JP6180451B2 - Polarizing plate, method for producing the polarizing plate, optical film, and image display device - Google Patents

Description

  The present invention relates to a polarizing plate and a method for producing the same. The polarizing plate can form an image display device such as a liquid crystal display device (LCD), an organic EL display device, a CRT, or a PDP alone or as an optical film in which the polarizing plate is laminated.

  Liquid crystal display devices are rapidly expanding in watches, mobile phones, PDAs, notebook computers, personal computer monitors, DVD players, TVs, and the like. The liquid crystal display device visualizes the polarization state by switching of the liquid crystal, and a polarizer is used from the display principle. In particular, in applications such as TVs, higher brightness, higher contrast, and wider viewing angles are required, and polarizing plates are also required to have higher transmittance, higher degree of polarization, and higher color reproducibility.

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

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

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

  In addition, as represented by TVs in particular, as the screen size of image display devices has increased in recent years, it has become very important to increase the size of polarizing plates in terms of productivity and cost (yield and increase in number of products). Yes. However, in the polarizing plate using the water-based adhesive described above, the so-called light leakage (unevenness) that the polarizing plate causes a dimensional change due to the heat of the backlight and becomes uneven and the black display appears white in a part of the entire screen. ) Becomes prominent.

  In order to solve the above-described problems in wet lamination, an active energy ray-curable adhesive that does not contain water or an organic solvent has been proposed. Such an active energy ray-curable adhesive is roughly classified into a photocationic polymerization type and a photoradical polymerization type.

  Photocationic polymerization is generally known to inhibit the polymerization reaction in the presence of water. Therefore, there is no problem when the wet-stretched PVA polarizer is completely dried and the curable component in the adhesive is polymerized. However, when the transparent protective film is laminated through the adhesive layer in a state where the PVA polarizer is not sufficiently dried and the water content is high, the photocationic polymerization of the curable component is inhibited, and the adhesive layer causes poor curing. There is a case. In addition, as described in Patent Document 3 below, when the curable component is composed of an epoxy resin, the polymerization rate of the cationic photopolymerization is slow, and the polarizing plate is produced continuously by roll-to-roll (Roll To Roll). Curing may progress even after winding, and curling may occur in the polarizing plate. For this reason, the photo cationic polymerization type is not suitable for roll-to-roll production of polarizing plates. In addition, many low-molecular-weight and low-viscosity epoxy resins commonly used in the cationic photopolymerization type have toxic properties such as mutagenicity and irritation, and problems have been pointed out in terms of safety. .

  On the other hand, in the photo-radical polymerization type, the polymerization reaction is not inhibited by water. Therefore, there is no problem even if the transparent protective film is laminated through the adhesive layer in a state where the moisture content of the PVA polarizer is high. Moreover, since the polymerization rate of radical photopolymerization is faster than that of photocationic polymerization, it is suitable for roll-to-roll production of polarizing plates. Moreover, the toxicity of the curable component used in the radical photopolymerization type is lower than that of the epoxy resin.

  In the following Patent Document 4, a cured layer of a photo radical polymerization type adhesive composition containing a hydroxy group-containing alkyl (meth) acrylate, a photopolymerization initiator, an acryloxy group or a methacryloxy group-containing silane coupling agent is used as an adhesive layer. The polarizing plate provided as is described. However, when the hydroxy group-containing alkyl (meth) acrylate described in this document is used as the main component of the curable component, the glass transition temperature of the adhesive layer is lowered, and as a result, the durability of the adhesive layer is deteriorated. Is concerned. In addition, in this document, it is described that a photoacid generator is added as an optional component to the adhesive composition, but this photoacid generator is a curing catalyst for making the silane coupling agent function more effectively. It is only used as.

  On the other hand, the present inventors have developed a photo radical polymerization type active energy ray curable adhesive using an N-substituted amide monomer as a curable component (Patent Document 5 below). Such an adhesive exhibits excellent durability under harsh environments under high humidity and high temperature. However, in the market, there is a demand for an adhesive that can further improve adhesiveness and / or water resistance. There was a real situation.

JP 2006-220732 A JP 2001-296427 A Japanese Patent No. 4306270 JP 2010-18721 A JP 2008-287207 A

  The present invention has been made in view of the above circumstances, and its purpose is to improve the adhesion between the polarizer and the transparent protective film layer, and to have a polarizing plate having an adhesive layer with improved durability and water resistance, and The manufacturing method, the optical film, and the image display device are provided.

The above object can be achieved by the present invention as described below. That is, the polarizing plate according to the present invention is a polarizing plate in which a transparent protective film is provided on at least one surface of a polarizer via an adhesive layer,
The glass transition temperature (Tg) of the adhesive layer is 60 ° C. or higher,
The adhesive layer is formed by a cured product layer formed by irradiating an active energy ray-curable resin composition with active energy rays,
The active energy ray-curable resin composition has the following components (A) to (C):
(A) a radically polymerizable compound,
It contains (B) a photoradical generator and (C) a photoacid generator.

In the above polarizing plate, the active energy ray-curable resin composition is, as (A), represented by the following general formula (1): CH ₂ = C (R ¹ ) —CONH _2−m — (X—O—R ^2). _M (1)
(R ¹ represents a hydrogen atom or a methyl group, X represents a —CH ₂ — group or a —CH ₂ CH ₂ — group, R ² represents a — (CH ₂ ) _n —H group (where n is 0, 1 Or an N-substituted amide monomer represented by 2) and m is 1 or 2.

  In the polarizing plate, the active energy ray-curable resin composition preferably contains N-hydroxyethyl (meth) acrylamide as the N-substituted amide monomer. In the present invention, (meth) acrylamide means acrylamide and / or methacrylamide.

  In the polarizing plate, it is preferable that the active energy ray-curable resin composition contains an acylphosphine oxide-based photoradical generator as the (B).

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

  In the polarizing plate, it is preferable that the active energy ray-curable resin composition further contains (E) a monomer having two or more carbon-carbon double bonds as a radical polymerizable compound.

  Moreover, the optical film according to the present invention is characterized in that at least one polarizing plate as described above is laminated.

  Furthermore, the image display device according to the present invention is characterized by using any of the polarizing plates described above and / or the optical film described above.

  In the polarizing plate according to the present invention, by irradiating the active energy ray-curable resin composition with active energy rays, (B) the photoradical generator generates radicals, and (A) the radical polymerizable compound is photoradical polymerized. By doing so, an adhesive layer is formed. In the present invention, the active energy ray-curable resin composition contains (C) a photoacid generator in addition to (A) a radical polymerizable compound and (B) a photoradical generator. Compared to the case where no generator is contained, the water resistance and adhesiveness of the adhesive layer can be dramatically improved. The reason why the water resistance and adhesion are improved is not clear, but by irradiation with active energy rays, (C) the polymer of the radical polymerizable compound is crosslinked (photoacid) in the presence of a photoacid generator. It is assumed that this is caused by crosslinking.

  The active energy ray-curable resin composition according to the present invention contains (A) a radically polymerizable compound as a main component of a curable component, substantially does not contain an epoxy group-containing compound, and temporarily contains it. However, the content is limited to 0 to 5% by mass. For this reason, since the active energy ray-curable resin composition according to the present invention is cured by a photo-radical polymerization type, as compared with a photo-cationic polymerization type that contains an epoxy group-containing compound as a main component of a curable component. The polymerization rate is fast, and the productivity of the cured product layer is excellent. Moreover, unlike the photocationic polymerization type cured product layer, there is no fear of causing poor curing of the cured product layer.

