.05-5 parts by weight, and particularly preferably 0.1~ 3 parts by weight.

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

The active energy ray curable adhesive may contain a compound (C) containing either an alkoxy group or an epoxy group. For example, in the relationship with the hydroxyl group of the PVA-based polarizer, the alkoxy-containing compound (C1) will undergo the condensation reaction of the alkoxy group and the hydroxyl group, and the epoxy-containing compound (C2) will undergo the epoxy group The addition reaction with hydroxyl group can give the active energy ray hardening adhesive stronger adhesion. When using the epoxy-containing compound (C2), by the addition reaction of the epoxy group and the hydroxyl group, a secondary hydroxyl group is formed after the reaction, and the overall water absorption rate of the present invention may increase. Therefore, it is more suitable to use Alkoxy compound (C1). That is, a polarizer and a transparent protective film are laminated via an active energy ray curable adhesive containing a photoacid generator (B) and a compound having an alkoxy group (C1), and the active energy ray is irradiated by From the acid of the photoacid generator (B), the alkoxy group of the alkoxy compound (C1) and the hydroxyl group of the polarizing member undergo condensation reaction, and the polarizing member and the transparent protective film exhibit good adhesion. In addition, by the condensation reaction of the compounds (C1) having alkoxy groups with each other, an adhesive layer with lower water absorption is formed, and the optical durability under severe environments under high temperature and high humidity can be satisfied.

In the aforementioned active energy ray-curable adhesive, the compound (C) containing either an alkoxy group or an epoxy group may be used alone or in combination of plural kinds. Moreover, the compound (C) containing either an alkoxy group and an epoxy group can also use the compound (C1) containing an alkoxy group and the compound (C2) containing an epoxy group together. In addition, the compound (C) containing either an alkoxy group or an epoxy group may be used in combination with or without the photoacid generator (B). However, if the hydroxyl group and the alkoxy group of the PVA-based polarizer are promoted From the viewpoint 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).

(Compounds with alkoxy groups (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 known ones can be used. For example, it can be exemplified by the general formula: -(CH ₂ ) _n -OR (wherein n is an integer of 1 to 3, and R represents an alkyl group with 1 to 4 carbon atoms or H. In the aforementioned formula R is preferably a methyl group.) A compound having an alkoxy group as a substituent. Specifically, for example, alkoxyalkyl (meth)acrylates, alkoxyalkyl (meth)acrylamides and other radically polymerizable compounds containing alkoxy groups, hydroxymethyl Melamine compounds such as melamine, alkoxymethylated melamine, amine-based resins and silane coupling agents. Specific examples of radical polymerizable compounds containing alkoxy groups include: WASMER 2MA, WASMER 3MA, WASMER IBM, N-isobutoxymethacrylamide, WASMER EMA, N-MAM manufactured by Kasano Kosan Co., Ltd. -PC, MM90, WASMER A, etc. Specific examples of melamine compounds can be exemplified: SUMITEX RESIN series M-3, MK, M-6, M-100, MC, etc. manufactured by Sumitomo Chemical Corporation, or NIKALAC MW-30, MW-100LM manufactured by Sanwa Chemical Co., Ltd. , MX-750LM, MX-280, MX-270, etc. Among these, from the viewpoint of reactivity, WASMER 2MA, N-MAM-PC, MX-750LM, etc. are suitable. In addition, when calculating the glass transition temperature Tg of the adhesive layer, the compound having an alkoxy group and the polymer (C1) were not included in the calculation.

(Compounds with epoxy groups (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 reactive with epoxy groups in the molecule may also be used in combination. Here, for example, the functional group having reactivity with an epoxy group includes a carboxyl group, a phenolic hydroxyl group, a mercapto group, and a primary or secondary aromatic amine group. In consideration of three-dimensional hardenability, these functional groups are particularly preferably those having two or more in one molecule.

For example, polymers with more than one epoxy group in the molecule include epoxy resins, and include: bisphenol A epoxy resins derived from bisphenol A and epichlorohydrin, and bisphenol A epoxy resins derived from bisphenol A and epichlorohydrin. Bisphenol F epoxy resin of phenol F and epichlorohydrin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, bisphenol F Phenolic type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, sulphur type epoxy resin, three Multifunctional epoxy resins such as functional epoxy resin or tetrafunctional epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, allantoin epoxy resin, trimeric isocyanate epoxy resin Resins, aliphatic chain epoxy resins, etc., and these epoxy resins may be halogenated or hydrogenated. For example, commercially available epoxy resin products can include: JER paint 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000, EPICLON830, EXA835LV, HP4032D, HP820 made by DIC Co., Ltd., EP4100 series, EP4000 series, EPU series made by Adike Co., Ltd., CELLOXIDE series made by DAICEL Chemical Co., Ltd. (2021, 2021P, 2083) , 2085, 3000, etc.), EPOLEAD series, EHPE series, YD series, YDF series, YDCN series, YDB series, phenoxy resin (polyol synthesized from bisphenols and epichlorohydrin) manufactured by Nippon Steel Chemical Company Polyether and epoxy groups at both ends; YP series, etc.), DENACOL series manufactured by Nagase Chemtex, EPOLIGHT series manufactured by Kyoeisha Chemical Company, etc., however, it is not limited to these. These epoxy resins can also use 2 or more types together. In addition, when calculating the glass transition temperature Tg of the adhesive layer, the compound (C2) having an epoxy group was not included in the calculation.

The blending amount of the compound (C) containing either an alkoxy group or an epoxy group is usually 30 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component. If the active energy ray hardening adhesive contains the aforementioned If the content of the compound (C) is too much, the adhesiveness will decrease, and the impact resistance to the drop test may deteriorate. The content of the aforementioned compound (C) in the active energy ray hardening 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 2 parts by weight or more of the aforementioned compound (C), and more preferably 5 parts by weight or more.

<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 hydroxyl group on the surface of the polarizer interacts with the isocyanate group to give the polarizing film stronger adhesiveness and water resistance. In addition, when the active energy ray-curable adhesive contains an N-hydroxyalkyl group-containing (meth)acrylamide derivative as a radical polymerizable compound, if the N-hydroxyalkyl group-containing (meth)acrylamide derivative As the content of the amine derivative increases, 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 under severe humidified environments tends to decrease. By using the N-hydroxyalkyl group-containing (meth)acrylamide derivative and the compound having an isocyanate group together, it does not help the hydroxyl group and the isocyanate group that are attached to the polarizer to form a urethane bond, and It can maintain adhesion while reducing overall water absorption.

Examples of the isocyanate compound (D) include polyfunctional isocyanate compounds, active energy ray-curable isocyanate compounds, and the like. For example, the polyfunctional isocyanate compound may include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate; Cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, hydrogenated phenylene diisocyanate, hydrogenated xylene diisocyanate and other alicyclic polyisocyanates; 2,4-phenylene diisocyanate Aromatic polyisocyanates such as diisocyanate, 2,6-tolylphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, and stubbyl diisocyanate. For example, the aforementioned isocyanate compound (D) may also be exemplified as: trimethylolpropane/phenylene diisocyanate adduct [manufactured by Japan Polyurethane Industry Co., Ltd., trade name "CORONATE L" ], Trimethylolpropane/hexamethylene diisocyanate adduct [manufactured by Japan Polyurethane Industry Co., Ltd., trade name "CORONATE HL"], trade name "CORONATE HX" (Japanese polyamino Formate Industry Co., Ltd.), trimethylolpropane/diisocyanate adduct [manufactured by Mitsui Chemicals Co., Ltd., trade name "TAKENATE110N"] and other commercially available products. Examples of the active energy ray-curable isocyanate compound (D) include isocyanates having (meth)acryloyl groups, for example, KARENZ AOI (manufactured by Showa Denko Co., Ltd.), KARENZ BEI (Showa Denko) Commercial products such as Co., Ltd. and Laromer LR9000 (BASF).

