TW200949317A - Polarizer, optical component and liquid crystal display device - Google Patents

Abstract

The present application provides a polarizer, and an optical component and a liquid crystal display device using the same. The polarizer is characterized by having a polarizing film being a polyvinyl alcohols resin film in which a dichromic pigment is absorbed and orientated, and a protective layer being formed from a curable resin composition containing active energy ray curable compounds, wherein the active energy ray curable compounds contains compounds having at least one epoxy group, and (meta)acrylic acid compounds having at least one (meta)acryloxy group, and the elastic coefficient of the protective layer is 3300 to 10000 MPa. By providing the polarizer, and the optical component and the liquid crystal display device using the same, the maintenance of the good adhesion between the polarizing film and the protective layer, and also the thinning and lightening and the improvement of the hardness of the protective layer could be achieved.

Description

200949317 VI. Description of the Invention: [Technical Field of the Invention] A light plate is a liquid crystal display device having a protective layer on one or both sides of a polarizing film.光学About the optical component using the deflecting plate and the prior art. The polarizing plate can be used as a protective layer formed on the one or both sides of the polarizing film as the liquid crystal display device. Polarizer. As for this, the tree H has excellent optical transparency and transparency, so it is more than the film of the cellulose film (10). The polarizing plate can be attached to the liquid crystal display device with an adhesive as needed. In recent years, with the notebook type of the liquid crystal display device, the car, the car navigator, and the like can be used for the machine: the thin plate, the light weight and the high durability (high mechanical strength) The liquid used for portable use is used, and for the polarizing plate used therein, it is also required to be straight, and the property is 'but the polarizing plate of the past is exposed to high humidity for a long time, especially when it is under the south temperature and high humidity. There is a decrease in polarizing performance or a contraction of the polarizing film. Therefore, for the protective layer laminated on the polarizing film, in addition to being thin, it is also required to increase its hardness to improve mechanical strength and inhibit the shrinkage of the polarizing film (shrinkage suppression). force). However, in the case of the polarizing plate of the TAC film which has been bonded to the protective layer, it is difficult to make the thickness of the protective layer 20 or less in terms of handling property or durability in the case of 321008 4 200949317, and the thickness is lighter and thinner. limit. As for the technique for solving the above problems, there is, for example, Japanese Unexamined Patent No. 2, No. 19, No. 9 (Specially for the towel, the age of the resin is coated on the side of the parent-child: Ϊ of the polarizing film on one or both sides of the ' When a transparent film is formed, the Japanese Patent Laid-Open No. 3_.42 (patent document i contains a second-line residue or ^ energy line polymerization - hardenability - material hardening) In the technique of laminating a film, Patent Document 3 discloses a polarizing plate which is formed on at least one side of a polarizing film and has a protective film mainly composed of a tree gambling. In the Japanese Patent Publication No. 92112 (Patent Document 4), it is disclosed that the active energy ray-curable resin composition is protected by a cured product [Patent Document U Japanese Patent Publication No. 2_199819] [Patent Document 3] JP-A-2005-92112 (Patent Document 4) JP-A-2005-92112 (Summary of the Invention) Provided - aspects can maintain the polarizing film and protective layer = = good adhesion ... has been thin A polarizing plate that quantifies and protects the hardness of the layer. Further, another object of the present invention is to provide an optical component and a liquid crystal display device using the polarizing plate. (Means for Solving the Problem) 321008 5 200949317 The polarizing plate of the present invention is provided a polarizing film that adsorbs a dichroic dye in a polyvinyl alcohol-based resin film, and a protective layer formed on at least one surface of the polarizing film, wherein the protective layer is hardened by a curable resin composition containing an active energy ray-curable compound The present invention, wherein the active energy ray-curable compound contains a compound having at least one epoxy group in the molecule and a (meth)acrylic compound having at least one (fluorenyl) acryloxy group in the molecule, and the aforementioned protection The elastic modulus of the layer is 3,300 to 10, OOO MPa. In the polarizing plate of the present invention, the (meth)acrylic compound is contained in an amount of 10 to 70 parts by weight based on 100 parts by weight of the active energy ray-curable compound. In the polarizing plate of the present invention, the aforementioned (fluorenyl)acrylic compound is compounded only by the (fluorenyl)acrylic acid. And the cured product formed by the polymerization initiator is preferably a modulus of 3, OOO MPa or more. In the polarizing plate of the present invention, the (meth)acrylic compound is represented by the following formulas (1) to (4). At least one compound is preferred. 6 321008 (1) 200949317