  In the present invention, when the content of the epoxy group-containing compound in the active energy ray-curable resin composition increases, the proportion of the epoxy group-containing compound that undergoes cationic photopolymerization in the presence of (C) a photoacid generator increases. The durability and water resistance of the adhesive layer are deteriorated. Accordingly, even if the active energy ray-curable resin composition contains an epoxy group-containing compound, the ratio of the epoxy group-containing compound to the total amount of the (A) radical polymerizable compound and the epoxy group-containing compound is It is important that the amount be 5% by mass or less, preferably 1% by mass or less, and particularly preferably not contain an epoxy group-containing compound.

Moreover, the active energy ray-curable resin composition according to the present invention has the following general formula (1): CH ₂ ═C (R ¹ ) —CONH _2-m — (X—O) as the radically polymerizable compound (A). -R ²⁾ _m (1)
(R ¹ represents a hydrogen atom or a methyl group, X represents a —CH ₂ — group or a —CH ₂ CH ₂ — group, R ² represents a — (CH ₂ ) _n —H group (where n is 0, 1 Or 2) and m represents 1 or 2), the durability and adhesiveness of the adhesive layer are further improved. The reason why the durability and adhesiveness are improved may be that the polymerized polymer of the N-substituted amide monomer has high polarity and high Tg. Here, although a polymer having a high Tg is generally considered to have poor adhesion, the polymer of such an N-substituted amide monomer is characterized in that both durability and adhesion are improved. . In addition, when the active energy ray-curable resin composition contains the N-substituted amide monomer, the reaction rate is fast, and the time for forming the adhesive layer can be shortened. Also excellent.

  Among the N-substituted amide monomers represented by the general formula (1), when N-hydroxyethyl (meth) acrylamide, particularly N-hydroxyethylacrylamide is used, the adhesiveness of the adhesive layer is improved. preferable. In the present invention, (meth) acrylamide means acrylamide and / or methacrylamide.

  In the present invention, the active energy ray-curable resin composition preferably contains an acylphosphine oxide photoradical generator. The acylphosphine oxide-based photoradical generator absorbs ultraviolet rays having a wavelength range of 380 to 440 nm. In the present invention, a polarizing plate is produced by irradiating an active energy ray curable resin composition with an active energy through a transparent protective film, and is generally composed of a material such as triacetyl cellulose (TAC). Many transparent protective films have an ultraviolet absorbing ability of 380 nm or less, and when irradiated with ultraviolet rays of less than 380 nm, the transparent protective film may be curled or wrinkled. However, when the active energy ray-curable resin composition contains an acylphosphine oxide photoradical generator, the cured product layer (adhesive layer) of the active energy ray-curable resin composition even when irradiated with ultraviolet rays exceeding 380 nm. Can be sufficiently formed, and curling and wrinkling of the transparent protective film can be prevented.

As described above, in the present invention, by irradiation with active energy rays, (C) the polymer of the radical polymerizable compound is crosslinked (photoacid crosslinking) in the presence of the photoacid generator, and as a result, It is characterized in that the water resistance and durability of the adhesive layer are improved. (C) When the photoacid generator generates a stronger acid, (A) the photoacid crosslinking of the polymer of the radical polymerizable compound proceeds more reliably, and as a result, the water resistance and durability of the adhesive layer are increased. More improved. (C) The strength of the acid generated by the photoacid generator is at least one selected from the group consisting of PF ₆ ⁻ , SbF ₆ ^— and AsF ₆ ^— where the strength of the acid varies depending on the type of counter anion. In this case, since a stronger acid can be generated from the photoacid generator, the water resistance and durability of the adhesive layer are further improved, which is preferable.

  In addition, the active energy ray-curable resin composition according to the present invention includes (E) a monomer having two or more carbon-carbon double bonds, particularly preferably a polyfunctional (meth) as the radically polymerizable compound (A). When the acrylate monomer is contained, the water resistance of the adhesive layer is particularly improved. When the composition forming the cured product layer contains a monomer having two or more carbon-carbon double bonds, particularly preferably a polyfunctional (meth) acrylate monomer, the moisture absorption amount of the cured product layer is appropriately reduced. And water resistance can be improved, improving adhesiveness. In order to further improve the water resistance, it is more preferable to use a hydrophobic polyfunctional (meth) acrylate monomer. In the present invention, (meth) acrylate means acrylate and / or methacrylate.

  The method for producing a polarizing plate according to the present invention is a method for producing a polarizing plate in which a transparent protective film is provided on at least one surface of a polarizer via an adhesive layer, and the adhesive layer of the polarizer is The active energy ray-curable resin composition is coated on the surface to be formed and / or the surface on which the adhesive layer of the transparent protective film is formed, and then a laminating step in which the polarizer and the transparent protective film are bonded, then active energy rays A curing step of curing the active energy ray-curable resin composition by irradiation to form an adhesive layer.

In the present invention, electron beams and / or ultraviolet rays can be used as the active energy rays. As ultraviolet rays, the ratio of the integrated illuminance in the wavelength range of 380 to 440 nm to the integrated illuminance in the wavelength range of 250 to 370 nm is 100: 0 to 100: 50, and the peak illuminance in the wavelength range of 380 to 440 nm is 1000 to 2000 mW / cm ^2. It is preferable to use ultraviolet rays.

  As described above, many of the transparent protective films have ultraviolet absorption ability of 380 nm or less, but the ratio of the integrated illuminance in the wavelength range of 380 to 440 nm and the integrated illuminance in the wavelength range of 250 to 370 nm is 100: 0 to 100: 50. When the ultraviolet ray is used, curling and wrinkling of the transparent protective film can be prevented. In the present invention, ultraviolet rays exceeding 440 nm can also be used. However, ultraviolet rays exceeding 440 nm cannot be absorbed by the (B) photoradical generator, and the energy efficiency is reduced. It is preferred to use no ultraviolet light.

Moreover, the adhesiveness of an adhesive bond layer can be improved by using the ultraviolet-ray whose peak illumination intensity of wavelength range 380-440nm is 1000-2000 mW / cm < ² >. In general, when an active energy ray-curable resin composition is irradiated with ultraviolet light having a high peak illuminance through a transparent protective film, the heat generated in the transparent protective film increases, and curling and wrinkles of the transparent protective film occur. Although it is a concern, since ultraviolet rays having a wavelength range of 380 to 440 nm are out of the ultraviolet absorption region of the transparent protective film, heat generation of the transparent protective film can be minimized. As a result, it is possible to prevent the transparent protective film from curling and wrinkling while enhancing the adhesiveness of the adhesive layer. In addition, the use of high-intensity ultraviolet light can reduce the number of lamps required to irradiate the required amount of ultraviolet light (the number of lamps of the ultraviolet ray generator), thereby improving energy efficiency. .

  Further, in the present invention, when ultraviolet rays emitted from a gallium-encapsulated metal halide lamp or an LED light source that emits light in the wavelength range of 380 to 440 nm are used as the light source, the above-described relationship between the integrated illuminance of ultraviolet rays and the peak illuminance is more reliably satisfied. Therefore, it is preferable. In addition, as a light source, a bandpass filter that cuts ultraviolet light of 380 nm or less is mounted between the light source and the object to be irradiated, so that a gallium-encapsulated metal halide lamp or an ultraviolet lamp other than the LED light source (for example, a high-pressure mercury lamp) can be used. Is possible. However, in view of energy efficiency, it is preferable to use a gallium-encapsulated metal halide lamp or an LED light source that can emit ultraviolet light having a wavelength range of 380 to 440 nm.