The blending amount of the isocyanate compound (D) is usually 30 parts by weight or less relative to 100 parts by weight of the total amount of the curable component. If the content of the aforementioned compound (D) in the active energy ray-curable adhesive is too large, the adhesiveness will be poor Decrease, and the impact resistance of the drop test may deteriorate. The content of the aforementioned compound (D) in the active energy ray hardening 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 part by weight or more of the aforementioned compound (D), more preferably 1 part by weight or more.

<Silane Coupling Agent (E)>

When the curable adhesive for polarizing films of the present invention is an active energy ray curable type, the silane coupling agent (E) is preferably an active energy ray curable compound. However, even if it is not active energy ray curable, the same Water resistance.

As a specific example of the silane coupling agent (E), the active energy ray-curable compound may include vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, 2-(3,4 epoxy) Cyclohexyl) ethyl trimethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl methyl diethoxy silane, 3-glycidoxy propyl Triethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, etc.

More desirable are 3-methacryloxypropyl trimethoxysilane and 3-acryloxypropyl trimethoxysilane.

A specific example of a silane coupling agent that is not curable by active energy rays is preferably a silane coupling agent having an amino group (E1). Specific examples of the silane coupling agent (E1) having an amino group include: γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-Aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-amine ethyl) Yl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane , Γ-(2-aminoethyl)aminopropyl triisopropoxysilane, γ-(2-(2-aminoethyl)aminoethyl)aminopropyl trimethoxysilane, γ-(6-amine Hexyl)aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, γ-ureapropyltrimethoxysilane, γ-ureapropyltriethoxy Silane, N-phenyl-γ-aminopropyl trimethoxysilane, N-benzyl-γ-aminopropyl trimethoxysilane, N-vinylbenzyl-γ-aminopropyl triethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) Aminomethyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine and other silanes containing amino groups; N-(1,3-dimethylbutylene )-3-(Triethoxysilyl)-1-propylamine and other ketimine silanes.

The silane coupling agent (E1) having an amine group may be used only by one type, and plural types may be used in combination. Among them, in order to ensure good adhesion, γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl) Aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, N -(1,3-Dimethylbutylene)-3-(triethoxysilyl)-1-propylamine.

The blending amount of the silane coupling agent (E) is preferably in the range of 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, and more preferably 0.1 to 10 parts by weight relative to 100 parts by weight of the total amount of the curable component. This is because when the blending amount exceeds 20 parts by weight, the storage stability of the adhesive deteriorates, and when it is less than 0.1 parts by weight, the effect of water-resistant adhesiveness cannot be fully exhibited. In addition, when calculating the glass transition temperature Tg of the adhesive layer, the silane coupling agent (E) was not included in the calculation.

Specific examples of silane coupling agents that are not curable with active energy rays other than the foregoing include: 3-ureapropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxy Triethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, imidazole silane, etc.

For the aforementioned photoacid generator (B), compound (C) containing any of alkoxy group and epoxy group, isocyanate compound (D), silane coupling agent (E), the logPow value of each component is also preferably 1 Above, and more preferably 2 or more. In addition, the photoacid generator (B) and the silane coupling agent (E) are not included in the calculation of the logPow value of the curable adhesive for polarizing films. On the other hand, the compound (C) and the isocyanate compound (D) containing any one of an alkoxy group and an epoxy group are included in the calculation of the logPow value of the curable adhesive for polarizing films.

<Additives other than the foregoing>

In addition, in the curable adhesive for polarizing films of the present invention, various additives can be blended as other optional components within a range that does not impair the purpose and effects of the present invention. The aforementioned additives may include, for example: polyamide, polyamide imide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer Polymers or oligomers such as materials, petroleum resins, xylene resins, ketone resins, cellulose resins, fluorine-based oligomers, polysiloxane-based oligomers, and polysulfide-based oligomers; phenothiazine, 2, 6-di-t-butyl-4-cresol and other polymerization inhibitors; polymerization initiation aids; leveling agents; wettability modifiers; surfactants; plasticizers; ultraviolet absorbers; inorganic fillers; pigments; Dyes, etc. Among various additives, the one with higher logPow value is also suitable. The logPow value of various additives is preferably 2 or more, more preferably 3 or more, and most preferably 4 or more. In addition, these additives are not included in the calculation of the logPow value of the hardening adhesive for polarizing films.

The aforementioned additives are usually 0-10 parts by weight, preferably 0-5 parts by weight, and most preferably 0-3 parts by weight, relative to 100 parts by weight of the total amount of the curable component.

<Viscosity of Adhesive>

The curable adhesive for polarizing films of the present invention contains the aforementioned curable component. However, from the viewpoint of coating properties, the viscosity of the adhesive is preferably 100 cp or less at 25°C. On the other hand, when the curable adhesive for polarizing films of the present invention is as large as 100 cp at 25°C, the temperature of the adhesive can also be adjusted to 100 cp or less during coating. The more ideal range of viscosity is 1~80cp, and the most ideal is 10~50cp. Viscosity can be measured using the E-type viscometer TVE22LT manufactured by Toki Sangyo Co., Ltd.

In addition, from the viewpoint of safety, it is preferable that the curable adhesive for polarizing films of the present invention uses a material with low skin irritation as the curable component. Skin irritation can be judged by the so-called P.I.I. P.I.I is widely used to show the degree of skin disorders, and is measured by Cui's method. The measured value is expressed in the range of 0-8. The smaller the value, the lower the irritation. However, since the error of the measured value is large, it can be used as a reference value. P.I.I is preferably 4 or less, more preferably 3 or less, and most preferably 2 or less.

<Polarizing Film>

In the polarizing film of the present invention, a transparent protective film is bonded to an adhesive layer formed by interposing the cured material layer of the aforementioned curable adhesive for polarizing film on at least one side of a polarizer. As described above, the adhesive layer belonging to the cured product layer has an overall water absorption rate of 10% by weight or less.

<Adhesive layer>

The thickness of the adhesive layer formed by the aforementioned hardening type adhesive is preferably controlled to 0.1~3μm. The thickness of the adhesive layer is more preferably 0.3 to 2 μm, and further preferably 0.5 to 1.5 μm. In order to suppress the occurrence of poor adhesion or appearance defects (bubbles) during lamination by the cohesive force of the adhesive layer, the thickness of the adhesive layer is preferably 0.1 μm or more. On the other hand, if the adhesive layer is thicker than 3 μm, the polarizing film may not satisfy the durability.

In addition, the hardening type adhesive should preferably be selected so that the Tg of the adhesive layer formed by this will constitute 60°C or higher, and more preferably 70°C or higher, and more preferably 75°C or higher, furthermore 100°C or higher, even Above 120°C. On the other hand, if the Tg of the adhesive layer is too high, the flexibility of the polarizing film will decrease. Therefore, the Tg of the adhesive layer should be set below 300°C, and then 240°C or less, or even 180°C or less. Tg<Glass transition temperature> is measured by the following measurement conditions using the dynamic viscoelasticity measuring device RSAIII manufactured by TA Instruments.

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

The dynamic viscoelasticity is measured and the temperature Tg of the peak top of tan δ is used.

In addition, it is preferable that the hardening type adhesive is 1.0×10 ⁶ Pa or more in the area where the storage modulus of the adhesive layer formed by this is below 70°C. Furthermore, it is more preferably 1.0×10 ⁷ Pa or more. The storage modulus of the adhesive layer will affect the cracks of the polarizer when the polarizing film is subjected to thermal cycling (-40°C to 80°C, etc.). When the storage modulus is low, the problem of polarizer cracks is likely to occur. The temperature range with high storage modulus is more preferably below 80°C, most preferably below 90°C. The storage modulus is measured simultaneously with Tg<glass transition temperature> using a dynamic viscoelasticity measuring device RSAIII made by TA Instruments and under the same measuring conditions. Perform dynamic viscoelasticity measurement, and use the value of storage modulus (E'').