Qi t2-ch2ch2 (2) ❹

^〇Η2〇Η2**Τ ^ ch2-t CH2=CHCO-CH2-C-CH2-〇CCHsCH2 (3) (4) :h2-〇cch*ch2 i In the above formulas (1) and (2), QlAQ2 Independent of each other, means (meth) propylene oxime or (meth) propylene oxyalkyl group, wherein the carbon number of the alkyl group is 丨 to 丨〇; in the above formula (2), R represents hydrogen or carbon number. a hydrocarbon group of 1 to 1 Torr; wherein, in the above formula (3), T!, T2 and TS independently represent a (meth)acryloxy group; in the above formula (4), T represents a hydroxyl group or a (decyl)propene group.醯oxy). In the polarizing plate of the present invention, the above-mentioned curable resin composition is preferably a compound containing an oxetane compound. In the polarizing plate of the present invention, the curable resin composition is preferably one containing fine particles. In this case, the curable resin composition is preferably contained in an amount of 5 to 250 parts by weight based on 100 parts by weight of the active energy ray-curable compound. In the polarizing plate of the present invention, the microparticles are preferably oxidized granules of the granules 1 321 〇 〇 〇 nm 7 321 008 200949317. In this case, the fine particles of the oxidized fine particles are more preferably one or more functional groups selected from the group consisting of a hydroxyl group, an epoxy group, a (meth)acryloxy group, and a vinyl group. In the polarizing plate of the present invention, the thickness of the protective layer is preferably from 1 to 35 μm. The present invention can simultaneously provide an optical component formed of the laminate of the above-described polarizing plate and optical functional layer of the present invention. The optical functional layer in the optical module of the present invention is preferably any one of a retardation layer, a brightness enhancement film, and a surface treatment layer. The present invention further provides a liquid crystal display device in which the polarizing plate of the present invention or the optical component of the present invention described above is disposed on one surface or both sides of a liquid crystal cell. (Effect of the Invention) According to the present invention, since the thickness of the protective layer can be made smaller than that of the conventional TAC film or the like, the polarizing plate can be made thinner and lighter, and the adhesion between the polarizing film and the protective layer is good. Further, since the hardness of the protective layer can be increased, the mechanical strength of the polarizing plate can be improved, and even when the thickness of the protective layer is reduced as compared with the prior art, the shrinkage of the polarizing film can be effectively suppressed under high temperature and high humidity. The polarizing plate of the present invention and the optical component using the same are suitably used for, for example, a liquid crystal display device for portable use. [Embodiment] <Polarizing Plate> The basic composition of the polarizing plate of the present invention includes a polarizing film in which a dichroic dye is adsorbed on a polyvinyl alcohol resin film, and 8321008' 200949317 formed in the polarizing film. A protective layer on the surface or on both sides, the protective layer being formed of a cured product of a curable resin composition containing an active energy ray-curable compound. In the polarizing plate of the present invention, the active energy ray-curable compound used in the protective layer contains a compound having at least one epoxy group in the molecule and at least one (meth) acryloxy group in the molecule (A) The acrylic compound... and the protective layer has an elastic modulus of 3,300 to 10,000 MPa. At the same time, the "elasticity rate" in οr = 曰 is the meaning of the (four) rate of the normal temperature polarized light unless otherwise specified. In the case of the present invention, the polarizing film in the middle of the present invention is formed by a polyvinyl alcohol-based resin to form a polyethylene resin-based dye which is adsorbed and oriented in a uniaxially stretched poly resin ^=, (4) a vinyl alcohol resin' Polyvinyl acetate Ο ! 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚, vinyl acetate, olefins, ethyl, bovine and carboxylic acids, unsaturated sulphate is about 85 S 1 〇〇 mol % 弊 树 月 月 旨 旨 通 通 通 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯 聚乙烯〇 耳 % is better. Polyvinyl formal is cut into B;; if the quality can be modified with aldehydes, 1 〇 = often about r, 00 〇 i1 〇, _, m__n " U, 00 〇 is preferred. The film of about 1,500 to 'this kind of polyacetyl alcohol tree can be used' can be used as the original film of polarizing film 321008 9 200949317. The method of forming the film of the polyvinyl alcohol-based resin is not particularly limited, and a known method can be used. The thickness of the original film formed of the polyvinyl alcohol-based resin is not particularly limited, and is, for example, about 10 to 15 0 // m. The production of the polarizing film is generally a step of uniaxially stretching the original film formed of the above polyvinyl alcohol-based resin, and dyeing the polyvinyl alcohol-based resin film with a dichroic dye to adsorb the dichroic dye. And a step of treating the polyvinyl alcohol-based resin film having adsorbed the dichroic dye with a boric acid aqueous solution, and a water washing step after the boric acid aqueous solution treatment. The uniaxial stretching may be carried out before the dyeing with the dichroic dye, or simultaneously with the dyeing, or after the dyeing. When the uniaxial stretching is carried out after the dyeing of the dichroic dye, the uniaxial stretching may be carried out before the boric acid treatment or in the boric acid treatment. Alternatively, uniaxial stretching can be performed at the complex stages of such processing. The uniaxial extension can be extended uniaxially between rollers of different peripheral speeds, or it can be extended on a single axis using a hot roller. Meanwhile, it may be a dry stretching method such as stretching in the atmosphere, or a wet stretching method in which it is extended in a state of being expanded in a solvent. The stretching ratio is usually about 4 to 8 times. When the polyvinyl alcohol-based resin film is dyed with a dichroic dye, for example, the polyvinyl alcohol-based resin film may be impregnated into an aqueous solution containing a dichroic dye. As the dichroic dye, iodine, a dichroic dye or the like can be used. Prior to the dyeing treatment, the polyvinyl alcohol-based resin film should be first treated by dipping in water. When iodine is used as the dichroic dye, a method in which a polyvinyl alcohol resin film is impregnated in an aqueous solution containing iodine and potassium iodide is usually used as a method of dyeing. The content of potassium iodide is usually about 0.5 to 10 parts by weight, based on 100 parts by weight of the water, and the amount of potassium iodide is usually from about 0.5 to about 10 parts by weight. The temperature of the aqueous solution used for dyeing is usually about 20 to 40 ° C, and the time (dyeing time) of impregnation in the solution is usually about 30 to 300 seconds. On the other hand, when a dichroic dye is used as the dichroic dye, the dyeing method is usually a method in which a polyvinyl alcohol-based resin film is impregnated into an aqueous dye solution containing a water-soluble dichroic dye. The content of the dichroic dye in the aqueous dye solution is usually about 1×1 (Γ3 to lxl CT2 parts by weight relative to 100 parts by weight of water. The aqueous dye solution may also contain an inorganic salt such as sodium sulfate as a dyeing aid. Usually, it is about 20 to 80 ° C, and the time (dyeing time) of impregnation in the aqueous dye solution is usually about 30 to 300 seconds. The treatment with boric acid after dyeing with dichroic dye is the dyed polyethylene. The alcohol resin film is impregnated in an aqueous solution containing boric acid, and the boric acid content in the aqueous solution containing boric acid is usually about 2 to 15 parts by weight, and preferably about 5 to 12 parts by weight, based on 100 parts by weight of water. When iodine is used as the dichroic dye, the aqueous solution containing boric acid is preferably another potassium iodide. The potassium iodide content in the aqueous solution containing boric acid is usually about 2 to 20 parts by weight with respect to 100 parts by weight of water. Preferably, it is about 5 to 15 parts by weight. The time of impregnation in the aqueous solution containing boric acid is usually about 100 to 1,200 seconds, preferably 150 to 600 seconds, and preferably about 200 to 400 seconds. The temperature of the aqueous solution is usually 50 ° C or higher, preferably 50 to 85 ° C. The boric acid-treated polyvinyl alcohol resin film is usually washed with water, 321 008 π. 200949317. For example, boric acid treated The polyvinyl alcohol resin film is impregnated and washed with water in water. The water temperature during the water washing treatment is usually about 5 to 40 ° C, and the immersion time is about 2 to 120 seconds. After washing with water, the polarizing film can be obtained. The drying treatment can be carried out using a hot air dryer or a far infrared heater. The drying temperature is usually about 40 to 100 ° C. The drying treatment time is usually about 120 to 600 seconds. After the above operation, it can be obtained through a single shaft. The extended polyvinyl alcohol resin film adsorbs the polarizing film of the directional dichroic dye. The thickness of the polarizing film may be about 5 to 40 // m. (Protective layer) In the present invention, one or both of the above polarizing films are used. In the surface, a protective layer formed of a cured product of a curable resin composition containing an active energy ray-curable compound is laminated to form a polarizing plate. The active energy ray-curable compound in the present invention contains an intramolecular device. a compound having at least one epoxy group (hereinafter, also referred to as "epoxy compound") and a (fluorenyl) acryl compound having at least one (meth) acryloxy group in the molecule (hereinafter, also referred to as "(曱) "Acrylic compound"). At this time, the elastic modulus of the protective layer is 3,300 to 10, OOOMPa, preferably 3,500 to 8, OOOMPa. If the elastic modulus of the protective layer is less than 3,300 MPa, The ability to suppress shrinkage of the polarizing film under high temperature and high humidity is lowered, and as a result, the polarizing property is lowered. When the elastic modulus of the protective layer exceeds 10,000 MPa, the adhesion between the polarizing film and the protective layer is deteriorated, and peeling of the protective layer may occur. And other issues. Further, the protective layer, particularly in the case of shrinking the polarizing film 12 321008 200949317 in order to suppress the high temperature, is preferably such that the elastic modulus does not become too low even at high temperatures before and after. Specifically, the storage modulus at 80 C is preferably in the range of 1,500 MPa. Moreover, in the case of obtaining the elastic modulus of the front and back, especially when it is difficult to accurately measure the pre-test degree, it can be easily measured here at a high temperature, and the day + ± ^, and the sample is indicated. The stiffness is approximately similar to the storage elastic modulus of the tensile modulus concept. τ ❹ The epoxy resin is contained in the curable resin composition. The polarizing film and the retardation film have excellent adhesion properties, such as properties, mechanical strength, thermal stability, and moisture barrier properties. Here, the term "a compound of a durable epoxy group" as used in the present invention means having one in a molecule; and having more than one active energy ray (for example, ultraviolet ray, visible light, methoxyl group) a compound that hardens by irradiation with a line, etc.). At the same time, an epoxidized=, X-ray-based acryl compound and a propylene-propylene compound to be described later: (a-type energy ray-curable compound). For the above-mentioned epoxy compound, there is no specificity and refraction. Rate, cationic polymerizability, etc. _ θ is limited, but it is preferably an epoxide resistant epoxy compound. As for the bismuth, the aryl group does not contain an aryloxy compound, and the paste may be a hydrogenated epoxy 77+ oxime containing an aromatic ring. A cycloaliphatic epoxy compound, etc. s an 'aliphatic epoxy compound, in the presence of a catalyst, the aromaticity = hydrogenation reaction, then hydrogen can be selected under the ink to select a group of epoxy compounds, for example Such as double: σ. As for the fragrance

Di-glycidyl ether, double-conceived water 2 glycerol hydrazine, double sulphate F glycidyl ether and other bisphenol-type epoxy tree 321008 13 200949317 曰 曰, age secret oxy-resin, age-old epoxy resin epoxy Resin, etc., type epoxidized glycerol, tetrahydroxy A-float _ "multi-functional bismuth glycerol oxime, such as dehydrogenated water, epoxidized polyethylene _ 1 W. Hydrogenated two-year-old dehydroglycerin is preferred. In terms of mouth, = in the fat compound, can be phased (four) into:: poly-dehydration glycerol - more to say, for example, 14 butyl alcohol Two dehydroglyceryl ether, three oils of oil, m propane; ^: dehydrated water (four), glycerol - dehydrated water deglycerin scale, polyethylene 2: propylene glycol di-glycidyl ether, in B Addition of diols or aliphatic polyols such as propylene glycol and glycerol: = oxy-oxo-alcohol: = alicyclic epoxy compound means epoxy having at least η π: epoxy group Compound. "Combined in the county of the alicyclic ring

The structure of one or a plurality of chlorines in (CH2)ffi is removed from the formula 7. In the formula, m is an integer of 2 to 5. Therefore, the alicyclic epoxy compound means a compound having at least a structure represented by the above formula in the molecule. More specifically, after the above == or the above-mentioned formula removes one or a plurality of hydrogens in the formula: I, a compound having a group having another chemical structure, can be an alicyclic epoxy compound. ((5) Heart-- or multiple hydrogens, 321008 14 200949317 is suitably substituted with a linear alkyl group such as methyl or ethyl. * In the above epoxy compound, it is an alicyclic epoxy. The compound is preferably i-less than one epoxy group is a compound bonded to an alicyclic ring: especially having oxabicyclohexanone (m=3 in the above formula) or oxadanthrene (for the above formula) The epoxy compound which is m=4 in the middle is more suitable because it has a high modulus of elasticity and is excellent in adhesion to the fineness, and is more suitable for use in the present invention. Specific examples of the structure of the alicyclic oxime epoxy compound, but the present invention is not limited to the compound.

(wherein R1 and R2 independently of each other represent an old-fashioned base). (4) Epoxy cyclohexane (tetra) epoxycyclohexyl methacrylate represented by the following formula (1): a non-halogen atom or a linear chain having a carbon number of 1 to 5.

'An oxygen-free atom or a linear integer with a carbon number of 1 to 5.) (wherein 'R3 and R4 independently of each other represent a hydrogen atomic alkyl group, and η represents an integer of 2 to 20). (c) a di-acidified epoxy represented by the following formula (III)

Epoxycyclohexylmethyl ester of monocarboxylic acid. 321008 15 200949317 (wherein R5 and R6 independently of each other represent a hydrogen atom or a straight bond group having a carbon number of 丨5, and P represents an integer of 2 to 20).