  In the method for producing a polarizing plate according to the present invention, after the lamination step, when the active energy ray-curable resin composition is heated to 40 to 50 ° C. or higher and then irradiated with active energy rays, (C) light This is preferable because the effect of improving adhesiveness by the acid generator is particularly enhanced. Furthermore, when the adhesive layer is heated to 40 to 50 ° C. or higher after the curing step, the moisture content of the polarizing plate is further decreased, which is preferable.

  When the adhesive layer according to the present invention is provided, a polarizing plate with a small dimensional change can be produced, so that it is possible to easily cope with an increase in the size of the polarizing plate, and it is possible to suppress the production cost from the viewpoint of yield and number of production. Further, since the polarizing plate according to the present invention has good dimensional stability, it is possible to suppress the occurrence of unevenness in the image display device due to the external heat of the backlight.

  The polarizing plate according to the present invention is a polarizing plate in which a transparent protective film is provided on at least one surface of a polarizer via an adhesive layer, and the adhesive layer is an active energy ray-curable resin composition. It is formed by the hardened | cured material layer formed by irradiating an active energy ray to a thing.

  The curable component used in the active energy ray-curable resin composition is selected so that the Tg of the adhesive layer formed thereby is 60 ° C. or higher. From the viewpoint of durability, the Tg of the adhesive layer is preferably 70 ° C. or higher, more preferably 75 ° C. or higher, further 100 ° C. or higher, and further preferably 120 ° C. or higher. On the other hand, if the Tg of the adhesive layer becomes too high, the flexibility of the polarizing plate is lowered. Therefore, the Tg of the adhesive layer is preferably 300 ° C. or lower, more preferably 240 ° C. or lower, and further preferably 180 ° C. or lower.

  The adhesive layer formed by the active energy ray-curable resin composition has higher durability than the aqueous adhesive layer. In the present invention, it is preferable to use an adhesive layer having a Tg of 60 ° C. or higher and to control the thickness of the adhesive layer to be 0.01 to 7 μm. As described above, in the polarizing plate of the present invention, the active energy ray-curable resin composition having an adhesive layer having a high Tg of 60 ° C. or higher is used, and the thickness of the adhesive layer is controlled within the above range. In addition, the durability under harsh environments under high humidity and high temperature can be satisfied. In consideration of the durability of the polarizing plate, in the present invention, in particular, when Tg (° C.) of the adhesive layer is defined as A and the thickness (μm) of the adhesive layer is defined as B, Formula (1): A− It is preferable that 12 × B> 58 is satisfied.

  As described above, the active energy ray-curable resin composition is preferably selected such that the Tg of the adhesive layer formed thereby is 60 ° C. or higher, more preferably 70 ° C. or higher. Further, it is preferably 75 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 120 ° C. or higher. On the other hand, if the Tg of the adhesive layer becomes too high, the flexibility of the polarizing plate is lowered. Therefore, the Tg of the adhesive layer is preferably 300 ° C. or lower, more preferably 240 ° C. or lower, and further preferably 180 ° C. or lower.

  Moreover, as above-mentioned, the thickness of an adhesive bond layer becomes like this. Preferably it is 0.01-7 micrometers, More preferably, it is 0.01-5 micrometers, More preferably, it is 0.01-2 micrometers, Most preferably, it is 0.01-1 micrometer. When the thickness of the adhesive layer is smaller than 0.01 μm, the cohesive force of the adhesive force itself cannot be obtained, and the adhesive strength may not be obtained. On the other hand, if the thickness of the adhesive layer exceeds 7 μm, the polarizing plate cannot satisfy the durability.

  The active energy ray-curable resin composition according to the present invention contains (A) a radical polymerizable compound, (B) a photo radical generator, and (C) a photo acid generator.

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

  Specific examples of the N-substituted amide monomer represented by the general formula (1) include, for example, N-hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, etc. are mentioned. These N-substituted amide monomers can be used singly or in combination of two or more.

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

  As the N-substituted amide monomer represented by the general formula (1), N-hydroxyethyl (meth) acrylamide is suitable. The N-substituted amide-based monomer exhibits good adhesion to a transparent protective film using a low moisture content polarizer or a material with low moisture permeability. Among the monomers exemplified above, N- Hydroxyethyl acrylamide exhibits particularly good adhesion.

  The active energy ray-curable resin composition according to the present invention comprises (A) a radical polymerizable compound having N-substituted amide monomers other than those represented by the general formula (1), various aromatic rings and hydroxy groups. Monofunctional (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, compounds having various (meth) acryloyl groups, and the like may be contained. However, when the adhesiveness and water resistance of the adhesive layer are taken into consideration, the ratio of the N-substituted amide monomer represented by the general formula (1) to the total amount of the (A) radical polymerizable compound is 50 to 99. It is preferable that it is mass%, and it is more preferable that it is 60-90 mass%.

  Examples of N-substituted amide monomers other than those represented by the general formula (1) include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N, N-diethyl (meth) acrylamide. , N-isopropylacrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, mercaaptomethyl (meth) acrylamide, mercaptoethyl (meth) acrylamide N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine and the like.

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

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

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

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

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

  In this invention, it is preferable that the ratio of the monomer which has a 2 or more carbon-carbon double bond with respect to the total amount of (A) radically polymerizable compound is 5-50 mass%, and is 9-40 mass%. More preferably. When this ratio is less than 5% by mass, sufficient water resistance may not be obtained. On the other hand, when it exceeds 50% by mass, sufficient adhesion may not be obtained.

  In the present invention, (A) the polymer of the radical polymerizable compound is cross-linked (photo-acid cross-linked) in the presence of the photoacid generator by irradiation with active energy rays, and as a result, the adhesive layer It is characterized by improved water resistance and durability. Therefore, if the (C) photoacid generator is consumed in the cationic photopolymerization of the epoxy group-containing compound, the water resistance and durability of the adhesive layer described above are not sufficiently improved, which is not preferable. For this reason, it is important that the ratio of the epoxy group-containing compound to the total amount of the (A) radical polymerizable compound and the epoxy group-containing compound in the active energy ray-curable resin composition is 5% by mass or less. The content is preferably at most mass%, and particularly preferably no epoxy group-containing compound.

  The active energy ray-curable resin composition according to the present invention contains (B) a photoradical generator. (B) The photo radical generator generates radicals by irradiating active energy rays. In the present invention, examples of the (B) photo radical generator include a hydrogen abstraction type photo radical generator and a cleavage type photo radical generator.

  Examples of the hydrogen abstraction type photo radical generator include 1-methylnaphthalene, 2-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, 1-iodonaphthalene , 2-iodonaphthalene, 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, naphthalene derivatives such as 1,4-dicyanonaphthalene, anthracene, 1,2-benzanthracene, 9,10-dichloroanthracene , 9,10-dibromoanthracene, 9,10-diphenylanthracene, 9-cyanoanthracene, 9,10-dicyanoanthracene, 2,6,9,10-tetracyanoanthracene, anthracene derivatives, pyrene derivatives, carbazole 9-methylcarbazole, 9-phenylcarbazole, 9-prop-2-ynyl-9H-carbazole, 9-propyl-9H-carbazole, 9-vinylcarbazole, 9H-carbazole-9-ethanol, 9-methyl-3-nitro -9H-carbazole, 9-methyl-3,6-dinitro-9H-carbazole, 9-octanoylcarbazole, 9-carbazolemethanol, 9-carbazolepropionic acid, 9-carbazolepropionitrile, 9-ethyl-3,6 -Dinitro-9H-carbazole, 9-ethyl-3-nitrocarbazole, 9-ethylcarbazole, 9-isopropylcarbazole, 9- (ethoxycarbonylmethyl) carbazole, 9- (morpholinomethyl) carbazole, 9-acetylcarbazole, 9- Allyl Rubazole, 9-benzyl-9H-carbazole, 9-carbazoleacetic acid, 9- (2-nitrophenyl) carbazole, 9- (4-methoxyphenyl) carbazole, 9- (1-ethoxy-2-methyl-propyl) -9H -Carbazole, 3-nitrocarbazole, 4-hydroxycarbazole, 3,6-dinitro-9H-carbazole, 3,6-diphenyl-9H-carbazole, 2-hydroxycarbazole, 3,6-diacetyl-9-ethylcarbazole, etc. Carbazole derivatives, benzophenone, 4-phenylbenzophenone, 4,4'-bis (dimethoxy) benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, methyl 2-benzoylbenzoate Ester, 2- Benzophenone derivatives such as methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, aromatic carbonyl compounds, [4- (4-methyl Phenylthio) phenyl] -phenylmethanone, xanthone, thioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 1- Examples include thioxanthone derivatives such as chloro-4-propoxythioxanthone and coumarin derivatives.