The polarizing film related to the present invention has the steps of: applying a hardening type adhesive on the surface where the adhesive layer has been formed on the polarizer and/or the surface where the adhesive layer is formed on the transparent protective film, and then bonding the polarizer and the transparent protective film; , The step of hardening the curing adhesive to form an adhesive layer.

Polarizers and transparent protective films can also be subjected to surface modification treatment before coating the aforementioned hardening adhesive. Specific treatments can be exemplified by corona treatment, plasma treatment, saponification treatment, etc.

The coating method of the hardening adhesive can be appropriately selected according to the viscosity of the hardening adhesive or the target thickness. For example, examples of coating methods include: reverse coater, gravure coater (direct, reverse, or indirect), bar reverse coater, roll coater, die coating Machine, bar coater, rod coater, etc. In addition, for coating, a dipping method or the like can be appropriately used.

The polarizer and the transparent protective film are bonded through the hardened adhesive that has been applied as described above. The adhesion of the polarizer and the transparent protective film can be carried out by a roll laminator or the like.

<Hardening of Adhesive>

The curable adhesive for polarizing films of the present invention can be used as an active energy ray curable adhesive or a thermosetting adhesive. Among the active energy ray hardening adhesives, it can be used in electron beam hardening, ultraviolet hardening, and visible light hardening. From the viewpoint of productivity, the state of the aforementioned curable adhesive is that the active energy ray curable adhesive is better than the thermosetting adhesive. Furthermore, from the viewpoint of productivity, the active energy ray The hardening adhesive is preferably a visible light hardening adhesive.

"Active energy ray hardening type"

In the active energy ray hardening adhesive, after bonding the polarizer and the transparent protective film, irradiate active energy rays (electron rays, ultraviolet rays, visible rays, etc.) to harden the active energy ray hardening adhesive to form an adhesive layer . The irradiation direction of active energy rays (electron rays, ultraviolet rays, visible rays, etc.) can be irradiated from any suitable direction. It is preferable to irradiate from the side of the transparent protective film. If irradiated from the side of the polarizer, the polarizer may be degraded by active energy rays (electron beams, ultraviolet rays, visible rays, etc.).

"Electron beam hardening type"

In the electron beam hardening type, any appropriate conditions can be adopted as long as the electron beam irradiation conditions can harden the aforementioned active energy ray hardening adhesive. For example, the accelerating voltage for electron beam irradiation is preferably 5kV~300kV, and more preferably 10kV~250kV. When the accelerating voltage is less than 5kV, the electron beam cannot reach the adhesive and there is a risk of insufficient curing. If the accelerating voltage is greater than 300kV, the penetration force through the sample is too strong and the transparent protective film or the polarizer may be damaged. The amount of irradiation is 5-100kGy, and more preferably 10-75kGy. When the amount of irradiation is less than 5kGy, the adhesive will be insufficiently cured. If it is greater than 100kGy, it will damage the transparent protective film or polarizer, reduce the mechanical strength or yellow, and fail to obtain the predetermined optical properties.

Electron beam irradiation is usually carried out in an inert gas, however, if necessary, it can also be carried out in the atmosphere or under the condition of introducing a small amount of oxygen. Although it differs according to the material of the transparent protective film, by appropriately introducing oxygen, the surface of the transparent protective film irradiated by the electron beams is intentionally suppressed by oxygen, and the damage to the transparent protective film can be prevented and effectively The electron beam is irradiated only to the adhesive.

"Ultraviolet curing type, visible light curing type"

In the manufacturing method of the polarizing film of the present invention, the active energy line preferably contains the visible light in the wavelength range of 380nm~450nm, especially the active energy line that has the largest amount of visible light in the wavelength range of 380nm~450nm. In the ultraviolet curable type and visible light curable type, when using a transparent protective film that has been endowed with ultraviolet absorbing ability (ultraviolet non-transmissive transparent protective film), it absorbs light with a wavelength shorter than 380nm, so light with a wavelength shorter than 380nm It does not reach the active energy ray-curable adhesive and does not contribute to the polymerization reaction. Furthermore, the light with a wavelength shorter than 380nm absorbed by the transparent protective film will be converted into heat, and the transparent protective film itself will generate heat, which can cause defects such as curling and wrinkles of the polarizing film. Therefore, when the ultraviolet curing type and the visible light curing type are used in the present invention, the active energy ray generating device should preferably use a device that does not emit light with a wavelength shorter than 380nm. More specifically, the cumulative illuminance of the wavelength range of 380~440nm and The ratio of accumulated illuminance in the wavelength range of 250~370nm should be 100:0~100:50, and more preferably 100:0~100:40. The active energy line related to the present invention is preferably a gallium-enclosed metal halide lamp and an LED light source with a luminous wavelength range of 380 to 440 nm. Or, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, incandescent lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser or Sunlight and other light sources include ultraviolet rays and visible rays, and band-pass filters can also be used to block ultraviolet rays with a wavelength shorter than 380nm. In order to improve the bonding performance of the adhesive layer between the polarizer and the transparent protective film, and to prevent the curling of the polarizing film, the following active energy rays should be used, namely: use a metal halide lamp enclosed in gallium and pass through a wavelength shorter than 380nm The active energy line obtained from the bandpass filter of the light, or the active energy line with the wavelength of 405nm obtained from the LED light source.

In the ultraviolet curing type or visible light curing type, it is better to heat the active energy ray curing adhesive before irradiating ultraviolet or visible light (heating before irradiation). At this time, the temperature should be above 40℃, and more preferably The heating is above 50°C. In addition, it is also suitable to heat the active energy ray hardening adhesive after irradiating ultraviolet rays or visible rays (heating after irradiation). In this case, the temperature should be above 40°C, and more preferably above 50°C.

The active energy ray-curable adhesive of the present invention can be suitably used in the following situations, namely: forming an adhesive layer that adheres to a polarizer and a transparent protective film with 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 aforementioned general formula (1), whereby it can be cured by irradiating ultraviolet rays through a transparent protective film with UV absorbing ability to form an adhesive layer . According to this, even if a transparent protective film with UV absorbing ability is already laminated on the polarizing film on both sides of the polarizer, the adhesive layer can be hardened. However, it is of course possible to harden the adhesive layer in a polarizing film that has been laminated with a transparent protective film without UV absorption capability. In addition, the so-called transparent protective film with UV absorption capacity means a transparent protective film with a transmittance of less than 10% to 380nm light.

The method of imparting UV absorbing ability to the transparent protective film can include, for example, a method of containing an ultraviolet absorber in the transparent protective film, or a method of laminating a surface treatment containing an ultraviolet absorber on the surface of the transparent protective film.

For example, specific examples of ultraviolet absorbers include: conventionally known oxybenzophenone compounds, benzotriazole compounds, salicylate compounds, benzophenone compounds, and cyanoacrylates. Based compounds, nickel complex salt based compounds, triazine based compounds, etc.

After bonding the polarizer and the transparent protective film, irradiate active energy rays (electron rays, ultraviolet rays, visible rays, etc.), and harden the active energy ray hardening adhesive to form an adhesive layer. The irradiation direction of active energy rays (electron rays, ultraviolet rays, visible rays, etc.) can be irradiated from any suitable direction. It is preferable to irradiate from the side of the transparent protective film. If irradiated from the side of the polarizer, the polarizer may be degraded by active energy rays (electron beams, ultraviolet rays, visible rays, etc.).