CRT) (4) Epoxycyclohexylmethyl bond of polyethylene glycol represented by the following formula (IV): ^N^CH2-(0C2H4)q-0-CH2,

R (wherein 'R7 and R8 independently of each other represent a hydrogen atom or a linear alkyl group having a carbon number of 丨5, and q represents an integer of 2 to 10). (e) Epoxy ring of alkanediol represented by the following formula (V): ^v^CH2»0-(CH2)r-〇-CH2, ^ soil T soil 1 (V) R9 Ri〇 (in the formula R9 and R1, which independently represent a hydrogen atom or a linear alkyl group having a carbon number of i to 5, represent an integer of 2 to 20. (f) A diepoxy trispirate compound represented by the following formula (VI): (VI) vood R11 to 5 straight (wherein R and R independently of each other represent a hydrogen atom or a carbon number chain alkyl group). (g) a diepoxy single spiro compound represented by the following formula (VII):

(W) Straight to 5 (wherein R13 and R14 independently of each other represent a hydrogen atom or a carbon number of 1 321008 16 200949317 chain-like alkyl group). (h) Ethylene cyclohexane diepoxide represented by the following formula (VIII): (VE) (wherein R15 represents a hydrogen atom or a linear alkyl group having a carbon number of 丨 to 5) (i) The epoxycyclopentyl ether represented by the formula (IX): W R16 R17 (wherein R16 and R17 independently of each other represent a hydrogen atom or a chain alkyl group having a carbon number of i to 5). ' (j) Diepoxy tricyclic terbene represented by the following formula (X): 0:...

❹ (K)

(X) ❹ (wherein R18 represents a hydrogen atom or a carbon number! to a linear alkyl group of 5). Among the alicyclic epoxy compounds exemplified above, an epoxy compound is preferably used in the following formula because it is commercially available or relatively easy to obtain an analog thereof. (A) 7 oxa bis% [4·1· 〇] 庚 _ 3_ 酸酸和 (7 ～: yl) methanol acetate [formula (1) ... omo compound], ^ methyl L 赖 4 · 丨.G] Glycol I3-Nu and (4-methyl, oxabicyclo "4 1 Oil q ΓΠ = ) methanol esterification [in formula (1), heart H3 'R = 4-CH3 compound], 321〇〇8 17 200949317 (An ester of 〇7-oxabicyclo[4.1.0]heptane_3_carboxylic acid with 1,2-ethanediol [Formula (II), compound of n=2], (D) (7-oxabicyclo[4·1〇]heptyl-3-yl) ester of decyl alcohol with adipic acid [Compound of formula 'III, p=4], (E) (4 methyl Esterified product of 7oxabicyclo[4.1.0]heptyl)methanol and adipic acid [Compounds of 'R5=4_CH3, R6=4_CH3, P=4 in formula (111)], (F) (7-oxalate Bicyclo[4. 1〇]hepta-3-yl) etherate of u-ethylene glycol [compound of n=H, r=2 in formula (v)]. Each epoxy compound in the present invention may be In the curable resin composition used in the present invention, the ratio of the epoxy compound to the active energy ray-curable compound is 0 to 9 G by weight in 1 part by weight of the active energy ray-curable compound. Share Preferably, it is preferably in a proportion containing parts by weight of the money, and more preferably in a proportion of 40 to 70 parts by weight. For example, when the content of the epoxidized person is less than 30 parts by weight, the density between the polarizing film and the protective layer is When the amount exceeds 9° by weight, the performance of the cured layer of the cured product tends to decrease due to the vaporization of the protective layer. The properties are also the same as the above epoxy compound. The compound of the epoxy type can reduce the viscosity of the curable resin composition, thereby making the hardening faster, and at the same time, preventing the yellowing of the protective layer of the cured product, and improving ^ 321008 18 200949317

Burned, 1,4-bis[(3-ethyl_3_epoxypropyl)methoxymercapto] stupid, 3-~ethyl-3-(phenoxymethyl)epoxypropanol, two [(3-Ethyl-3-epoxymethane)methyl]ether, 3-ethyl-3-(2-ethylhexyloxymethyl)3⁄4 oxypropanone, phenol aldehyde propylene oxide, and the like. As such a propylene oxide compound, a commercially available product can be easily obtained, and for example, "ARON OXETANE OXT-101" and "from 〇N" are commercially available.

0XE1TANE 0XT-121", "ARON OXETANE 0XT-211", "ARON OXETANE 0H-221", "AR0N OXETANE 0XT-212" (all of which are manufactured by East Asia Synthetic Co., Ltd.). The compounding amount of the epoxigenic compound is not particularly limited, and is usually preferably 30 parts by weight or less, and preferably 10 parts by weight or more, based on 100 parts by weight of the active energy ray-curable compound. When the curable resin composition used in the present invention contains a cationic curable compound such as an epoxide or a propylene oxide compound, a photocationic polymerization initiator is preferably added to the curable resin composition. When light or an ion polymerization initiator is used, since protection can be formed at normal temperature, the heat resistance of the polarizing film or the necessity of skew due to expansion is reduced, and a protective layer having good adhesion can be formed on the polarizing film. . At the same time, since the photo-ion polymerization initiator is a photocatalytic activator, it is a kind of resin, which is good for the preservation of the shirt. (4) New handle: the hardened photo-cationic polymerization initiator is by visible light, ultraviolet light, Irradiation of an active energy ray such as an electron beam to produce a cationic species or a compound for starting an epoxy compound and/or a propylene oxide compound: : Reactor. In the present invention, any type of photocationic polymerization can be used, and it is not particularly limited, and examples thereof include an aromatic diazo drill salt, an aromatic ^ 32 ΐ〇〇 δ 19 200949317 iodine rust salt, an aromatic rust salt, and the like. Strontium salt; iron-propadiene (allene) wrong salt and the like. Examples of the aromatic diazonium salt include benzodiazepine hexafluoroantimonate, benzodiazepine hexafluorophosphate, and benzodiazepine hexafluoroborate. Meanwhile, examples of the aromatic iodonium salt include diphenyl iodonium salt of ruthenium (pentafluorophenyl) borate, diphenyl iodonium hexafluorophosphate, diphenyl iodine hexafluoroantimonate, and six A bis(4-mercaptophenyl) iodonium fluorophosphate salt or the like. As the aromatic sulfonium salt, for example, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium sulfonate (pentafluorophenyl)borate, and bishexafluoride Phosphate 4, 4'-bis[diphenylthio]diphenyl sulfide, bishexafluoroantimonate 4,4'-bis[bis(/3-hydroxyethoxy)phenylthio)] Phenyl sulfide salt, 4,4'-bis[bis(/3-hydroxyethoxy)phenylthio)diphenyl sulfide salt of hexafluorophosphate, hexafluoroantimonic acid 7-[two (pair Phenylphenyl)thiol]-2-isopropylthioxanthone salt, ruthenium (pentafluorophenyl)boronic acid 7-[bis(p-phenylphenyl)sulfide]-2-isopropylthioxanthone salt , 4-phenylcarbonyl-4'-diphenylsulfanyl-diphenyl sulfide salt of hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenyl hexafluoroantimonate Thiosulfonyl-diphenyl sulfide salt, bismuth(pentafluorophenyl)boronic acid 4-(p-tert-butylphenylcarbonyl)-4'-di(p-phenylene)thiolocene-diphenyl Base thioether salt and the like. As the iron-propadiene salt, for example, xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, diterpene Benzene-cyclopentadienyl iron (II) ginseng (trifluoromethylsulfonyl) decane compound and the like. Such a photo-cationic polymerization initiator can be easily obtained as a commercial product, for example, "KAYARAD PCI-220" and "KAYARAD PCI-2012008 200949317 620" (the above-mentioned "Nippon Chemical Co., Ltd.") "UVI-6990" (made by Union Carbide), "ADEKA 0PT0MER SP-150", "ADEKA 0PT0MER SP-170" (above, ADEKA), "CI-5102", "CIT-1370", "CIT-1682", "CIP-1866S", "CIP-2048S", "CIP-2064S" * (above, Japan's Soda (share) system), "DPI-101", "DPI-102", "DPI- 103", "DPI-105", "MPI-103", "MPI-105", "BBI-101", "BBI-102", "BBI-103", "BBI-105", "TPS-101" "TPS-102", "TPS-103", "TPS-105", "MDS-103", "MDS-105", "DTS-102", "DTS-103" (above, Midori Chemical) )), "PI-2074" (made by Rhodia Corporation), "UVACURE 1590" (DAICEL-CYTEC system). These photocationic polymerization initiators may be used singly or in combination with one or more other kinds. Among these, in particular, an aromatic sulphur salt has ultraviolet absorbing properties in a wavelength region of f 300 nm or more, and provides excellent adhesion, excellent mechanical strength, or good adhesion to enthalpy between polarizing films. Hardened, so it is more suitable. It is hardened with respect to a cationic compound such as an epoxy compound or a propylene oxide compound, and the total amount of the raw material is 1 part by weight, and the photocationic polymerization initiator is *5 to 20 parts by weight, and is 1 It is preferably up to 6 parts by weight. The mechanical strength or protective layer is obtained when the amount of the stone photocationic polymerization initiator is less than 5 parts by weight, and the mechanical strength or protective layer is set to be less than 5 parts by weight based on the total amount of the oxygen compound and the epoxy compound. Z with the polarizing film: there is a tendency to decrease. At the same time, compared with the total amount of the cationic hardening compound, if the amount of the photocationic polymerization initiator is more than 20 parts by weight, the ionic substance may increase due to the hardening. Improve the hygroscopicity of the cured product, thereby reducing the durability. The curable resin composition used for forming the protective layer contains the above epoxy compound, or the above epoxy compound and propylene oxide compound, and is radically polymerizable and has at least one (meth) propylene oxide in the molecule. , a (meth)acrylic compound. Since the (meth)acrylic compound is contained, a protective layer having high hardness, excellent mechanical strength, and high durability can be obtained. Further, since the (meth)acrylic compound is contained, the viscosity and the curing rate of the curable resin composition, the surface hardenability of the protective layer, and the adhesion between the polarizing film and the like are more easily adjusted. . Further, the (fluorenyl) acrylic compound in the present invention can provide 3, OOO MPa or more (3, 100) by using a cured product formed only of a compound having the (meth)acryl fluorenyl group and a polymerization initiator. It is preferred that the modulus of elasticity is preferably MPa or more. When a (meth)acrylic compound having a modulus of elasticity of less than 3, 〇〇〇 MPa is used for a cured product formed only of a compound having the (meth) acrylonitrile group and a polymerization initiator, the protective film is used. The mechanical strength is insufficient, and the shrinkage of the polarizing film cannot be suppressed. ® Here, "(meth)acryloxy" means methacryloxy or propylene oxy. "(Meth)acrylic compound having at least one (meth)acryloxy group" means having at least one mercaptopropenyloxy group or acryloxy group in the molecule, respectively, which can be initiated at the photoradical polymerization. A methacrylate derivative or a propionate derivative which is hardened by irradiation with an active energy ray (for example, ultraviolet light, visible light, electron beam, xenon ray, etc.) in the presence of the agent. As the (meth) 22 321008 200949317 acrylic compound having at least one (meth) propylene fluorenyloxy group in the molecule, for example, (meth)acrylic acid having at least one (meth) propylene-olefinic oxy group in the molecule may be mentioned. An ester monomer (hereinafter referred to as "(meth)propionate-ester monomer"), or a (meth)acrylate oligomer having at least two (meth)acryloxy groups in the molecule (hereinafter A compound containing a (meth) acryloxy group, such as "(meth) acrylate oligomer"). These compounds may be used singly or in combination with one or more of them. The term "(meth)acrylic acid acrylate monomer" refers to an acrylate monomer or a T-propyl acetoacetate monomer, respectively, and a (meth) acrylate oligomer refers to an acryl vinegar oligomer. Or a methacrylate oligo. The above-mentioned (mercapto) acrylate monomer may, for example, be a (meth) acrylate monomer having one (meth) acryloxy group in the molecule (hereinafter, referred to as "monofunctional (meth) acrylate). (Ester monomer)), a (meth) acrylate monomer having two (meth) acryloxy groups in the molecule (hereinafter referred to as a difunctional (/) acrylate monomer), and three molecules in the molecule The above (fluorenyl) acryloxy (indenyl) acrylate monomer (hereinafter referred to as polyfunctional (meth) oxime-acid vine monomer). The (meth)acrylic acid vinegar monomer may be used alone or in combination of two or more. Specific examples of the monofunctional (meth) acrylate monomer include, for example, a gas-trapping methyl (mercapto) acrylic acid vinegar, and a 2-ethylidylethyl (meth) acrylic acid decyl propyl group. (Meth)acrylic acid vinegar, 3, propyl (meth) propylene oxime, 2-hydroxybutyl (fluorenyl) acrylate, 2 hydroxy _3 phenoxy propyl (meth) acrylate , isobutyl (meth) acrylate, tributyl (meth) acrylate, 2-ethylhexyl (decyl) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (A B) vinegar vinegar, stupid methyl (meth) propylene 321008 23 200949317 vinegar, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, dicyclopentenyl Oxyethyl (meth) acrylate, dimethylaminoethyl (decyl) acrylate, ethyl carbitol (meth) acrylate, trimethylol propyl mono(methyl) propylene glycol Ester, pentaerythritol mono (meth) acrylate vinegar, stupid oxy polyethylene glycol (meth) acrylate, and the like. As the monofunctional (meth) acrylate monomer, a carboxyl group-containing (methacrylate monomer) can be used. As for the monofunctional (meth) acrylate monomer having a carboxyl group, for example, 2-(meth) propylene oxime can be mentioned. Ethyl citric acid, 2_(methyl) propylene oxiranyl ethyl hexahydrophthalic acid, carboxyethyl (meth) acrylate, ❹ 2 (meth) propylene oxiranyl ethyl succinic acid, N_ ( Methyl) propylene aryloxy N, N - carboxy-p-phenylenediamine, 4-(methyl) propylene oxy oxyethyl trimellitic acid, etc. Further, monofunctional (meth) acrylate monomers are also available A monomer containing a (meth)propenylamine group such as 4-(methyl)propylamino group + silk methyl alcohol or the like is used. _ As for the above difunctional (meth) acrylate monomer, although The use of 1-alcoholic di(methyl)-propyl acetoacetate, polyoxyalkylene glycol di(meth)acrylic acid = class, substituted diol diol di(meth)acrylic acid vinegar, aliphatic plural a (meth) acrylate of a decyl alcohol, a di(meth) acrylate of a hydrogenated dicyclopentadiene or a tricyclic fluorenyl diol, and a dioxane diol (di〇Xanegly C) 〇l)