  The cleavage type photo radical generator is a type of photo radical generator that generates radicals by cleavage of the compound upon irradiation with active energy rays. Specific examples thereof include arylalkyls such as benzoin ether derivatives and acetophenone derivatives. Examples include, but are not limited to, ketones, oxime ketones, acylphosphine oxides, S-phenyl thiobenzoates, titanocenes, and derivatives obtained by increasing the molecular weight thereof. Commercially available cleavage type photo radical generators include 1- (4-dodecylbenzoyl) -1-hydroxy-1-methylethane, 1- (4-isopropylbenzoyl) -1-hydroxy-1-methylethane, 1-benzoyl. -1-hydroxy-1-methylethane, 1- [4- (2-hydroxyethoxy) -benzoyl] -1-hydroxy-1-methylethane, 1- [4- (acryloyloxyethoxy) -benzoyl] -1-hydroxy- 1-methylethane, diphenyl ketone, phenyl-1-hydroxy-cyclohexyl ketone, benzyldimethyl ketal, bis (cyclopentadienyl) -bis (2,6-difluoro-3-pyryl-phenyl) titanium, (η6-isopropylbenzene) -(Η5-cyclopentadienyl) -iron (II) hexaf Fluorophosphate, trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl) -phosphine oxide, bis (2,4,6-trimethylbenzoyl) -2, 4-dipentoxyphenylphosphine oxide or bis (2,4,6-trimethylbenzoyl) phenyl-phosphine oxide, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 4- (methylthiobenzoyl) -1 -Methyl-1-morpholinoethane may be mentioned, but is not limited thereto.

  The (B) photoradical generator used in the present invention, that is, the hydrogen abstraction type or cleavage type photoradical generator can be used alone or in combination. The combination of one or more cleavage-type photoradical generators is more preferable in terms of the stability of the generator alone and the curability of the composition in the present invention. Among the cleavage type photo radical generators, acylphosphine oxides are preferable. More specifically, trimethylbenzoyldiphenylphosphine oxide (trade name “DAROCURE TPO”; manufactured by Ciba Japan), bis (2,6-dimethoxy-benzoyl) )-(2,4,4-trimethyl-pentyl) -phosphine oxide (trade name “CGI 403”; manufactured by Ciba Japan) or bis (2,4,6-trimethylbenzoyl) -2,4-dipen Toxiphenylphosphine oxide (trade name “IRGACURE819”; manufactured by Ciba Japan Co., Ltd.) is preferable.

  (B) The content of the photoradical generator is preferably 0.01 to 10 parts by mass, and 0.05 to 5 parts by mass with respect to the total amount of the active energy ray-curable resin composition. Is more preferable, and 0.1 to 3 parts by mass is particularly preferable.

  In the present invention, since the active energy ray-curable resin composition contains (C) a photoacid generator in addition to (A) a radical polymerizable compound and (B) a photoradical generator, a photoacid generator is used. Compared with the case where it does not contain, the water resistance and durability of the adhesive layer can be dramatically improved. (C) The photoacid generator can be represented by the following general formula (2).

（ただし、Ｌ^＋は、任意のオニウムカチオンを表す。また、Ｘ⁻は、ＰＦ_６ ⁻、ＳｂＦ_６ ⁻、ＡｓＦ_６ ⁻、ＳｂＣｌ_６ ⁻、ＢｉＣｌ_５ ⁻、ＳｎＣｌ_６ ⁻、ＣｌＯ_４ ⁻、ジチオカルバメートアニオン、ＳＣＮ⁻よりからなる群より選択されるカウンターアニオンを表す。） General formula (2)

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

Preferred examples of the onium cation structure as the onium cation L ⁺ constituting the general formula (2) include onium cations selected from the following general formulas (3) to (11).

General formula (3)

General formula (4)

General formula (5)

General formula (6)

General formula (7)

General formula (8)

General formula (9)

General formula (10)

（上記一般式（３）−（１１）中、ただし、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ独立に、水素原子、置換もしくは未置換のアルキル基、置換もしくは未置換のアルケニル基、置換もしくは未置換のアリール基、置換もしくは未置換の複素環基、置換もしくは未置換のアルコキシル基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換の複素環オキシ基、置換もしくは未置換のアシル基、置換もしくは未置換のカルボニルオキシ基、置換もしくは未置換のオキシカルボニル基、またはハロゲン原子より選ばれる基を表す。Ｒ^４は、Ｒ^１、Ｒ^２およびＲ^３に記載した基と同様の基を表す。Ｒ^５は、置換もしくは未置換のアルキル基、置換もしくは未置換のアルキルチオ基を表す。Ｒ^６およびＲ^７は、それぞれ独立に、置換もしくは未置換のアルキル基、置換もしくは未置換のアルコキシル基を表す。Ｒは、ハロゲン原子、水酸基、カルボキシル基、メルカプト基、シアノ基、ニトロ基、置換もしくは未置換のカルバモイル基、置換もしくは未置換のアルキル基、置換もしくは未置換のアルケニル基、置換もしくは未置換のアリール基、置換もしくは未置換の複素環基、置換もしくは未置換のアルコキシル基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換の複素環オキシ基、置換もしくは未置換のアルキルチオ基、置換もしくは未置換のアリールチオ基、置換もしくは未置換の複素環チオ基、置換もしくは未置換のアシル基、置換もしくは未置換のカルボニルオキシ基、置換もしくは未置換のオキシカルボニル基のいずれかを表す。Ａｒ^４、Ａｒ^５は、置換もしくは未置換のアリール基、置換もしくは未置換の複素環基のいずれかを表す。Ｘは、酸素もしくは硫黄原子を表す。ｉは０〜５の整数を表す。ｊは０〜４の整数を表す。ｋは０〜３の整数を表す。また、隣接したＲ同士、Ａｒ^４とＡｒ^５、Ｒ^２とＲ^３、Ｒ^２とＲ^４、Ｒ^３とＲ^４、Ｒ^１とＲ^２、Ｒ^１とＲ^３、Ｒ^１とＲ^４、Ｒ^１とＲ、もしくはＲ^１とＲ^５は、相互に結合した環状構造であってもよい。） Formula (11)