"Thermosetting type"

On the other hand, in the thermosetting adhesive, after bonding the polarizer and the transparent protective film, heating is performed to start polymerization by the thermal polymerization initiator, and a cured layer is formed. The heating temperature can be set according to the thermal polymerization initiator, but is 60 to 200°C, and preferably 80 to 150°C.

When the polarizing film of the present invention is manufactured by a continuous line, although the line speed varies according to the curing time of the adhesive, it is preferably 1~500m/min, and more preferably 5~300m/min, and more preferably It is 10~100m/min. When the line speed is too low, productivity is lacking, or the damage to the transparent protective film is too great to make a polarizing film that can withstand durability tests, etc. When the line speed is too high, the curing of the adhesive is insufficient, and the target adhesiveness may not be obtained.

In addition, the polarizing film of the present invention is an adhesive layer formed by interposing the cured material layer of the active energy ray-curable adhesive. The polarizer and the transparent protective film are bonded together. However, it can be easily installed between the transparent protective film and the adhesive layer. Then layer. For example, the easy bonding layer can be formed by having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a polysiloxane system, a polyamide skeleton, a polyimide skeleton, and a polyethylene skeleton. It is formed by various resins such as alcohol skeleton. These polymer resins can be used individually by 1 type or in combination of 2 or more types. In addition, other additives may be added to the formation of the easily bonding layer. Specifically, stabilizers such as tackifiers, ultraviolet absorbers, antioxidants, and heat-resistant stabilizers can be further used.

The easy-to-bond layer is usually set on the transparent protective film in advance, and the easy-to-bond layer side of the transparent protective film and the polarizer are bonded by the adhesive layer. The easy adhesion layer is formed by coating and drying the easy adhesion layer forming material on the transparent protective film by a known technique. The forming material of the easy-bonding layer is usually adjusted to a solution of an appropriate concentration having considered the thickness after drying and the smoothness of the coating. The thickness of the easy bonding layer after drying is preferably 0.01-5 μm, more preferably 0.02-2 μm, and further preferably 0.05-1 μm. In addition, the easy-bonding layer can be provided with multiple layers. However, in this case, the total thickness of the easy-bonding layer should also be set to the aforementioned range.

<Polarizer>

There are no special restrictions on the polarizer, and various polarizers can be used. For example, the polarizing member may include: absorbing dichroic materials such as iodine or dichroic dyes on polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, and ethylene. Vinyl acetate copolymer is a hydrophilic polymer film such as a partially saponified film and uniaxially stretched, a polyene-based oriented film such as a dehydrated polyvinyl alcohol or a dehydrochloricated polyvinyl chloride. Among them, it is also suitable for a polarizer composed of a polyvinyl alcohol-based film and dichroic substances such as iodine. The thickness of these polarizers is not particularly limited, however, it is generally below 80 μm.

For example, a polarizer in which a polyvinyl alcohol-based film is dyed with iodine and uniaxially stretched can be produced as follows: dyed by immersing polyvinyl alcohol in an aqueous solution of iodine, and stretched to the original length 3~7 times. If necessary, it can also be immersed in aqueous solutions such as boric acid or potassium iodide. Furthermore, 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 dirt or anti-caking agent on the surface of the polyvinyl alcohol-based film can be cleaned. In addition, by swelling the polyvinyl alcohol-based film, it can also prevent uneven dyeing. Uniform effect. The extension can be performed after dyeing with iodine, or it can be extended while dyeing, or it can be dyed with iodine after extension. It can also be extended in aqueous solutions of boric acid or potassium iodide or in a water bath.

In addition, when the hardening adhesive of the present invention uses a thin polarizer with a thickness of 10 μm or less as a polarizer, its effect can be clearly exhibited (satisfying the optical durability under severe environments under high temperature and high humidity). Compared with the polarizers with a thickness of more than 10μm, the aforementioned polarizers with a thickness of 10μm or less have a greater impact on moisture, and have insufficient optical durability under high temperature and high humidity environments, and are likely to cause increase in transmittance or decrease in polarization . That is, when the above-mentioned polarizer of 10 μm or less is laminated by the adhesive having an overall water absorption rate of 10% by weight or less of the present invention, the movement of water toward the polarizer under the severe environment of high temperature and high humidity can be significantly suppressed. It suppresses the deterioration of optical durability such as increase in transmittance of polarizing film and decrease in polarization degree. From the viewpoint of thinning, the thickness of the polarizer is preferably 1~7μm. Such a thin polarizer has less unevenness in thickness, is distinguishable, and has less dimensional changes. Furthermore, the thickness of the polarizing film is ideal for achieving thinner thickness.

Representatively, thin polarizers can be listed as: disclosed in Japanese Patent Laid-Open No. 51-069644 or 2000-338329, or WO2010/100917, PCT/JP2010/001460, or Japanese The thin polarizing film of the special wish No. 2010-269002 or the special wish No. 2010-263692. These thin polarizing films can be obtained by a manufacturing method including the following steps, namely: a step of extending a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a resin substrate for stretching in the state of a laminate; And the steps of dyeing. According to this manufacturing method, even if the PVA-based resin layer is thin, by supporting it on the resin substrate for stretching, it can be stretched without problems such as cracks due to stretching.

In the manufacturing method including the step of stretching in the state of the laminate and the step of dyeing, from the point of view that it can be stretched to a high magnification to improve the polarization performance, the aforementioned thin polarizing film is also suitable for use such as WO2010/100917 The specification, the specification of PCT/JP2010/001460 or the specification of Japanese Patent Application No. 2010-269002 or Japanese Patent Application No. 2010-263692 can be obtained by the preparation method including the step of extending in the aqueous solution of boric acid. It is obtained by the preparation method disclosed in the specification No. 2010-269002 or the specification No. 2010-263692 that includes the auxiliary ground-to-air extension step in the boric acid aqueous solution.

The thin, high-performance polarizing film disclosed in the aforementioned specification of PCT/JP2010/001460 is integrally formed on a resin substrate, and is composed of PVA-based resin with dichroic substances oriented, and has a thickness of 7 μm or less, and It has the optical properties of monomer transmittance above 42.0% and polarization degree above 99.95%.

The aforementioned thin high-performance polarizing film can be manufactured as follows: by coating and drying a PVA-based resin, a PVA-based resin layer is formed on a resin substrate with a thickness of at least 20μm, and the generated PVA-based resin The layer is immersed in the dyeing solution of the dichroic substance, and the dichroic substance is adsorbed on the PVA resin layer, and in the boric acid aqueous solution, the PVA resin layer that has adsorbed the dichroic substance is integrally extended with the resin substrate The total stretch magnification constitutes more than 5 times the original length.

In addition, a method for manufacturing a laminate film containing a thin high-performance polarizing film with dichroic substances oriented, comprising the following steps, namely: a step of forming a laminate film, the laminate film including a resin substrate And a PVA-based resin layer, and the resin substrate has a thickness of at least 20 μm. The PVA-based resin layer is formed by coating and drying an aqueous solution containing PVA-based resin on one side of the resin substrate; the adsorption step is by The laminate film containing the resin substrate and the PVA-based resin layer formed on one side of the resin substrate is immersed in a dye solution containing a dichroic substance, so that the PVA-based resin layer contained in the laminate film is absorbed Chromatic substance; the stretching step is to stretch the aforementioned laminate film containing the PVA-based resin layer to which the dichroic substance has been adsorbed in an aqueous solution of boric acid so that the total stretching ratio is 5 times or more of the original length; and manufacturing the laminate In the step of forming a thin film, the laminate film is formed by integrally extending the PVA-based resin layer that has adsorbed the dichroic substance and the resin substrate to form a thin, high-performance polarizing film on one side of the resin substrate, and the thin and high The functional polarizing film is composed of a PVA-based resin layer with a dichroic material oriented, with a thickness of 7μm or less, and has the optical characteristics of a monomer transmittance of 42.0% or more and a polarization degree of 99.95% or more; Manufacture the aforementioned thin high-performance polarizing film.