Or di(meth) acrylates of decane dialtanol, di(meth) acrylates of bisphenol A or decane adducts of bisphenol f, bisphenol A or bisphenol F, The gas mono(meth)acrylic acid vinegar or the like is a representative monomer, but it is not limited thereto and various monomers can be used. Specific examples of the difunctional (meth) acrylate monomer include ethylene 321008 24 200949317 alcohol di(meth) acrylate, 1,3-butylene glycol di(decyl) acrylate, 1,4-butyl Diol (meth) acrylate, 1,6-hexanediol di(meth) acrylate, 1,9-nonanediol di(meth) acrylate, neopentyl glycol di(methyl) propyl _ enoate, trimethylolpropane bis(indenyl) acrylate, pentaerythritol di(meth) acrylate, bis(trimethylolpropane) bis(indenyl) acrylate, diethylene glycol di(a) Acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(decyl)acrylate, tripropylene glycol di(meth)acrylate, ruthenium polyethylene glycol di(meth)acrylate, Polypropylene glycol di(meth) acrylate, polybutylene glycol di(meth) acrylate, polyoxo bis (meth) acrylate, hydroxy trimethyl acetate neopentyl glycol di(a) Acrylate, 2, 2 bis[4-(methyl) propylene methoxy ethoxy ethoxy phenyl] propane, a pair of [4-(methyl) propyl Eneoxyethoxyethoxycyclohexyl]propane, hydrogenated dicyclopentadienyl di(meth)acrylate, tricyclodecane dimethanol di(meth) acrylate, 1,3-dioxene Alkane-2,5-diyldi(meth)acrylate [aka: dioxanediol di(meth)acrylate], acetal trimethylacetaldehyde and triterpene hydroxymethylpropane acetal compound [Chemical name: 2-(2-hydroxy-lvl-dimethyl'ylethyl)-5-ethyl-5-ylaminomethyl 3_di-drinking] di(meth)propene, etc. 1' 3 The di(methyl) propylene trifunctional or higher (meth) acrylate monomer of '5-g (2_M-ethylethyl) isocyanuric acid® 1 may be exemplified by glycerol tris(T-based) acrylate vinegar. Trimethyl methacrylate tris(methyl) acrylate vinegar, ": methicillin tris(methyl) propylene _, bis (trimethyl propylene hydride; = propionate, pentaerythritol three (a Acetate vinegar ^ base) propionate, dipentaerythritol tetra (methyl (tetra) (four) know four = 3210 〇 8 25 200949317 where L-methyl-pentaerythritol hexa(methyl) propyl vinegar and other three official two fat The poly(methyl) acetoacetate of the family polyol is replaced by: Body, others can be cited as a trifunctional or higher functional glyco-glycolic acid, glycerol, epoxy-based poly(methyl) tris(methyl)propyl-ester, three-worker The three (meth)acrylic acid vinegar, Wei 1 ginseng [(methyl) propylene methoxy ethoxy ethoxy] propane, U, Bulai: 2 monoethylidene) isocyanuric acid Triacetin (meth) acrylate vinegar, polyoxet hexamethyl (meth) acrylate, and the like. As the above (meth) acrylate oligomer, for example, an amine ester (meth) oxime acetoacetate oligomer, a polyester (meth) acetonate oligopolymer, an epoxy (meth) acrylate may be mentioned. Ester oligomers and the like. The (meth) acrylate oligomer may be used alone or in combination of two or more. The amine ester (meth) acrylate chelate is a compound having an amine ester bond (-NHC00-) and at least two (meth) propylene oxime groups in the molecule. Specifically, it is a product obtained by esterification of a (meth) acrylate monomer having at least one (meth) acryloxy group and at least one hydroxyl group in the molecule with a polyisocyanate by hydrazine, or a polyol. An amine-like compound which reacts with a polyisocyanate and which contains a terminally-isolated acid vine group, and an amine having a (meth) acrylate monomer having at least one (meth) acryloxy group and at least one hydroxyl group in the molecule A product of an esterification reaction. As the hydroxyl group-containing (meth) acrylate monomer used in the amine esterification reaction, for example, 2-hydroxyethyl (mercapto) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (decyl) acrylate, glycerol di(meth) acrylate, three 26 321008* 200949317 Ϊ methyl, pentaerythritol three (four)) Acrylic acid, pentaerythritol, penta (meth)acrylic acid vinegar, and the like. ❹ : : 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与Foshan diisocyanate, hexyl methacrylic acid diisocyanate, diisocyanate diisocyanate, diisocyanate benzoic acid: to make these diisocyanates G-hydrogen vinegar (10) obtained by hydrogenation, such as hydrogenated diteric acid, f-phenyl ester, hydrogenated diisocyanate, benzene, etc., triphenyl-triisocyanate Di- or triisocyanuric acid vinegar, such as dimethylenetriphenyl triisocyanate, diphenylmethyl-containing diterpene, earthenic acid, citric acid ester, and polyisocyanate obtained by quantifying diisocyanate Sour and so on.