(In the general formulas (3) to (11), R ¹ , R ² and R ³ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or An unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted acyl group, R ⁴ represents a group selected from a substituted or unsubstituted carbonyloxy group, a substituted or unsubstituted oxycarbonyl group, or a halogen atom, and R ⁴ represents a group similar to the groups described in R ¹ , R ² and R ^3. .R ⁵ is a substituted or unsubstituted alkyl group, is .R ⁶ and R ⁷ represents a substituted or unsubstituted alkylthio group, independently, be substituted Represents an unsubstituted alkyl group, a substituted or unsubstituted alkoxyl group, and R represents a halogen atom, a hydroxyl group, a carboxyl group, a mercapto group, a cyano group, a nitro group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted group. Alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxyl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted Heterocyclic oxy group, substituted or unsubstituted alkylthio group, substituted or unsubstituted arylthio group, substituted or unsubstituted heterocyclic thio group, substituted or unsubstituted acyl group, substituted or unsubstituted carbonyloxy group, substituted or ^.Ar 4 represent either a non-substituted oxycarbonyl group, Ar Represents a substituted or unsubstituted aryl group, .X represent either a substituted or unsubstituted heterocyclic group, an oxygen or sulfur atom .i is .j is 0-4 represents an integer of 0 to 5 K represents an integer of 0 to ^3. Adjacent Rs, Ar ⁴ and Ar ⁵ , R ² and R ³ , R ² and R ⁴ , R ³ and R ⁴ , R ¹ and R ² , R ¹ and R ³ , R ¹ and R ⁴ , R ¹ and R, or R ¹ and R ⁵ may be a cyclic structure bonded to each other.)

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

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

Onium cation (phosphonium cation) corresponding to the general formula (5):
Examples of phosphonium cations:
Trimethylphenylphosphonium, triethylphenylphosphonium, tetraphenylphosphonium, triphenyl (p-fluorophenyl) phosphonium, triphenyl (o-chlorophenyl) phosphonium, triphenyl (m-bromophenyl) phosphonium, triphenyl (p-cyanophenyl) phosphonium , Triphenyl (m-nitrophenyl) phosphonium, triphenyl (p-phenylsulfanylphenyl) phosphonium, (7-methoxy-2-oxo-2H-chromen-4-yl) triphenylphosphonium, triphenyl (o-hydroxyphenyl) ) Phosphonium, triphenyl (o-acetylphenyl) phosphonium, triphenyl (m-benzoylphenyl) phosphonium, triphenyl (p-methylphenyl) phospho Phonium, triphenyl (p-isopropoxyphenyl) phosphonium, triphenyl (o-methoxycarbonylphenyl) phosphonium, triphenyl (1-naphthyl) phosphonium, triphenyl (9-anthryl) phosphonium, triphenyl (2-thienyl) phosphonium , Triphenyl (2-furyl) phosphonium, triphenyl (9-ethyl-9Hcarbazol-3-yl) phosphonium, and the like, but are not limited thereto.

Onium cation corresponding to general formula (6) (pyridinium cation):
Examples of pyridinium cations:
N-phenylpyridinium, N- (o-chlorophenyl) pyridinium, N- (m-chlorophenyl) pyridinium, N- (p-cyanophenyl) pyridinium, N- (o-nitrophenyl) pyridinium, N- (p-acetylphenyl) ) Pyridinium, N- (p-isopropylphenyl) pyridinium, N- (p-octadecyloxyphenyl) pyridinium, N- (p-methoxycarbonylphenyl) pyridinium, N- (9-anthryl) pyridinium, 2-chloro-1- Phenylpyridinium, 2-cyano-1-phenylpyridinium, 2-methyl-1-phenylpyridinium, 2-vinyl-1-phenylpyridinium, 2-phenyl-1-phenylpyridinium, 1,2-diphenylpyridinium, 2-methoxy- 1-phenylpi Dinium, 2-phenoxy-1-phenylpyridinium, 2-acetyl-1- (p-tolyl) pyridinium, 2-methoxycarbonyl-1- (p-tolyl) pyridinium, 3-fluoro-1-naphthylpyridinium, 4-methyl Examples thereof include, but are not limited to, -1- (2-furyl) pyridinium, N-methylpyridinium, N-ethylpyridinium, and the like.

Onium cation (quinolinium cation) corresponding to general formula (7):
Examples of quinolinium cations:
N-methylquinolinium, N-ethylquinolinium, N-phenylquinolinium, N-naphthylquinolinium, N- (o-chlorophenyl) quinolinium, N- (m-chlorophenyl) quinolinium, N- (p -Cyanophenyl) quinolinium, N- (o-nitrophenyl) quinolinium, N- (p-acetylphenyl) quinolinium, N- (p-isopropylphenyl) quinolinium, N- (p-octadecyloxyphenyl) quinolinium, N- ( p-methoxycarbonylphenyl) quinolinium, N- (9-anthryl) quinolinium, 2-chloro-1-phenylquinolinium, 2-cyano-1-phenylquinolinium, 2-methyl-1-phenylquinolinium, 2-vinyl-1-phenylquinolinium, 2-phenyl-1-phenyl Norinium, 1,2-diphenylquinolinium, 2-methoxy-1-phenylquinolinium, 2-phenoxy-1-phenylquinolinium, 2-acetyl-1-phenylquinolinium, 2-methoxycarbonyl-1 -Phenylquinolinium, 3-fluoro-1-phenylquinolinium, 4-methyl-1-phenylquinolinium, 2-methoxy-1- (p-tolyl) quinolinium, 2-phenoxy-1- (2- Furyl) quinolinium, 2-acetyl-1- (2-thienyl) quinolinium, 2-methoxycarbonyl-1-methylquinolinium, 3-fluoro-1-ethylquinolinium, 4-methyl-1-isopropylquinolinium However, it is not limited to these.

Onium cation (isoquinolinium cation) corresponding to the general formula (8):
Examples of isoquinolinium cations:
N-phenylisoquinolinium, N-methylisoquinolinium, N-ethylisoquinolinium, N- (o-chlorophenyl) isoquinolinium, N- (m-chlorophenyl) isoquinolinium, N- (p-cyanophenyl) Isoquinolinium, N- (o-nitrophenyl) isoquinolinium, N- (p-acetylphenyl) isoquinolinium, N- (p-isopropylphenyl) isoquinolinium, N- (p-octadecyloxyphenyl) isoquinolinium, N- (p-methoxycarbonyl) Phenyl) isoquinolinium, N- (9-anthryl) isoquinolinium, 1,2-diphenylisoquinolinium, N- (2-furyl) isoquinolinium, N- (2-thienyl) isoquinolinium, N-naphthylisoquinolinium, etc. To mention That, without being limited thereto.

Onium cation corresponding to general formula (9) (benzoxazolium cation, benzothiazolium cation):
Examples of benzoxazolium cations:
N-methylbenzoxazolium, N-ethylbenzoxazolium, N-naphthylbenzoxazolium, N-phenylbenzoxazolium, N- (p-fluorophenyl) benzoxazolium, N- (p- Chlorophenyl) benzoxazolium, N- (p-cyanophenyl) benzoxazolium, N- (o-methoxycarbonylphenyl) benzoxazolium, N- (2-furyl) benzoxazolium, N- (o -Fluorophenyl) benzoxazolium, N- (p-cyanophenyl) benzoxazolium, N- (m-nitrophenyl) benzoxazolium, N- (p-isopropoxycarbonylphenyl) benzoxazolium, N- (2-thienyl) benzoxazolium, N- (m-carboxyphenyl) ben Oxazolium, 2-mercapto-3-phenylbenzoxazolium, 2-methyl-3-phenylbenzoxazolium, 2-methylthio-3- (4-phenylsulfanylphenyl) benzoxazolium, 6-hydroxy-3- (P-tolyl) benzoxazolium, 7-mercapto-3-phenylbenzoxazolium, 4,5-difluoro-3-ethylbenzoxazolium, and the like can be mentioned, but are not limited thereto. Absent.