The thin polarizing film of the aforementioned Japanese Patent Application No. 2010-269002 or Japanese Patent Application No. 2010-263692 is a continuous base polarizing film composed of PVA-based resins with dichroic substances oriented, and includes The laminate of the PVA-based resin layer of the amorphous ester-based thermoplastic resin substrate is stretched by a two-stage stretching step, whereby a thickness of 10μm or less is made, and the two-stage stretching step is assisted by aerial stretching and boric acid Constructed by water extension. When the transmittance of the monomer is T and the degree of polarization is P, the aforementioned thin polarizing film should be made to satisfy P>-(10 ^{0.929T-42.4-1} )×100 (however, T<42.3) and P≧99.9 (However, T≧42.3) conditions of optical characteristics.

Specifically, the aforementioned thin polarizing film can be manufactured by a thin polarizing film manufacturing method that includes the following steps, namely: one step, by applying an amorphous ester-based thermoplastic resin film formed on a continuous base The PVA-based resin layer of the base material is stretched at high temperature in the air to generate an extended intermediate product composed of the oriented PVA-based resin layer; one step is to absorb the dichroic substance of the extended intermediate product to generate A colored intermediate product composed of a PVA-based resin layer with a dichroic substance (preferably iodine or a mixture of iodine and organic dye) oriented; and a step, which is formed by extending the colored intermediate product in boric acid water A polarizing film with a thickness of 10 μm or less composed of a PVA-based resin layer with a dichroic substance aligned.

In this manufacturing method, the total extension ratio of the PVA-based resin layer that has been formed into a film on the amorphous ester-based thermoplastic resin substrate using air-temperature extension and boric acid water extension is preferably made more than 5 times. The liquid temperature of the boric acid aqueous solution for extension in boric acid water can be made above 60℃. Before extending the colored intermediate product in the boric acid aqueous solution, the colored intermediate product is preferably insolubilized. In this case, it is preferable to immerse the colored intermediate product in the boric acid aqueous solution whose liquid temperature is not higher than 40°C. The aforementioned amorphous ester-based thermoplastic resin base material can be made into copolymerized polyethylene terephthalate by copolymerizing isophthalic acid, and copolymerized polyethylene terephthalate by copolymerizing cyclohexane dimethanol. Or other non-crystalline polyethylene terephthalate copolymerized with polyethylene terephthalate, and preferably made of transparent resin, the thickness of which can be made into a film at least 7 times the thickness of the PVA-based resin layer . In addition, the stretching ratio of high-temperature stretching in the air is preferably 3.5 times or less, and the stretching temperature of high-temperature stretching in the air is preferably higher than the glass transition temperature of the PVA-based resin, specifically in the range of 95°C to 150°C. When performing high-temperature stretching in the air by uniaxial stretching of the free ends, the total stretching ratio of the PVA-based resin layer that has been filmed on the amorphous ester-based thermoplastic resin substrate is preferably 5 times or more and 7.5 times or less. In addition, when performing high-temperature stretching in the air by uniaxial stretching of a fixed end, the total stretching ratio of the PVA-based resin layer that has been filmed 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 manufactured by the following method.

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

Prepare 200μm thick amorphous PET substrate, and 4~5% concentration of PVA aqueous solution in which PVA powder with polymerization degree above 1000 and saponification degree above 99% is dissolved in water. Secondly, the PVA aqueous solution was coated on a 200μm thick amorphous PET substrate and dried at a temperature of 50-60°C to prepare a laminate with a 7μm thick PVA layer formed on the amorphous PET substrate.

The laminate including the PVA layer with a thickness of 7 μm is subjected to the following steps including a two-stage extension step including aerial auxiliary extension and extension in boric acid water, and a thin high-performance polarizing film with a thickness of 3 μm is produced. Through the air-assisted stretching step in the first stage, a laminate including a 7 μm thick PVA layer and an amorphous PET substrate are integrally extended, and an extended laminate including a 5 μm thick PVA layer is formed. Specifically, the stretched laminate is a stretcher equipped with a laminate containing a 7μm thick PVA layer placed in an oven, and uniaxially stretched at the free end to a stretch magnification of 1.8 times, and the oven is set to 130 ℃ extended temperature environment. Through this stretching process, the PVA layer contained in the stretched laminate is changed into a 5 μm thick PVA layer in which PVA molecules have been oriented.

Secondly, through the dyeing step, a colored laminate having a 5 μm thick PVA layer in which iodine has been adsorbed on the PVA molecules has been oriented. Specifically, for the colored laminate, the stretched laminate is immersed in a dyeing solution containing iodine and potassium iodide at a liquid temperature of 30°C for an arbitrary period of time so that the monomer transmittance of the PVA layer that constitutes the final high-performance polarizing film Composition 40~44%, by this, iodine is absorbed in the PVA layer contained in the stretch laminate. In this step, the dyeing solution uses water as a solvent, and the iodine concentration is set to be in the range of 0.12 to 0.30 wt%, and the potassium iodide concentration is set to be in the range of 0.7 to 2.1 wt%. The concentration ratio of iodine to potassium iodide is 1:7. Incidentally, when you want to dissolve iodine in water, potassium iodide is necessary. In more detail, by immersing the stretched laminate in a dyeing solution with an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.1% by weight for 60 seconds, a 5μm thick PVA layer in which iodine has been adsorbed on the PVA molecules is formed. Colored laminated body.

Furthermore, through the second stage of the boric acid water extension step, the colored laminate and the amorphous PET substrate are further extended integrally, and an optical thin film laminate including a PVA layer constituting a 3μm-thick high-performance polarizing film is produced . Specifically, the optical thin film laminate is a stretching device equipped with a colored laminate in a processing device, and uniaxially stretched at the free end to a stretch magnification of 3.3 times, and the processing device is set to contain boric acid and potassium iodide The liquid temperature range of the boric acid solution is 60~85℃. More specifically, the liquid temperature of the boric acid aqueous solution is 65°C. In addition, the content of boric acid was set to 4 parts by weight based on 100 parts by weight of water, and the content of potassium iodide was set to 5 parts by weight based on 100 parts by weight of water. In this step, the colored layered body with the adjusted iodine adsorption amount is first immersed in the boric acid aqueous solution for 5 to 10 seconds. Then, the colored layered body is directly passed between a plurality of rollers with different peripheral speeds belonging to the stretching device equipped in the processing device, and it takes 30 to 90 seconds to uniaxially stretch at the free end to a stretching ratio of 3.3 times. Through this stretching process, the PVA layer contained in the colored laminate is changed into a 3 μm thick PVA layer that is oriented in one direction multiple times by adsorbing iodine to form a polyiodide ion complex. The PVA layer constitutes the high-performance polarizing film of the optical thin film laminate.

Although it is not a necessary step for the manufacture of the optical film laminate, it is preferable to take out the optical film laminate from the boric acid aqueous solution by the washing step, and wash it with the potassium iodide aqueous solution to adhere to the amorphous PET substrate. Boric acid on the surface of the 3μm thick PVA layer. Then, the cleaned optical film laminate is dried by a drying step using warm air at 60°C. In addition, the washing step is a step to solve the appearance defects such as boric acid precipitation.

Although the same is not a necessary step for the manufacture of optical film laminates, it is also possible to apply adhesion and/or transfer steps to the surface of the 3μm thick PVA layer that has been formed on the amorphous PET substrate. For cloth adhesive, after bonding an 80μm thick triacetyl cellulose film on one side, the amorphous PET substrate is peeled off, and the 3μm thick PVA layer is transferred to the 80μm thick triacetyl cellulose film.