At the same time, in the case of the polyisocyanate which is obtained by the isocyanic acid corresponding to (iv) the terminal isocyanate group-containing amine ester compound, in addition to the aromatic, aliphatic and halo-type polyols, for example, polyester Polyol, polyether polyol, and the like. As the fat (iv) and the alicyclic polyol, for example, n-but, alcohol, 1:6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, 'propylene glycol, neopentyl glycol, and three By methyl ketone, tribasin propylene, bis (trimethoprim), quaternary alcohol, diquaternol, dimethylglycol, dimethyl methacrylate, dimethylolbutanoic acid , glycerin, hydrogenated bisphenol hydrazine, and the like. The polyester polyol is a product obtained by a condensation reaction of the above polyol with a polyvalent carboxylic acid or an anhydride thereof. Examples of the polyvalent carboxylic acid or an anhydride thereof include succinic acid (anhydride), adipic acid, maleic acid (anhydride), itaconic acid (anhydride), trimellitic acid (anhydride), and pyromellitic acid ( Anhydride), hexahydrophthalic acid (anhydride), citric acid (Xuan), meta-antimonic acid, p-citric acid, and the like. 321008 27 200949317 As the above polyether polyol, in addition to the polyalkylene glycol, for example, the above polyterpene alcohol or a polyoxyalkylene-modified polyol obtained by reacting a dihydroxy phenyl group with an alkylene oxide can be exemplified. The polyester (fluorenyl) acrylate-polymerized polymer refers to a compound having an ester bond and at least two (meth) acryloxy groups in the molecule. Specifically, it can be known from the condensation reaction of (fluorenyl)acrylic acid, polybasic acid or its anhydride, and polyol. As the polyvalent carboxylic acid or its anhydride used in the condensation reaction, for example, succinic acid (anhydride), adipic acid, maleic acid (anhydride), itaconic acid (anhydride), and phthalic acid (anhydride) may be mentioned. , pyromellitic acid (anhydride), hexahydrofurfuric acid (anhydride), citric acid (anhydride), stagnation, equivalence. Meanwhile, the polyhydric alcohol used in the condensation reaction may, for example, be 1,4-butanediol, 1,6-hexanediol, ethylene glycol ethyl alcohol, diethyl alcohol, propylene glycol, neopentyl glycol, or the like. Hydroxyalkyl bromide, 4-methylpropane, di(trimethylene methacrylate, pentaerythritol, dipentaerythritol, dimethylol heptane, dihydroxymethylpropionic acid, dimethylolbutanoic acid, glycerol hydrogenation Bisphenolphthalein, etc. The % oxy (meth) acrylate condensate can be obtained by addition reaction of polydehydraffinol oxime (meth) propyl benzoic acid, which has at least two (methyl) groups in the molecule. Propylene oxime. As for the polydehydroglycerin scale used in the addition reaction, for example, ethylene glycol di-dehydroglycerin scale 'propylene glycol di-dehydroglycerol test, dipropylene glycol di-glycidyl ether, hexanediol two go Glycidyl ether, indophenol A, dehydroglycerin, etc. ^ Also phenolphthalein (four) Γ () Among the acrylic compounds, especially the adhesion, the elastic modulus is excellent (four), is the money less - species The (meth)(10) acid compound is preferred. Cut) to (4) 321008 28 ¢1) 200949317