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

Onium cation corresponding to general formula (10) (furyl or thienyl iodonium cation):
Difuryl iodonium, dithienyl iodonium, bis (4,5-dimethyl-2-furyl) iodonium, bis (5-chloro-2-thienyl) iodonium, bis (5-cyano-2-furyl) iodonium, bis (5- Nitro-2-thienyl) iodonium, bis (5-acetyl-2-furyl) iodonium, bis (5-carboxy-2-thienyl) iodonium, bis (5-methoxycarbonyl-2-furyl) iodonium, bis (5-phenyl) -2-furyl) iodonium, bis (5- (p-methoxyphenyl) -2-thienyl) iodonium, bis (5-vinyl-2-furyl) iodonium, bis (5-ethynyl-2-thienyl) iodonium, bis ( 5-cyclohexyl-2-furyl) iodonium, bis (5-hydroxy-2-thio) Nyl) iodonium, bis (5-phenoxy-2-furyl) iodonium, bis (5-mercapto-2-thienyl) iodonium, bis (5-butylthio-2-thienyl) iodonium, bis (5-phenylthio-2-thienyl) Although iodonium etc. can be mentioned, it is not limited to these.

Onium cation corresponding to general formula (11) (diaryliodonium cation):
Diphenyliodonium, bis (p-tolyl) iodonium, bis (p-octylphenyl) iodonium, bis (p-octadecylphenyl) iodonium, bis (p-octyloxyphenyl) iodonium, bis (p-octadecyloxyphenyl) iodonium, phenyl (P-octadecyloxyphenyl) iodonium, 4-isopropyl-4′-methyldiphenyliodonium, (4-isobutylphenyl) -p-tolyliodonium, bis (1-naphthyl) iodonium, bis (4-phenylsulfanylphenyl) iodonium, Phenyl (6-benzoyl-9-ethyl-9H-carbazol-3-yl) iodonium, (7-methoxy-2-oxo-2H-chromen-3-yl) -4'-isopropylphenyliodonium Although and the like, but is not limited thereto.

Next, the counter anion X ⁻ in the general formula (2) will be described.

The counter anion X ⁻ in the general formula (2) is not particularly limited in principle, but a non-nucleophilic anion is preferable. When the counter anion X ⁻ is a non-nucleophilic anion, the nucleophilic reaction in the cations coexisting in the molecule and various materials used in combination is unlikely to occur. As a result, the photoacid generator itself represented by the general formula (2) It is possible to improve the aging stability of a composition using the same. The non-nucleophilic anion here refers to an anion having a low ability to cause a nucleophilic reaction. Examples of such anions include PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, SCN ^{− and the} like.

Among the above-mentioned exemplary anions, particularly preferable as the counter anion X ⁻ in the general formula (2) include PF ₆ ⁻ , SbF ₆ ⁻ , and AsF ₆ ⁻ , and particularly preferably PF ₆ ⁻ , SbF ₆ ^- is mentioned.

Therefore, as a specific example of a preferable onium salt constituting the (C) photoacid generator of the present invention, a specific example of the structure of the onium cation represented by the above general formula (2) to general formula (11) An onium salt composed of an anion selected from PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, and SCN ⁻ .

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

  (C) The content of the photoacid generator is preferably 0.01 to 10 parts by mass, and 0.05 to 5 parts by mass with respect to the total amount of the active energy ray-curable resin composition. Is more preferable, and 0.1 to 3 parts by mass is particularly preferable.

  Further, in the active energy ray-curable resin composition according to the present invention, in addition to the photo radical generator, a sensitizer that increases the curing rate and sensitivity of the electron beam represented by a carbonyl compound may be added. .

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

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

  When adding a sensitizer, it is preferable that the content is 0.01-20 mass parts with respect to the active energy ray-curable resin composition whole quantity, and it is 0.01-10 mass parts. More preferred is 0.1 to 3 parts by mass.

  Moreover, various additives can be mix | blended with the active energy ray hardening-type resin composition which concerns on this invention as another arbitrary component in the range which does not impair the objective and effect of this invention. Such additives include polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, silicone-based oligomer. Polymers such as polysulfide oligomers or oligomers; Polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiators; leveling agents; wettability improvers; UV absorbers; silane coupling agents; inorganic fillers; pigments; dyes and the like. However, in the active energy ray-curable resin composition, the content of the above-described additive is preferably 0.005 to 20 parts by mass with respect to the total amount of the active energy ray-curable resin composition, 0.01 to More preferably, it is 10 mass parts, and it is especially preferable that it is 0.1-5 mass parts.

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

  In the electron beam curable type, any appropriate condition can be adopted as the irradiation condition of the electron beam as long as the active energy ray curable resin composition can be cured. For example, in the electron beam irradiation, the acceleration voltage is preferably 5 kV to 300 kV, and more preferably 10 kV to 250 kV. If the acceleration voltage is less than 5 kV, the electron beam may not reach the adhesive and may be insufficiently cured. If the acceleration voltage exceeds 300 kV, the penetration force through the sample is too strong and the electron beam rebounds, There is a risk of damaging the polarizer. The irradiation dose is 5 to 100 kGy, more preferably 10 to 75 kGy. When the irradiation dose is less than 5 kGy, the adhesive becomes insufficiently cured, and when it exceeds 100 kGy, the transparent protective film and the polarizer are damaged, resulting in a decrease in mechanical strength and yellowing, thereby obtaining predetermined optical characteristics. I can't.

  Electron beam irradiation is usually performed in an inert gas, but if necessary, it may be performed in the atmosphere or under a condition in which a small amount of oxygen is introduced. Depending on the material of the transparent protective film, by appropriately introducing oxygen, the transparent protective film surface where the electron beam first hits can be obstructed to prevent oxygen damage and prevent damage to the transparent protective film. An electron beam can be irradiated efficiently.

  On the other hand, in the case of using an ultraviolet curable protective film having an ultraviolet absorbing ability, light having a wavelength shorter than about 380 nm is absorbed, so that light having a wavelength shorter than 380 nm cannot reach the active energy ray curable resin composition. And does not contribute to the polymerization reaction. Furthermore, light having a wavelength shorter than 380 nm absorbed by the protective film is converted into heat, and the protective film itself generates heat, causing defects such as curling and wrinkling of the polarizing plate. Therefore, when the ultraviolet curable type is adopted in the present invention, it is preferable to use an apparatus that does not emit light having a wavelength shorter than 380 nm as the ultraviolet ray generating apparatus, and more specifically, the integrated illuminance and wavelength in the wavelength range of 380 to 440 nm. The ratio with the integrated illuminance in the range of 250 to 370 nm is preferably 100: 0 to 100: 50, and more preferably 100: 0 to 100: 40. As the ultraviolet ray satisfying such a relationship of integrated illuminance, a gallium-filled metal halide lamp and an LED light source that emits light in the wavelength range of 380 to 440 nm are preferable. Alternatively, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, incandescent lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser or sunlight as the light source, It is also possible to use a light having a wavelength shorter than 380 nm by using a band pass filter.

  The method for producing a polarizing plate according to the present invention comprises applying an active energy ray-curable resin composition to a surface on which an adhesive layer of a polarizer is formed and / or a surface on which an adhesive layer of a transparent protective film is formed. A laminating step of bonding the child and the transparent protective film, and then a curing step of curing the active energy ray-curable resin composition by irradiation with active energy rays to form an adhesive layer.

  The polarizer and the transparent protective film may be subjected to a surface modification treatment before applying the active energy ray-curable resin composition. Specific examples of the treatment include corona treatment, plasma treatment, and saponification treatment.