[Other steps]

In addition to the aforementioned steps, the aforementioned thin polarizing film manufacturing method may include other steps. For example, other steps may include: insolubilization step, cross-linking step, drying (adjustment of water content) step, etc. Other steps can be performed at any appropriate time.

Representatively, the aforementioned insolubilization step is performed by immersing the PVA-based resin layer in a boric acid aqueous solution. The insolubilization treatment can impart water resistance to the PVA-based resin layer. The concentration of the boric acid aqueous solution is preferably 1 part by weight to 4 parts by weight relative to 100 parts by weight of water. The temperature of the insolubilization bath (aqueous solution of boric acid) should be 20℃~50℃. Preferably, the insolubilization step is performed after the laminate is made, before the dyeing step or the water extension step.

Representatively, the aforementioned crosslinking step is performed by immersing the PVA-based resin layer in a boric acid aqueous solution. The cross-linking treatment can impart water resistance to the PVA-based resin layer. The concentration of the boric acid aqueous solution is preferably 1 part by weight to 4 parts by weight relative to 100 parts by weight of water. In addition, when the cross-linking step is performed after the aforementioned dyeing step, it is more preferable to blend iodide. By blending iodide, the elution of iodine that has been adsorbed on the PVA-based resin layer can be suppressed. The blending amount of iodide is preferably 1 part by weight to 5 parts by weight relative to 100 parts by weight of water. Specific examples of iodide are as described above. The temperature of the cross-linking bath (aqueous solution of boric acid) should be 20℃~50℃. Preferably, the cross-linking step is performed before the second boric acid water extension step. In an ideal embodiment, the dyeing step, the cross-linking step, and the second boric acid water extension step are performed in this order.

<Transparent protective film>

The material for forming the transparent protective film provided on one or both sides of the aforementioned polarizer is preferably a material with excellent transparency, mechanical strength, thermal stability, moisture barrier, and isotropy. For example, polyester polymers such as polyethylene terephthalate or polyethylene naphthalate, cellulosic polymers such as diacetyl cellulose or triacetyl cellulose, and Acrylic polymers such as methacrylate, polystyrene or acrylonitrile. Styrenic polymers such as styrene copolymer (AS resin), polycarbonate polymers, etc. Also, examples of polymers forming the aforementioned transparent protective film are: such as polyethylene, polypropylene, polyolefins with cyclic or norbornene structures, and ethylene. Polyolefin-based polymers of propylene copolymers, vinyl chloride-based polymers, amide-based polymers such as nylon or aromatic polyamides, imine-based polymers, chrysene-based polymers, polyether chrysene-based polymers, Polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, aryl ester polymer, polyoxymethylene polymer, epoxy A polymer or a blend of the aforementioned polymers, etc. The transparent protective film can also contain one or more arbitrary appropriate additives. For example, the additives may include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, anti-coloring agents, flame retardants, nucleating agents, anti-charge agents, pigments, coloring agents, and the like. The content of the aforementioned thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, further preferably 60 to 98% by weight, and particularly preferably 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 inherent in the thermoplastic resin may not be fully expressed.

In addition, the transparent protective film includes, for example, the polymer film disclosed in Japanese Patent Application Laid-Open No. 2001-343529 (WO01/37007), for example, a thermoplastic film containing (A) side chains with substituted and/or unsubstituted imino groups Resin and (B) a resin composition of a thermoplastic resin having substituted and/or unsubstituted phenyl groups and nitrile groups in the side chain. Specific examples can include, for example: an alternating copolymer composed of isobutylene and N-methyl maleimide and acrylonitrile. Film of styrene copolymer resin composition. As the film, a film composed of a mixed extruded product of a resin composition can be used. These films have a small retardation and a small photoelastic coefficient, so they can solve the problem of unevenness caused by the strain of the polarizing film. In addition, since the moisture permeability is low, the humidification durability is excellent.

In the aforementioned polarizing film, the moisture permeability of the aforementioned transparent protective film is preferably 150 g/m ² /24h or less. With the aforementioned structure, it is difficult for the 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 curling or dimensional changes of the polarizing film caused by the storage environment.

The material for forming the transparent protective film on one or both sides of the aforementioned polarizer is preferably a material with excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, etc., especially the moisture permeability is It is 150 g/m ² /24h or less, and 140 g/m ² /24h or less is particularly preferable, and 120 g/m ² /24h or less is more preferable. The moisture permeability can be obtained by the method disclosed in the embodiment.

For example, the forming material of the transparent protective film that satisfies the aforementioned low moisture permeability can be used: polyester resin such as polyethylene terephthalate or polyethylene naphthalate; polycarbonate resin; arylate resin; Amine resins such as polyester or aromatic polyamides; such as polyethylene, polypropylene, ethylene. Polyolefin-based polymer of propylene copolymer, cyclic olefin-based resin with cyclic or norbornene structure, (meth)acrylic resin or a mixture of these. Among the aforementioned resins, polycarbonate resins, cyclic polyolefin resins, and (meth)acrylic resins are also preferable, and cyclic polyolefin resins and (meth)acrylic resins are particularly preferable.

The thickness of the transparent protective film can be appropriately determined. Generally speaking, it is 1 to 100 μm from the viewpoint 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.

In addition, when transparent protective films are provided on both sides of the polarizer, a transparent protective film composed of the same polymer material on the front and back can be used, or a transparent protective film composed of different polymer materials can also be used.

Functional layers such as hard coating, anti-reflection layer, anti-adhesion layer, diffusion layer or anti-glare layer can be arranged on the surface of the transparent protective film that is not attached to the polarizer. In addition, functional layers such as the aforementioned hard coat, anti-reflection layer, anti-adhesion layer, diffusion layer, or anti-glare layer can be provided in addition to the transparent protective film itself, and can also be provided separately from the transparent protective film.

<Optical Film>

The polarizing film of the present invention can be used as an optical film that is practically laminated with other optical layers. There are no special restrictions on the optical layer. For example, one or more layers of reflectors, semi-transmissive plates, retardation plates (including 1/2 or 1/4 wavelength plates) or viewing angle compensation can be used Films and the like are used for optical layers formed in liquid crystal display devices. Particularly desirable is a reflective polarizing film or a semi-transmissive polarizing film composed of a reflective plate or a semi-transmissive reflector in the polarizing film of the present invention, and an elliptical polarizing film or a circular polarizing film composed of a retardation plate in the polarizing film. A film, a wide viewing angle polarizing film formed by laminating a viewing angle compensation film on a polarizing film, or a polarizing film formed by laminating a brightness enhancement film on a polarizing film.

The optical film in which the aforementioned optical layer has been laminated on the polarizing film can also be formed by sequentially layering the optical film in the manufacturing process of liquid crystal display devices, etc. However, the optical film that has been laminated in advance has quality stability or assembly operations, etc. Excellent and can improve the advantages of the manufacturing steps of liquid crystal display devices. For the build-up layer, an appropriate bonding mechanism such as an adhesive layer can be used. When bonding the aforementioned polarizing film or other optical films, the optical axes can be arranged at an appropriate angle according to the target retardation characteristics and the like.

The above-mentioned polarizing film or the optical film laminated with at least one layer of polarizing film can also be provided with an adhesive layer for bonding with other components such as liquid crystal cells. The adhesive forming the adhesive layer is not particularly limited. For example, acrylic polymers, silicone polymers, polyesters, polyurethanes, polyamides, and polyamides can be appropriately selected and used. Ether, fluorine-based or rubber-based polymers are used as adhesives for base polymers. In particular, it is suitable to use an adhesive that has excellent optical transparency like an acrylic adhesive, exhibits moderate wettability, cohesiveness, and adhesive properties, and is excellent in weather resistance or heat resistance.