(2) (3) (4) In the above formulae (1) and (2), (^) and Q2 independently of each other represent (meth)propenyloxy or (fluorenyl)acryloxyalkylene. When hydrazine or Q2 is a (meth) propyl decyloxyalkyl group, the alkyl group may be a straight chain or a branched chain, and its carbon number is from j to ❹', usually at a carbon number of from about 〖 to about 6. Meanwhile, in the formula (2), a hydrocarbon group having a carbon number of 1 to 1 Å, the hydrocarbon group may be a straight chain or a branched group, and a typical group is an alkyl group. The alkyl group at this time is also usually at a carbon number of about 1 to 6. Further, in the formula (3), Τι, 1 and each independently represent a (meth) propylene decyloxy group, and in the formula (4), a hydroxy group or a (meth) acryloxy group is represented. ,. The compound represented by the formula (-1) is a -(meth)acrylic acid vinegar derivative of hydrogenated dicyclopentadiene or tricyclodecane bis-alcohol, and specific examples thereof have been given in the previous examples, including hydrogenated dicyclopentane Alkenyl di(meth) acrylate [in the formula (1), a compound of a fluorenyloxy group], a tricyclodecane dialkyl alcohol (a 32 l 〇〇g 29 200949317 yl) acrylate The ester [in the formula (1), Q1 = Q2 = (indenyl) propylene methoxymethyl group], and the like. The compound represented by the formula (2) is a di(meth) acrylate derivative of dioxane diol or dioxane dialtanol, and specific examples thereof have been exemplified above, including 1,3-dioxane-2. 5-diyldi(meth)acrylate [aka: dioxane di, alcohol di(meth)acrylate] in formula (2), Q1 = q2 = (fluorenyl) propylene decyloxy, hydrazine a compound], a secret compound of a triterpene group and a trimethyl ketone compound [Chemical name: 2-(2-transyl-1,1-dimethylethyl)-5-ethyl_5-hydroxyl Di-(indenyl) acrylate of methyl-1,3-dioxene-depleted] [In the formula (2), ❹(methyl)acryloxycarbonyl group, Q2=2-(indenyl) propylene oxime a compound of a dimethyl group, an ethyl group, and the like. The compound represented by the formula (3) has been exemplified previously, and it is a tris-acrylic acid or trimethyl acrylate vinegar of ruthenium, 3,5-parameter (2-monoethylidene)-isocyanuric acid vinegar. Meanwhile, the compound represented by the formula (4) is a tris or tetra(meth) acrylate of pentaerythritol, and specific examples thereof have been exemplified above, including pentaerythritol tri(meth) acrylate and pentaerythritol tetra(meth) acrylate. In the curable resin composition used in the present invention, the (meth)acrylic compound is preferably 10 to 2 parts by weight, and 2 to 65 parts by weight, based on 100 parts by weight of the active energy ray-hardenable compound. Preferably, it is particularly good when the reset is made up to 6 inches. When the content of the (meth)acrylic compound is less than 10 parts by weight, the shrinkage ratio of the polarizing plate may be increased. Meanwhile, when the content of the (meth)acrylic compound exceeds 7 parts by weight, the adhesion between the polarizing plate and the protective layer may be insufficient. When the curable resin composition contains the above-mentioned (meth) acid compound 321008 30 200949317, such as a radical polymerizable compound, it is preferable to use a photoradical polymerization initiator as a photoradical polymerization initiator. It is sufficient to start polymerization of a radical polymerization property of a (meth)acrylic compound by irradiation with an active energy ray, and a conventionally known polymerization initiator can be used. Specific examples of the photoradical polymerization initiator include, for example, acetophenone, 3 to methyl acetophenone, benzoquinone dimethyl ketal, and 1-(4-isopropylphenyl)-2 to interesting groups. _2 1-Methylpropan-1-yrylate, 2_indolyl-^4-(methylthio)phenyl-2~?-linylpropionate, 2-hydroxy-2-indenyl-1-benzene Propylbenzene starter of propane-1-one - starting with benzophenone of benzophenone, 4- gas benzophenone, 4, 4,-diaminobenzophenone Such as benzoin isopropyl ether, benzoin B. benzoin test starter; such as 4-isopropyl thioxanthone thioxanthone starter; other such as xanthone, fluorenone, camphorquinone ), stupid, and so on. The amount of the photoradical polymerization initiator to be added is usually from 〇 5 to ❹ 20 parts by weight and is preferably from 1 to 6 parts by weight based on 100 parts by weight of the radically polymerizable compound such as a (meth)acrylic compound. When the amount of the photoradical polymerization initiator is less than 0.5 parts by weight relative to 100 parts by weight of the radically polymerizable compound, the hardening is insufficient, and it is possible to impart mechanical strength or a protective layer to the polarizing film. The adhesion between them is reduced. Meanwhile, when the amount of the photoradical polymerization initiator is more than 20 parts by weight based on 100 parts by weight of the acrylic compound, it is possible to lower the durability of the obtained polarizing plate. The curable resin composition used in the present invention may further contain fine particles. The hardenable resin composition will have a higher hardness and mechanical strength of the resulting protective layer of 321008 31 200949317 due to the inclusion of fine particles. Therefore, the ability to suppress the shrinkage of the polarizing film under temperature and humidity can be further improved. As the microparticles, for example, inorganic microparticles, organic microparticles, and inorganic/organic hybrid microparticles can be sandwiched: Since the protective layer is preferably optically transparent, the microparticles used are optically transparent without causing light scattering to hinder the protective layer. The inorganic fine particles are not particularly limited, and examples thereof include metal oxide fine particles such as cerium oxide microparticles, oxidized microparticles, tin oxide microparticles, oxide recording microparticles, and the like; tin oxide-ride oxide microparticles: emulsified indium- The composite oxide fine particles such as tin composite oxide fine particles have a low refractive index and a high strength, and are oxidized. The oxygen-cut microparticles may also have filaments on their surface. In the meantime, the machine recording may be, for example, a micro styrene resin, a resin, an organic polyfluorene fine particle, or a milk crystal. In the case of inorganic/organic hybrid fine particles, the base is based on a 2-based oxy group and a vinyl group (tetra) ❹, and "the tongue is crosslinked by the reaction of the linear hardening compound* 5, and the u surface has The above-mentioned microparticles such as _ 〇〇 测定 are determined by mrr dynamic light scattering method (10) method in which a hydroxyl group, an epoxy group, a oxidized stone atomic group of a reactive functional group such as a methyl group and a methyl group is more suitable for a methyl group. Ηπι or less is preferable, and preferably 70 rim or less. Guaranteed protection:: diameter: when r: when there is no optical transparency, and 'the particle size is usually 3 nm or more. The composition of the month:: Machine: The teacher can add solid microparticles to the curable tree, and can be dispersed in a solvent to form a colloid. 321008 32 200949317 As for the solvent, since the drying is relatively easy, it is preferable to use an organic dissolved gas. Inorganic micro-teachers in a suitable organic solvent. For example, a colloidal silica, a cerium oxide colloid, and a cerium oxide concentration are not particularly limited, and for example, about 20 to 20 of the commercially available hydrazine 2 can be used. 40% by weight of oxygen The ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ruthenium ^ ' 矽 矽 矽 particle size 1〇 to 15|1111, solid content 30% by weight), "] ^, to 1 ^ (Nissan Chemical Industry Co., Ltd., cerium oxide particle size 2 〇 to 25 nm, solid parts) weight %), "0SCAL 1132" (catalyzed into a chemical (stock) system, 10 to 20 nm for oxidized stone, 30 to 31% by weight of solid content); "0SCAL 1232" (organic solvent is ethanol) )), 矽 〇 〇 〇 〇 〇 〇 〇 〇 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; 〇 to ® 2〇nm, solid content 30 to 31% by weight); organic solvent is isopropyl alcohol "IPA ~ ST" (manufactured by Nissan Chemical Industry Co., Ltd., cerium oxide particle size 10 to 15nm, solid content 30% by weight ), "〇SCAL 1432" (catalytic chemical industry), oxidized stone particle size 10 to 20ητη, solid content 30 to 31 %); the organic solvent is n-butanol "NBA-ST" (manufactured by Nissan Chemical Industries Co., Ltd., cerium oxide particle size 10 to 15 nm, solid content 20% by weight), "0SCAL 1532" (catalytic chemical industry ( )), oxidation; e-particle size 1 〇 to 20 nm 'solid content 30 to 31% by weight); organic solvent is ethylene glycol "EG_ST" (曰 化学 化学 化学 ' ' 氧化 氧化 氧化 氧化 氧化 10 10 10 To [5nm, 20% by weight solids); organic solvent 33 • 321008 200949317 The agent is "OSCAL 1632" (catalytic chemical industry), cerium oxide particle size 10 to 20 nm, solid content 30 to 31% by weight); the organic solvent is "NPC-ST" of ethylene glycol mono-n-propyl ether (manufactured by Nippon Chemical Industry Co., Ltd., cerium oxide particle size 10 to 15 nm, solid content 30% by weight); organic solvent "MAC-ST" of dimethyl acetamide (manufactured by 曰Chem Chemical Industry Co., Ltd., oxide oxide particle size 10 to 15 nm, solid content 20% by weight), "DMAC-ST-ZL" (Nissan Chemical Industry) (Stock), cerium oxide particle size 70 to 100 nm, solid content 20% by weight); organic solvent is a mixture of diphenylbenzene and n-butanol "XBA-ST" (Nissan) Chemical industry (stock), cerium oxide particle size 10 to 15nm, solid content 30% by weight); organic solvent is methyl isobutyl ketone "MIBK-ST" (manufactured by 化学Chemical Industry Co., Ltd., cerium oxide "MEK-ST" having a diameter of 10 to 15 nm and a solid content of 30% by weight) and an organic solvent of mercaptoethyl ketone (manufactured by Seiko Chemical Industry Co., Ltd., having a cerium oxide particle size of 10 to 15 nm and a solid content of 30% by weight) "SP-1120" (made by Xiaoxi Chemical Industry Co., Ltd., cerium oxide particle size 15 to 20 nm, solid content 5 to 10% by weight), "SP-6120" (small chemistry industry), cerium oxide particle size 15 to 20 ηιη, 5 to 10% by weight of solid content; "SN0WTEX 20" (made by Nissan Chemical Industries Co., Ltd., cerium oxide particle size 10 to 20 nm), "SNOWTEX C" (Nissan Chemical Industry Co., Ltd.) The system has a cerium oxide particle size of 10 to 20 nm or the like, and these cerium oxide colloids may be used alone or in combination of two or more. In the case of the commercially available product of the solid cerium oxide microparticles, for example, the "AER0SIL" series of Japanese AER0SIL (shares) such as "AEROSIL 50" and "AEROSIL 130", "Nipsil E 150K", "Nipsil" Such products may also be used for the sale of Japanese niobium oxide products (shares) of the "Nipsil" series such as E 200". 34 321008 200949317 It is preferable to add 5 to 250 parts by weight of the above-mentioned fine particles with respect to the active energy ray-hardening agent contained in the hard-cured 1±tree v* product. The above-mentioned fine particles are preferably added in an amount of 10 to 100 parts by weight. When the amount of fine particles added is less than 5 parts by weight based on 100 parts by weight of the active energy ray-curable compound, the hardness of the protective layer may not be sufficiently increased by the addition of fine particles. On the other hand, when the addition of fine particles = more than 250 parts by weight with respect to 1 part by weight of the active energy ray-curable compound, there is a possibility that the adhesion between the polarizing film and the protective layer is lowered. When the amount of the fine particles added exceeds the by weight, the dispersion stability of the fine particles in the curable resin composition may be lowered, or the viscosity of the curable resin composition may be excessively increased. The sclerosing tree remnant may further contain a photosensitive ruthenium as needed (Photosensitize small use of a photosensitizer to improve the reactivity of the active energy ray-hardening S compound by cationic polymerization and/or radical polymerization, thereby improving the protective layer machinery The strength and the adhesion of the layer and the partial yarn. As the photosensitizer, for example, a few base compound, an organic sulfur compound, a ruthenium persulfide, a redox compound, an azo or a diazo compound, a tooth compound, a photoreduction For the specific photosensitizer, for example, a benzoin mystery, benzoin isopropyl ether, ", a benzoin derivative such as α-dimethoxyphenyl acetophenone; benzophenone, 2, 4- Dibenzophenone, methyl phthalate, 4,4, bis(dimethylamino)benzophenone, ", _bis(ethylethylamino)benzhydryl equivalent Phenyl ketone derivative, 2_chloridox oxime, 2-isopropylxanthone and the like; the same derivative; 2_ chlorophyll quinone, 2 _ methyl en brewing and other awakening derivatives; N - decyl ketone derivatives such as hydrazine, N-butyl, and ketone; others such as α,α-diethoxyacetic acid benzene Stuffed 321008 35 200949317 (benzil), ketone ketone, xanthone, uranyl compound, halide, etc. These photosensitizers may be used alone or in combination with one or more of the other. The energy ray-curable compound is preferably used in an amount of from 1 to 20 parts by weight, based on 1 part by weight of the photo-curable compound. The 'curable resin composition may also contain an anti-static property against the anti-static property of the polarizing plate. The antistatic agent is not particularly limited, and a well-known antistatic agent can be used. For example, acyloyl amide propyl dimethyl hydroxy ethyl ammonium nitrate can be used. Cationic surfactants such as guanidinopropyltrimethylammonium sulfate, cetyim〇rph〇i iummethosul fate; linear alkyl potassium phosphate, polyoxygen An anionic surfactant such as a potassium sulphate or an alkane sulfonate; N, N-bis(transethyl)-N-alkylamine, a fatty acid ester derivative thereof, a fatty acid partial vinegar Nonionic surfactant activity The compounding ratio of the antistatic agents may be appropriately determined depending on the desired properties, but is usually about 0.1 to 100 parts by weight with respect to 100 parts by weight of the active energy ray-curable compound. As the resin composition, a known polymer additive which is usually used in a polymer material may be added, for example, a primary antioxidant such as a sulfonate or a secondary antioxidant such as a sulfur; a hindered amine light stabilizer; A UV absorber such as a clopidogone, a benzotriazole or a benzoate, etc. The "curable resin composition" may also contain a leveling agent as needed. When the curable resin composition is applied to a polarizing film or a substrate, the case where the polarizing film 3632100849317 film or the substrate lacks wettability, or the hardened property of the curable resin composition is poor. 'After adding the leveling agent, you can change these phenomena. Various compounds such as polyfluorene, fluorine, polyether, acrylic copolymer, and titanate can be used as the leveling agent. These leveling agents may be used singly or in combination of two or more. The amount of the above-mentioned leveling agent is preferably from 0.1 to 1 part by weight, and preferably from 0.1 to 0.7 parts by weight, based on 100 parts by weight of the active energy ray-curable compound contained in the curable resin composition. More preferably, it is 0.2 to 0.5 part by weight. For example, when the amount of the leveling agent added is less than 0.01 part by weight based on 1 part by weight of the active energy ray-curable compound, there is a possibility that the improvement in wettability and surface properties is insufficient. At the same time, when the amount of the leveling agent added is more than 1 part by weight based on 1 part by weight of the active energy ray-curable compound, the adhesion between the polarizing film and the protective layer may be lowered. Further, the curable resin composition may contain a solvent as needed. The solvent is appropriately selected depending on the solubility of the components constituting the curable resin composition. The solvent to be used in the general state may, for example, be an aliphatic hydrazine such as hexazone or cyclohexan, or an aromatic smog such as toluene or dimethyl benzene; methanol, ethanol, propanol, iso-alcohol, n-butanol, etc. Alcohols; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and hexanone; methyl ketone, ethyl acetate, acetic acid, etc., sulphonic acid such as vinyl chloride or chloroform; . The blending ratio of the solvent is suitably determined from the viewpoints of the processability such as film formation property and the viscosity of the active energy ray-curable resin composition required. The method of forming the protective layer on one side or both sides of the polarizing film is as follows. First, the curable resin composition is applied to a substrate such as polyethylene terephthalate (PET film) by applying 321008 200949317. If necessary, after drying to remove the solvent, the coating film surface = the base of the coating material formed by the photo-degradable resin composition is required to have the protective layer laminated on both sides of the polarizing film, the double side of L Further, the two substrates are bonded to each other, and the protective layer is formed by peeling off the curable resin composition after being exposed to visible light, ultraviolet rays, X-rays, or lightning. Finally, the base plate will be used. Consider the preference of the protective layer on the early or double side of the thin film. If the thickness of the protective layer is as thin as possible, the thickness of the protective layer is too strong, and the polarizing film cannot be fully protected. The thickness of this protective layer is preferably about 1 to 3'. ,