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

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

  After the lamination step, when the active energy ray-curable resin composition is heated to 40 to 50 ° C. or higher and then irradiated with active energy rays, (C) the effect of improving the adhesion by the photoacid generator is particularly It is preferable because it increases.

  After laminating the polarizer and the transparent protective film (after the lamination process), the active energy ray (electron beam, ultraviolet ray, etc.) is irradiated to cure the active energy ray-curable resin composition to form an adhesive layer. . The irradiation direction of active energy rays (electron beam, ultraviolet ray, etc.) can be irradiated from any appropriate direction. Preferably, it irradiates from the transparent protective film side. When irradiated from the polarizer side, the polarizer may be deteriorated by active energy rays (electron beams, ultraviolet rays, etc.).

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

  Furthermore, when the adhesive layer is heated to 40 to 50 ° C. or higher after the curing step, the moisture content of the polarizing plate is further decreased, which is preferable.

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

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

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

  The polarizer is not particularly limited, and various types can be used. Examples of the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film, and two colors such as iodine and dichroic dye. And polyene-based oriented films such as those obtained by adsorbing a functional material and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 1 to 80 μm.

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

  As a material for forming the transparent protective film provided on one side or both sides of the polarizer, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is preferable. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) And polymers based on polycarbonate and polycarbonate. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or the above Examples of the polymer that forms the transparent protective film include polymer blends. One or more kinds of arbitrary appropriate additives may be contained in the transparent protective film. Examples of the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, an anti-coloring agent, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent. The content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by mass, more preferably 50 to 99% by mass, further preferably 60 to 98% by mass, and particularly preferably 70 to 97% by mass. . When content of the said thermoplastic resin in a transparent protective film is 50 mass% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.

  Moreover, as a transparent protective film, the polymer film as described in Unexamined-Japanese-Patent No. 2001-343529 (WO01 / 37007), for example, (A) thermoplastic resin which has a substituted and / or unsubstituted imide group in a side chain, ( B) Resin compositions containing a thermoplastic resin having substituted and / or unsubstituted phenyl and nitrile groups in the side chain. Specific examples include a film of a resin composition containing an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile / styrene copolymer. As the film, a film made of a mixed extruded product of the resin composition or the like can be used. Since these films have a small phase difference and a small photoelastic coefficient, problems such as unevenness due to the distortion of the polarizing plate can be eliminated, and since the moisture permeability is small, the humidification durability is excellent.

  Although the thickness of a transparent protective film can be determined suitably, generally it is about 1-500 micrometers from points, such as workability | operativity, such as intensity | strength and handleability, and thin-layer property. 1-300 micrometers is especially preferable, and 5-200 micrometers is more preferable.

  In addition, when providing a transparent protective film on both surfaces of a polarizer, the transparent protective film which consists of the same polymer material may be used by the front and back, and the transparent protective film which consists of a different polymer material etc. may be used.

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

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

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

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

  The pressure-sensitive adhesive layer can be provided on one side or both sides of a polarizing plate or an optical film as a superimposed layer of different compositions or types. Moreover, when providing in both surfaces, it can also be set as adhesive layers with a different composition, a kind, thickness, etc. in the front and back of a polarizing plate or an optical film. The thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the purpose of use and adhesive force, and is generally 1 to 500 μm, preferably 1 to 200 μm, and particularly preferably 1 to 100 μm.

  The exposed surface of the adhesive layer is temporarily covered with a separator for the purpose of preventing contamination until it is put into practical use. Thereby, it can prevent contacting an adhesion layer in the usual handling state. As the separator, except for the above thickness conditions, for example, a suitable thin leaf body such as a plastic film, rubber sheet, paper, cloth, non-woven fabric, net, foamed sheet, metal foil, laminate thereof, and the like, silicone type or Appropriate ones according to the prior art, such as those coated with an appropriate release agent such as long-chain alkyl, fluorine-based or molybdenum sulfide, can be used.

  The polarizing plate or the optical film of the present invention can be preferably used for forming various devices such as a liquid crystal display device. The liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, a polarizing plate or an optical film, and an illumination system as necessary, and incorporating a drive circuit. There is no limitation in particular except the point which uses the polarizing plate or optical film by invention, and it can apply according to the former. As the liquid crystal cell, any type such as a TN type, an STN type, or a π type can be used.

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

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

<Tg: Glass transition temperature>
It measured with the temperature increase rate of 10 degree-C / min using the glass transition point temperature differential scanning calorimeter (DSC). As a sample, 5 mg of a sample was placed in an aluminum press-lid container and crimped.

<Polarizer>
A polyvinyl alcohol film having an average polymerization degree of 2400 and a saponification degree of 99.9 mol% and a thickness of 75 μm was immersed in warm water at 30 ° C. for 60 seconds to swell. Next, the film was dyed while being immersed in an aqueous solution of 0.3% concentration of iodine / potassium iodide (weight ratio = 0.5 / 8) and stretched to 3.5 times. Then, it extended | stretched so that the total draw ratio might be 6 times in 65 degreeC borate ester aqueous solution. After extending | stretching, it dried for 3 minutes in 40 degreeC oven, and obtained the polarizer.

<Transparent protective film>
As a first protective film, a triacetyl cellulose film (TAC) having a thickness of 80 μm was immersed in a 10% by mass aqueous solution of sodium hydroxide heated to 60 ° C. for 30 seconds, and then dried by a hot air dryer. As the second protective film, a 60 μm thick ZEONOR film (manufactured by Nippon Zeon Co., Ltd.) subjected to corona treatment was used. The contact angle at 23 ° C. was 32 °.

<Active energy rays>
The following (A), (B) and (C) were used as active energy rays. In addition, the illumination intensity of (A) and (B) was measured using the Sola-Check system made from Solatell.

(A) Ultraviolet light (gallium filled metal halide lamp) Irradiation device: Fusion UV Systems, Inc. Light HAMMER10 bulb: V bulb Peak illuminance: 1600 mW / cm ² , integrated irradiation amount 1000 / mJ / cm ² (wavelength 380 to 440 nm)
(B) Ultraviolet light (LED light source (LED light source having a peak illuminance at 385 nm)) Irradiation device: Panasonic Electric Works Aicure UD80 Peak illuminance: 3900 mW / cm ² , integrated irradiation amount 300 / mJ / cm ² (wavelength 380 to 440 nm)
(C) Electron beam irradiation device: Electron beam irradiation device manufactured by Eye Electron Beam Co., Ltd. Acceleration voltage: 250 kV Irradiation dose 20 kGy

(Adjustment of active energy ray-curable resin composition)
According to the recipe shown in Table 1, the components were mixed and stirred at 50 ° C. for 1 hour to obtain active energy ray-curable resin compositions (a) to (e). Each component used is as follows.