The adhesive layer can also be made into overlapping layers of different compositions or types, etc., and set on one or both sides of a polarizing film or an optical film. Moreover, when it is installed on both sides, adhesive layers of different composition, type or thickness can also be made on the front and back of the polarizing film or optical film. The thickness of the adhesive layer can be appropriately determined according to the purpose of use or adhesion, etc. However, it is generally 1 to 500 μm, preferably 1 to 200 μm, and particularly preferably 1 to 100 μm.

During the period until it is put into practical use, for the purpose of preventing its pollution, etc., the exposed surface of the adhesive layer is temporarily adhered and covered with the separator. This prevents contact with the adhesive layer under conventional processing conditions. In addition to the aforementioned thickness conditions, the separator can be used, for example, by using suitable release agents such as polysiloxane-based or long-chain alkyl-based, fluorine-based or molybdenum sulfide, as required, to combine plastic films, rubber sheets, paper, cloth, non-woven fabrics, Appropriate sheets such as nets, foamed sheets, metal foils, laminates of these, etc., are coated in accordance with the previous standards.

<Image display device>

The polarizing film or optical film of the present invention can be ideally used for the formation of various devices such as liquid crystal display devices. The formation of the liquid crystal display device can be carried out in accordance with previous standards. That is, generally speaking, the liquid crystal display device is formed by appropriately assembling the liquid crystal cell, the polarizing film or the optical film, and the component parts such as the lighting system as required, and incorporating the driving circuit, etc., however, in the present invention, except There are no special restrictions on the use of the polarizing film or optical film according to the present invention, and it can comply with previous standards. For example, the liquid crystal cell can also be of any type such as TN type, STN type or π type.

It can be formed into a liquid crystal display device in which a polarizing film or an optical film is arranged on one or both sides of the liquid crystal cell, or an appropriate liquid crystal display device such as a backlight or a reflector used in the lighting system. At this time, the polarizing film or optical film according to the present invention can be disposed on one side or both sides of the liquid crystal cell. When polarizing films or optical films are arranged on both sides, they may be the same or different. Furthermore, when the liquid crystal display device is formed, for example, suitable parts such as diffuser, anti-glare layer, anti-reflection film, protective plate, ridge array, lens array sheet, light diffuser, backlight, etc. can be used in Place 1 or 2 floors in a suitable location.

Example

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

<Production of Polarized Parts>

A 75μm thick polyvinyl alcohol film with an average degree of polymerization of 2400 and a degree of saponification of 99.9 mol% is immersed in warm water at 30°C for 60 seconds and swelled. Then, it was immersed in a 0.3% aqueous solution of iodine/potassium iodide (weight ratio=0.5/8), and the film was dyed while extending to 3.5 times. Then, it is stretched in a borate aqueous solution at 65° C. so that the total stretch magnification becomes 6 times. After the stretching, it was dried in an oven at 40° C. for 3 minutes, and a PVA-based polarizer X (thickness 23 μm) was prepared.

<Transparent protective film>

Transparent protective film 1: Triacetyl cellulose film with a thickness of 60 μm (water permeability 530 g/m ² /24h) was used without saponification, corona treatment, etc. (indicated as TAC in Table 1).

Transparent protective film 2: A (meth)acrylic resin with a lactone ring structure with a thickness of 40 μm (with a moisture permeability of 96 g/m ² /24h) was used after corona treatment (labeled as acrylic in Table 1).

Transparent protective film 3: Used by corona treatment on a cyclic polyolefin film with a thickness of 55μm (made by ZEON, Japan: ZEONOR, moisture permeability 11g/m ² /24h) (indicated as COP in Table 1) .

<The moisture permeability of transparent protective film>

The moisture permeability is measured according to the moisture permeability test of JIS Z0208 (moisture permeability cup method). Place the sample that has been cut into a diameter of 60mm in a moisture-permeable cup containing about 15g of calcium chloride, and put it in a thermostat with a temperature of 40℃ and a humidity of 90%RH, and measure the chlorine before and after being placed for 24 hours The weight of calcium chloride increases, and the moisture permeability (g/m ² /24h) is obtained from this.

<Active Energy Line>

The active energy line uses visible light (metal halide lamp enclosed in gallium), irradiation device: Fusion UV Systems, Inc. Light HAMMER10, valve: V valve, peak illuminance: 1600mW/cm ² , and cumulative irradiation amount is 1000mJ/cm ² ( Wavelength 380~440nm). In addition, the illuminance of visible light was measured using the Sola-Check system manufactured by Solarell.

Examples 1 to 4 and Comparative Examples 1 to 5

(Preparation of active energy ray hardening adhesive)

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

(Production of polarizing film)

Using an MCD coater (manufactured by Fuji Machinery Co., Ltd.) (unit cell shape: honeycomb, number of gravure rolls: 1000 pcs/inch, rotation speed 140%/pair line speed), apply the above-mentioned implementation on the transparent protective film The active energy ray curable adhesive of the example or the comparative example is coated to a thickness of 0.7 μm, and is bonded to both sides of the aforementioned polarizing member X by a roller machine. Then, using an IR heater, heat from the side (both sides) of the bonded transparent protective film to 50°C, and irradiate the above-mentioned visible light to both sides to make the active energy ray-curable adhesive of the above-mentioned embodiment or comparative example After curing, it was dried by hot air at 70°C for 3 minutes, and a polarizing film with transparent protective films on both sides of the polarizer was prepared. The linear speed of bonding is performed by 25m/min.

The production of the polarizing film is carried out separately for the aforementioned transparent protective films 1 to 3.

The following evaluations were performed on the polarizing films prepared by the foregoing Examples and Comparative Examples. Table 1 shows the evaluation results. In the evaluation of humidification durability and subsequent water resistance, the same polarizing films were separately produced.

<Overall water absorption>

Using the curable adhesive for polarizing film used in each example, it was sandwiched by two sheets of glass provided with 100μm spacers, and cured under the same active energy conditions as the examples to prepare an adhesive with a thickness of 100μm Agent layer (hardened substance). Use this as a sample. Make the weight of the sample M1g. The sample M1g was immersed in pure water at 23°C for 24 hours. Then, after taking it out of pure water and wiping with a dry cloth, the weight of the sample (M2g) was measured again within 1 minute. The overall water absorption rate is calculated from the results by the following formula, namely:

Formula: {(M2-M1)/M1}×100(%).

<hardening shrinkage>

It is measured by a hardening shrinkage sensor "Resin hardening shrinkage stress measuring device EU201C" manufactured by Santec. Specifically, the curing shrinkage rate was calculated by the method disclosed in JP 2013-104869. In addition, the curing shrinkage rate of the cured product formed from the active energy ray curable adhesive of Example 1 is 8.9%, and the curing shrinkage rate of the cured product formed from the active energy ray curable adhesive of Comparative Example 1 Is 11.9%.

<Adhesive force>

The polarizing film prepared in each example was cut out to a size of 200mm parallel to the extension direction of the polarizer and 20mm in the straight direction. With a cutting knife, a slit was added between the transparent protective film and the polarizer, and the polarized light The film is bonded to the glass plate. Using a universal testing machine (TENSILON), the transparent protective film and the polarizer were peeled off at a peeling speed of 500 mm/min in a 90-degree direction, and the peel strength was measured. In addition, the infrared absorption spectrum of the peeled surface after peeling was measured by the ATR method, and the peeled interface was evaluated based on the following criteria.

A: Cohesion destruction of transparent protective film

B: The interface between the transparent protective film/adhesive layer is peeled off

C: The interface between the adhesive layer/polarizer is peeled off

D: Condensation destruction of polarized parts

In the aforementioned criteria, A and D mean that the adhesive force is greater than the cohesive force of the film, so the adhesive force is very excellent. On the other hand, B and C mean that the adhesive force at the interface of the transparent protective film/adhesive layer (adhesive layer/polarizer) is insufficient (poor adhesive force). Considering this, the adhesive force when belonging to A or D is made ○, which will belong to A. B (At the same time, "the cohesive failure of the transparent protective film" and "the interface between the transparent protective film/adhesive layer peeling" are generated simultaneously) or When C (the cohesive failure of the transparent protective film and the peeling of the interface between the adhesive layer/polarizer" occur at the same time), the adhesive force is △, and the adhesive force when it belongs to B or C is ×.