..., " After applying the curable resin composition directly on the polarizing film, the protective layer is formed by hardening, but it is a curable resin composition! It must be dried to harden it. The film is: when the protective layer is formed on both sides of the polarizing film, the components contained in the curable resin composition may be cured by irradiation with active energy rays of the same or different vine layers, although And the light source used, but can use a light source having a wavelength-distributed, such as a low-pressure mixed-knife knives, a south-pressure mercury lamp, a chemical lamp, a black lamp, a microwave-excited mercury lamp, a metal lamp, and the like. Although the illuminating intensity of the curable resin composition may vary depending on the composition, it is effective for activation of a photo-radical polymerization initiator and/or photo-cationization 321 〇〇 8 38 200949317 polymerization initiator. The irradiation intensity in the wavelength domain is preferably from 1 2 to 2,500 mW/cm 2 . If the illuminating strength of the curable resin composition is less than 10 mW/cm2, the reaction time will be too long. If it exceeds 2, 5 〇〇/cm2, the radiant heat from the lamp and the curable resin composition will be polymerized. The heat is generated, which may cause yellowing of the curable resin composition or deterioration of the polarizing film. The illumination time of the curable resin composition is controlled independently according to the composition, and is not particularly limited, and is set so that the cumulative light represented by the product of the irradiation intensity and the irradiation time is 10 to 2,500 mj// It is better when cm2. If the cumulative brightness of the curable resin composition is less than 1 (m)/cm2, the production of the active species derived from the polymerization initiator will be insufficient, and the hardening of the resulting protective layer may be insufficient. At the same time, if the cumulative light exceeds 2, /cm2, the irradiation time will become very long, which is unfavorable for improving the yield. Further, the irradiation of the active energy ray is preferably carried out within a range that does not lower the various properties such as the degree of polarization of the polarizing film and the penetration rate. <Optical module and liquid crystal display device> 光学 The optical module of the present invention is composed of a laminate of the above-described partial plate and an optical functional layer, and specifically has a structure in which an optical functional layer is provided on a protective layer of the polarizing plate. The optical functional layer is not particularly limited, and a well-known optical functional layer can be used. Specific examples of the optical functional layer include a reflective layer, a semi-transmissive reflective layer, a light-diffusing layer, a phase difference plate, a concentrating plate, and a film for brightness enhancement. The reflective layer can be formed, for example, by forming a metal crucible or a vapor deposited film on the protective layer of the polarizing plate. The semi-transmissive reflective layer is formed by applying a reflective layer as a half mirror, and 321008 39 200949317 is provided on the protective layer to include a light-reflecting reflecting plate such as pearl pigment. The light-diffusing layer is formed on the protective layer by a method of performing a mat treatment, a method of applying a resin containing fine particles, a method of subsequently providing a film containing fine particles, and the like. The purpose of using the phase difference plate is to compensate for the phase difference from the liquid crystal cell, and it may be, for example, a birefringent film formed of a stretch film of various plastics or the like, or a discotic liquid crystal or a nematic type. (nematic) A film of a liquid crystal, or a liquid crystal layer formed on the film substrate. In this case, a cellulose substrate such as triacetyl cellulose is preferably used as the film substrate supporting the alignment liquid crystal layer. The purpose of using the concentrating sheet is to control an optical path or the like, which can be formed as a prism array sheet or a lens array sheet, or a dot-attached sheet. The purpose of use of the brightness enhancement film is to increase the brightness of a liquid crystal display device or the like, and examples thereof include a film formed by laminating a plurality of films having different anisotropy in refractive index, and a reflection type having an anisotropy in reflectance. A polarizing separation plate, a circularly polarizing separator obtained by supporting an oriented film of a cholesteric liquid crystal polymer or an oriented liquid crystal layer thereof on a film substrate. The above optical functional layers may be used singly or in combination of two or more. When the optical functional layer is bonded to the protective layer, if the protective layer has an adhesive force to the optical functional layer, the two may be directly bonded or may be bonded together using an adhesive or an adhesive. When the optical functional layers are bonded to each other, an adhesive or an adhesive may also be used. The method of directly bonding the protective layer to the optical functional layer is to apply a 40 321008 200949317 active energy ray-curable resin composition on one side of the optical functional layer, and after forming a coating film on the phase difference plate, A method in which a film is used as a bonding surface, and a phase difference plate is bonded to a polarizing film, and then the coating film is cured by irradiation with an active energy ray. According to such a production method, a polarizing film in which a polarizing film, a protective layer, and a phase difference plate are directly bonded without interposing another layer (e.g., an adhesive layer or an adhesive layer) can be obtained. At the same time, the optical functional layer can be directly used in the manufacture of the optical component related to the present invention, or can be subjected to electro-discharge treatment or plasma treatment on the bonding surface with the coating film forming the protective layer. The polarizing plate or optical module of the present invention can be applied to a liquid crystal display device. At this time, the polarizing plate or optical module of the present invention is disposed on one side or both sides of the liquid crystal cell. The polarizing plates or optical components disposed on both sides of the liquid crystal cell may be the same or different. (Embodiment) Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. In the examples, "parts" and "%" indicating the amount or content of use are based on weight unless otherwise specified. (Production Example 1: Production of polarizing film) A polyvinyl alcohol film having an average degree of polymerization of about 2,400, a degree of saponification of 99.9 mol% or more and a thickness of 75/zm was impregnated in pure water at 30 ° C, and then It was immersed in an aqueous solution of iodine/potassium iodide/water in a weight ratio of 0.02/2/100 at 30 °C. Then, it was further immersed in an aqueous solution of potassium iodide/boric acid/water in a weight ratio of 12/5/100 at 56.5 °C. Subsequently, after washing with pure water at 8 ° C, it was dried at 65 ° C to obtain a polarizing film (thickness 30 / zm) in which iodine had been adsorbed and oriented in polyvinyl alcohol 41 321008 200949317.倍倍。 The extension of the iodine dyeing and boric acid treatment step, the full extension ratio of 5.3 times. (Production Example 2: Preparation of Curable Resin Composition I) The following components were mixed to obtain a curable resin composition I. • 3, 4-epoxycyclohexyldecyl 3,4-epoxycyclohexanecarboxylate (1) & 丨^1 chemistry (stock), CELLOXIDE 2021P): 35 parts • bis (3-ethyl -3-epoxypropyl fluorenyl) 3⁄4 (manufactured by Toago Corporation, ar〇n OXETANE 0XT-221) : 15 parts

• Tricyclic tercene dimethanol dipropylene roasting acid g (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DCP): 50 parts • 2-carbyl-2-methyl-1-phenylpropanone-1- The ketone (Ciba Specialty Chemicals, manufactured by Ciba Specialty Chemicals, DAR0CUR 1Π3: Photoradical polymerization initiator): 2.5 parts

• Photocatalytic polymerization initiator of 4, 4'-bis[diphenylsulfanyl]diphenyl sulfide dihexafluorophosphate (made by ADEKA, ADEKA 0PT0MER SP-150): 2. 5 Part of polyoxymethane leveling agent (Toray Dow Corning), SH710): 0.2 part and the above acetal compound of A-D0GC hydroxytrimercaptoacetaldehyde and trishydroxypropyl propane Acrylate) is a compound having the structure of the following formula.