HEAA (hydroxyethyl acrylamide ((A) radical polymerizable compound, N-substituted amide monomer described in general formula (1))), 4HBA (4-hydroxybutyl acrylate ((A) radical) manufactured by Kojin Co., Ltd. Polymerizable compound)), NMMA (N-methoxymethylacrylamide ((A) radical polymerizable compound, and N-substituted amide monomer described in general formula (1)) manufactured by Osaka Organic Chemical Industry Co., Ltd.), MRC Unitech NBMA (N-butoxymethylacrylamide ((A) radical polymerizable compound, N-substituted amide monomer described in general formula (1))), MRC Unitech Light Acrylate 1,9ND-A ( 1,9-nonanediol diacrylate ((A) radical polymerizable compound, which is a polyfunctional (meth) acrylate Monomer)), Aronix M-220 (tripropylene glycol diacrylate ((A) radical polymerizable compound and polyfunctional (meth) acrylate monomer)) manufactured by Kyoeisha Chemical Co., Ltd. Celoxide 2021P (manufactured by Toagosei Co., Ltd.) 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate (epoxy group-containing compound) manufactured by Daicel Chemical Industries, Ltd. IRGACURE 819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (( B) Photoradical generator)) CPI-100P (triarylsulfonium-PF ₆ salt ((C) photoacid generator)) manufactured by Ciba Japan Co., Ltd. UVS-1221 (9,10-dipropoxyanthracene (photo) Sensitizer)) Made by Kawasaki Kasei

Examples 1-3, Comparative Examples 1-4
On the transparent protective film, the active energy ray-curable resin composition (a) shown in Table 1 (hereinafter simply referred to as “composition (a)”) to (e) is converted into an MCD coater (manufactured by Fuji Machine Co., Ltd.). (Cell shape: honeycomb, gravure roll wire number: 1000 lines / inch, rotational speed 140% / vs line speed), coating is performed to a thickness of 0.5 μm, and rolls are applied to both sides of the polarizer. I stuck together. Then, from the bonded transparent protective film side (both sides), it was heated to 50 ° C. using an IR heater (but not heated in Comparative Example 4), and the active energy rays (A) to (C) were applied to both sides. Irradiated to cure the compositions (a) to (e), and then dried with hot air at 70 ° C. for 3 minutes (no hot air drying in Example 2), and polarized light having a transparent protective film on both sides of the polarizer I got a plate. The line speed of bonding was 25 m / min.

[Evaluation]
The following evaluation was performed about the polarizing plate obtained by the Example and the comparative example. The results are shown in Table 2.

<Adhesion test of transparent protective film>
The polarizing plate is cut into a size of 200 mm parallel to the stretching direction of the polarizer and 20 mm in the perpendicular direction. The plate was bonded to a glass plate. With Tensilon, the protective film and the polarizer were peeled off at 90 ° direction at a peeling speed of 500 mm / min, and the peel strength was measured. Further, the peeled surface after peeling was evaluated according to the following criteria by the ATR method.
○: Cohesive failure of transparent protective film Δ: Cohesive failure of adhesive layer ×: Interfacial peeling between protective film and adhesive layer

<Hot water immersion test>
The polarizing plate was cut out to a size of 50 mm square, immersed in warm water at 60 ° C. for 6 hours, and the area residual ratio of the polarizer having a transmittance of 50% or less was measured. Each polarizing plate was evaluated according to the following criteria.
○: 90% or more △; 50-95%
×: Less than 50%

<Heat shock crack test>
A polarizing plate cut out to a size of 15 inches is attached to a glass plate, a heat cycle test from −40 ° C. to 80 ° C. is performed, and whether or not cracks are generated in the stretching direction of the polarizer after 100 cycles is determined. Visual evaluation was made according to the following criteria.
○: No occurrence of cracks in the polarizer Δ: Cracks are generated from one side of the polarizing plate, but have not reached the opposite sides ×: Cracks that have reached both opposite sides of the polarizing plate have occurred

  From the results in Table 2, it can be seen that the polarizing plates according to Examples 1 to 3 are excellent in adhesiveness, durability and water resistance. On the other hand, since the polarizing plate according to Comparative Example 1 has a low Tg of the adhesive layer, the durability is deteriorated and the proportion of —OH groups in the radically polymerizable monomer (A) constituting the adhesive layer is large. From this, the water resistance deteriorated. In the polarizing plate according to Comparative Example 2, the adhesive layer is composed of a hybrid of “photocationic polymerization polymer of epoxy group-containing compound” and “photoradical polymerization polymer of (A) radical polymerizable compound”. Therefore, water resistance and durability deteriorated. Furthermore, since the active energy ray-curable resin composition does not contain the (C) photoacid generator, the polarizing plate according to Comparative Example 3 has an adhesive layer as compared with the polarizing plates according to Examples 1 to 3. Water resistance did not improve.

Claims (6)

A method for producing a polarizing plate, wherein a transparent protective film is provided on at least one surface of a polarizer via an adhesive layer,
On the surface forming the adhesive layer of the polarizer and / or the surface forming the adhesive layer of the transparent protective film, the following components (A) to (C):
(A) The following general formula (1):
^{_{CH 2 = C (R 1)}} -CONH 2-m - (X-O-R 2) m (1)
(R ¹ represents a hydrogen atom or a methyl group, X represents a —CH ₂ — group or a —CH ₂ CH ₂ — group, R ² represents a — (CH ₂ ) _n —H group (where n is 0, 1 Or 2), m represents 1 or 2, and an N-substituted amide monomer represented by
(B) a photoradical generator, and (C) a photoacid generator,
An active energy ray-curable resin composition containing an active energy ray-curable resin composition containing 15 to 65% by weight of a cationic polymerizable compound having a (meth) acryl group in the molecule and a hydroxy group-containing alkyl ( (Excluding active energy ray curable resin composition containing 50-99% by weight of meth) acrylate), and then laminating a polarizer and a transparent protective film, followed by ultraviolet ray irradiation to cure active energy rays and curing the mold resin composition, the curing step of the glass transition temperature (Tg) to form an adhesive layer is 60 ° C. or higher, have a,
The said active energy ray hardening-type resin composition is a manufacturing method of the polarizing plate whose ratio of the epoxy group containing compound with respect to the total amount of (A) radically polymerizable compound and an epoxy group containing compound is 5 mass% or less .   The ultraviolet ray is generated by using an ultraviolet ray generator having a ratio of an integrated illuminance in a wavelength range of 380 to 440 nm and an integrated illuminance in a wavelength range of 250 to 370 nm of 100: 0 to 100: 50. The manufacturing method of the polarizing plate of description.   The method for producing a polarizing plate according to claim 1 or 2, wherein the ultraviolet ray is generated using a gallium-encapsulated metal halide lamp or an LED light source.   The method for producing a polarizing plate according to any one of claims 1 to 3, wherein a content of the photoacid generator is 0.01 to 10 parts by mass with respect to a total amount of the active energy ray-curable resin composition. A polarizing plate in which a transparent protective film is provided via an adhesive layer on at least one surface of a polarizer,
The glass transition temperature (Tg) of the adhesive layer is 60 ° C. or higher,
The adhesive layer is formed by a cured product layer formed by irradiating an active energy ray-curable resin composition with ultraviolet rays,
The active energy ray-curable resin composition has the following components (A) to (C):
(A) The following general formula (1):
^{_{CH 2 = C (R 1)}} -CONH 2-m - (X-O-R 2) m (1)
(R ¹ represents a hydrogen atom or a methyl group, X represents a —CH ₂ — group or a —CH ₂ CH ₂ — group, R ² represents a — (CH ₂ ) _n —H group (where n is 0, 1 Or 2), m represents 1 or 2, and an N-substituted amide monomer represented by
(B) a photo-radical generating agent, and (C) containing a photoacid generator (however, in the molecule (meth) active energy ray-curable resin containing 15 to 65 wt% cationically polymerizable compound having an acrylic group The composition and the active energy ray-curable resin composition containing 50 to 99% by weight of a hydroxy group-containing alkyl (meth) acrylate),
The active energy ray-curable resin composition is characterized in that the ratio of the epoxy group-containing compound to the total amount of the (A) radical polymerizable compound and the epoxy group-containing compound is 5% by mass or less . The polarizing plate according to claim 5 , wherein the content of the photoacid generator is 0.01 to 10 parts by mass with respect to the total amount of the active energy ray-curable resin composition.