<Humidification Durability: Measurement of monomer transmittance and polarization change>

By the same method as the embodiment and the comparative example, a polarizing film, which has been laminated with a transparent protective film 2 and 3 as a transparent protective film, on both sides of the polarizing member was made into a sample. Put the polarizing film (sample) into a constant temperature and humidity machine at 85°C/85%RH for 500 hours. Use a spectroscopic transmittance measuring device with an integrating sphere (Dot-3c of Murakami Color Technology Research Institute) to measure the monomer transmittance and polarization of the polarizing film before and after the input, and obtain: the change of the monomer transmittance Quantity (ΔT:%)=(Transmittance of monomer after input(%))-(Transmittance of monomer before input(%)); Change of polarization degree (ΔP:%)=(Polarization after input Degree (%))-(Polarization degree (%) before input).

In addition, the degree of polarization P is obtained by stacking two identical polarizing films to form a parallel transmittance (parallel transmittance: Tp) when their transmission axes are parallel and when the two transmission axes are orthogonal to each other. The transmittance (orthogonal transmittance: Tc) is calculated by applying the following formula.

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

Each transmittance is made 100% of the fully polarized light obtained by the Glan Taylor polarizer, and expressed by the Y value that has been corrected by the 2 degree field of view (C light source) of JIS Z8701.

<Next water resistance (warm water immersion test)>

By the same method as the embodiment and the comparative example, a polarizing film, which has been laminated with a transparent protective film 1 and 3 as a transparent protective film on both sides of the polarizing member, was made into a sample. The polarizing film (sample) was cut into a rectangle with a polarizer extending in a direction of 50 mm and a vertical direction of 25 mm. After immersing the aforementioned polarizing film in warm water at 60°C for 6 hours, the peeled length was visually measured with a magnifying glass. The measurement is made as the maximum value (mm) of the vertical distance of the section from the part causing the peeling.

<Adhesive water resistance (water peel resistance)>

By the same method as the embodiment and the comparative example, a polarizing film, which has been laminated with a transparent protective film 1 and 3 as a transparent protective film on both sides of the polarizing member, was made into a sample. The polarizing film (sample) was cut out to a size of 200 mm parallel to the extending direction of the polarizer and 20 mm in the straight direction. After immersing the polarizing film in pure water at 23°C for 24 hours, take it out of the pure water and wipe it with a dry cloth. With a cutter, a cut is added between the transparent protective film and the polarizer, and the polarizing film Bonded to the glass plate. The evaluation was performed within 1 minute after taking out the pure water. After that, the same evaluation as the aforementioned <adhesion force> was performed.

<Calculation of logPow>

The logPow value of each compound obtained by Chem Draw Ultra (manufactured by Cambridge Software Corporation) was used and calculated by the following formula. In addition, the polymerization initiator and photoacid generator will be deducted from the calculation.

Hardening adhesive logPow=Σ(logPowi×Wi)

logPowi: The logPow value of each component of the hardening adhesive

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

In Table 1, the radical polymerizable compound shows: HEAA: hydroxyethyl acrylamide, logPow=-0.56, homopolymer Tg=123°C, manufactured by Xingren; ACMO: propylene morpholine, logPow= -0.20, Tg of homopolymer=150℃, manufactured by Xingren; FA-THFM: Tetrahydrofurfuryl (meth)acrylate, logPow=1.13, Tg of homopolymer=45℃, manufactured by Hitachi Chemical; LIGHT ACRYLATE DCP-A: Tricyclodecane dimethanol diacrylate, logPow=3.05, Tg of homopolymer=134℃, manufactured by Kyoeisha Chemical Co., Ltd.; LIGHT ACRYLATE1,9ND-A: 1,9-nonanediol Diacrylate, logPow=3.68, homopolymer Tg=68℃, manufactured by Kyoeisha Chemical Co.; ARONIX M-220: Tripropylene glycol diacrylate, logPow=1.68, homopolymer Tg69℃, manufactured by Toagosei Co., Ltd. ; ARONIX M-306: Neopentylerythritol tri/tetraacrylate, logPow=1.04, Tg of homopolymer=250℃ or higher, manufactured by Toagosei.

Acrylic oligomer: ARUFON UP-1190, logPow=1.95 is manufactured by Toagosei Co., Ltd.; compound containing alkoxy group: NIKALAC MX-750LM, logPow=0.8 is manufactured by Japan Carbide Industry Co., Ltd.; containing epoxy group Compound: JER828, logPow=4.76 is made by Nihon Epoxy Co., Ltd.; isocyanate compound: KARENZ AOI, logPow=1.6 is made by Showa Denko Co., Ltd.

)，logPow=5.12，日本化藥公司製。 The photopolymerization initiator shows: IRGACURE907 (2-methyl-1-(4-methylthiophenyl)-2-morpholin-1-one), logPow=2.09, manufactured by BASF; KAYACURE DETX-S ( Diethyl 9-oxysulfur

), logPow=5.12, manufactured by Nippon Kayaku Corporation.

The photoacid generator is CPI-100P (a propylene carbonate solution containing 50% of the active ingredient with triaryl hexafluorophosphate as the main component), manufactured by Sanya Pro.

Claims (14)

A curable adhesive for polarizing films, which contains a curable component, the curable component is an active energy ray curable component, and further contains a compound (C) containing any one of an alkoxy group and an epoxy group. When the cured adhesive for thin films is immersed in pure water at 23°C for 24 hours, the overall water absorption expressed by the following formula is 10% by weight or less, octanol/ Water distribution coefficient (logPow value) is 1 or more; overall water absorption (%)={(M2-M1)/M1}×100 In the above formula, M1 represents the weight of the cured product before immersion, and M2 represents the weight of the cured product after immersion . The hardening adhesive for polarizing films of claim 1, wherein the compound (C) containing any one of an alkoxy group and an epoxy group is a compound (C1) containing an alkoxy group, and the aforementioned compound (C1) containing an alkoxy group The compound (C1) is a melamine compound containing an alkoxy group. The curable adhesive for polarizing films of claim 2, wherein the active energy ray curable component contains a radically polymerizable compound. According to claim 3, the curable adhesive for polarizing films, wherein the radically polymerizable compound contains a (meth)acrylamide derivative. According to claim 3, the curable adhesive for polarizing films, wherein the radically polymerizable compound contains a polyfunctional compound, and the polyfunctional compound has at least two radically polymerizable functional groups. Such as the hardening adhesive for polarizing films of claim 2, which further contains a photopolymerization initiator. The hardening adhesive for polarizing films of claim 2 further contains acrylic oligomer (A). Such as the hardening adhesive for polarizing films of claim 2, which further contains a photoacid generator (B). The hardening adhesive for polarizing films of claim 2 further contains an isocyanate compound (D). The curable adhesive for polarizing films of claim 1, wherein the curable component is a thermosetting component and further contains a thermal polymerization initiator. A polarizing film, in which at least one side of a polarizer is provided with a transparent protective film via an adhesive layer, and the adhesive layer is made of the hardening type adhesive for polarizing films as claimed in any one of claims 1 to 10 The hardened layer is formed. The polarizing film of claim 11, wherein the thickness of the cured adhesive layer is 0.1 to 3 μm. An optical film in which at least one polarizing film as in claim 11 or 12 is laminated. An image display device using a polarizing film such as claim 11 or 12, or an optical film such as claim 13.