CH CH2=CHCOO-CH2-C , ch2—ococh=ch2 ch2ch3 (Production Example 3: Preparation of Curable Resin Composition II) The following components were mixed to obtain a curable resin composition II. 42 321008 200949317 • 3,4-epoxycyclohexyldecyl 3,4-epoxycyclohexanecarboxylate (Daicel - Chemical, CELLOXIDE 2021P) : 35 parts • bis (3-ethyl-3) -Epoxypropylmethyl)ether (manufactured by Toago Chemical Co., Ltd., AR0N OXETANE 0XT-221): 15 parts of diacetate of acetal compound of hydroxytrimethylacetaldehyde and trihydroxydecylpropane (Xinzhongcun) Chemical Industry Co., Ltd., A-D0G): 50 parts • 2-Hydroxy-2-mercapto-1-phenylpropan-1-one (made by Ciba Specialty Chemicals Co., Ltd., DAR0CUR 1173: Photoradical polymerization initiation Agent: 2. 5 parts ® · 4, 4'-bis [diphenylthioindenyl] diphenyl sulfide bishexafluorophosphate photocationic polymerization initiator (made by ADEKA, ADEKA 0PT0MER) SP-150): 2. 5 parts • Polyfluorene-based leveling agent (manufactured by Toray Dow Corning, SH710): 0.2 part (manufacturing example 4: preparation of curable resin composition ill) After the components are mixed, a curable resin composition ΙΠ is obtained. ❹ · 3, 4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Daicel Chemical Co., Ltd., CELLOXIDE 2021P): 35 parts • bis (3-ethyl-3-epoxy) Propyl fluorenyl) oxime (made by East Asia Synthetic Co., Ltd., OXETANE 0XT-221) : 15 parts • 1,3, 5- cis (2-hydroxyethyl) isocyanurate triacrylate (Xin Nakamura Chemical Industrial (stock) system, A-9300) : 50 parts • 2-Hydroxy-2-methyl-1-phenylpropane 丨-ketone (made by Ciba Specialty Chemicals Co., Ltd., DAR0CUR 1173: Photoradical polymerization initiator) ): 2. 5 parts • 4' 4' - bis [diphenyl thiosyl] diphenyl sulphate bis hexafluorophosphate 321008. 43 200949317 photocationic polymerization initiator (shared by ADEKA, ADEKA 0PT0MER SP-150) : 2·5 parts • Ju Shi Xi Oxygen leveling agent (manufactured by Toray Dow Corning, SH710): 0.2 parts (manufacturing example 5: preparation of curable resin composition IV) The following components were mixed to obtain a curable resin composition IV. • 3,4-epoxycyclohexyldecyl 3,4-epoxycyclohexanecarboxylate (0&461 Chemical Co., Ltd., CELLOXIDE 2021P): 35 parts • bis (3-ethyl-3-ring) Oxypropyl decyl) ether (AS0N OXETANE OXT-221): 15 parts • pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A_TMMT): 50 parts 2-nonyl-2 - Methyl-1-phenylpropan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., DAR0CUR 1173: photoradical polymerization initiator): 2.5 parts

• Photocatalytic polymerization initiator of 4,4-bis[diphenylthiomethyl]diphenylsulfonium hexa-I phosphate ((ADE) 150): 2. 5 parts • Polyoxan A leveling agent (manufactured by Toray Dow Corning, SH710): 份. 2 parts (Production Example 6: Preparation of curable resin composition v) 73 parts of curable resin composition I and 3 parts (converted to solid form) The cerium oxide colloid (manufactured by Nissan Chemical Co., Ltd., MEK-ST 'yttrium oxide particle size 1 〇 to 15 nm) was mixed to obtain a curable resin composition v. (Production Example 7: Preparation of Curable Resin Composition VI) 44 321008 200949317 73 parts of curable resin composition II and 30 parts (converted into solid parts) Oxidation Dream Colloid (manufactured by Nissan Chemical Co., Ltd.) MEK-ST, After the oxidation dream particle size is 10 to 15 nm), the curable resin composition VI is obtained. (Production Example 8: Preparation of Curable Resin Composition VII) The following components were mixed to obtain a curable resin composition π. • 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexyl oleate (Daicel Chemical Co., Ltd., CELLOXIDE 2021P): 15 parts • 3-ethyl-3-hydroxymethyl epoxy Propane (ARON ® OXETANE OXT-101): 15 parts • Ethylene oxide modified diacrylate of bisphenol A (Aronix M-210), 49 parts • Trimethoprimic triacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., TMPTA): 21 parts • 2-Phenyl-2-mercapto-1-phenylpropan-1-one (Ciba refined) Company, DAR0CUR 1173 : Photoradical polymerization initiator): Photochemical polymerization of 3 parts of ❿ · 4, 4'-bis[diphenylthio-rutyl] diphenyl sulfide dihexafluorophosphate Starting agent (made by ADEKA, ADEKA 0PT0MER SP-150): 2 parts • Ju Shi Xi Oxygen leveling agent (manufactured by Toray Dow Corning, SH710): 0·2 parts (Manufacturing Example 9: Sturability) Preparation of Resin Composition VIII) After the following components were mixed, 'the curable resin composition V111 was obtained. • Nuclear hydrogenated dip-A di-glycidyl ether C Japanese epoxy resin (japan Epoxy Resin) (EPICOAT YX8000): 1 321 321008 45 200949317 • 4, 4 - bis [diphenyl sulphur Photopolymerization starter (diethyl benzoate, ADEKA 0PT0MER SP~ 150): 40 parts • polyfluorene leveling agent (to) Manufactured by Dow Corning, SH710): 0.2 parts (Production Example 10: Preparation of Curable Resin Composition IX) The following components were mixed to obtain a curable resin composition IX. • Dihydrodeglyceryl ether of nuclear hydrogenated bisphenol A (made by Japan Epoxy Resin Co., Ltd.)

EPICOAT YX8000) : 70 parts Q • 1,4-bis[{(3-ethyl-3-epoxypropyl)methoxy}methyl]benzene (AYO OXETANE 0XT-121) : 30 parts • 4, 4'-bis[diphenylthiomethyl]diphenyl sulfide bishexafluorophosphate photocationic polymerization initiator (made by ADEKA, ADEKA OPTOMER SP-150): 40 parts of polyoxymethane leveling agent (manufactured by Toray Dow Corning, SH710): 0.2 parts by weight (Production Example 11: Preparation of curable resin composition X) After mixing the following components, Curable resin composition X. • 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (1^1〇61 chemistry, CELLOXIDE 2021P): 35 parts • bis (3-ethyl-3) -Epoxypropylmethyl)ether (ARON OXETANE 0XT-221): 15 parts • 2-hydroxy-3-phenoxypropyl acrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 702A) : 50 parts 46 321008 200949317 • 2-Hydroxy-2-mercapto-1-phenylpropan-1-one (manufactured by Ciba Specialty Chemicals, DAR0CUR 1173: photoradical polymerization initiator): 2. 5 • 4, 4,-bis[diphenylsulfanyl]diphenyl sulfide bishexafluorophosphate photocationic polymerization initiator (made by ADEKA ADEKA 0PT0MER SP-150): 2. 5 parts of polyoxymethane leveling agent (manufactured by Toray Dow Corning, SH710) ··0. 2 parts <Example 1 &gt; ® Curable resin composition obtained in Production Example 2 using a bar coater I' was coated on a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., ESTER FILM E7002). Then, using a labeling device (made by FUJIPLA Co., Ltd., LPA3301), two PET films each having a coating film formed of a curable resin composition were attached to each other with the coating film side as a bonding surface. Both surfaces of the polarizing film obtained in Example 1 were produced. Then, by using D Valve manufactured by Fusion. UV Systems, the laminated body was irradiated with ultraviolet light at a cumulative light amount of 1,500 mJ/cm 2 to cure the coating film on both sides. Finally, after peeling the PET film on both sides, a polarizing plate having a protective layer on both surfaces of the polarizing film was obtained. &lt;Examples 2 to 6, Comparative Examples 1 to 4&gt; The same operations as in Example j were carried out except that the curable resin composition shown in Table 1 to be described later was used instead of the curable resin composition I. And made into a polarizing plate. &lt;Example 7&gt; The curable resin composition V obtained in Production Example 6 was applied to a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., 321008 47 200949317 FILM E7002) using a bar coater )on. Next, it was dried at 80 ° C for 3 minutes to remove the solvent. Next, a PET film in which two coating films formed of a curable resin composition were formed by using a bonding apparatus (manufactured by FUJIPLA Co., Ltd., LPA3301) was attached to the coating film side as a bonding surface. Both sides of the polarizing film obtained in Example 1 were produced. Then, the laminated body was irradiated with ultraviolet light at a cumulative light amount of 1,500 mJ/cm 2 by D Valve manufactured by Fusion UV Systems, and the coating films on both sides were cured. Finally, after peeling off the PET film on both sides, a polarizing plate having a protective layer on both surfaces of the polarizing film was obtained. &lt;Example 8&gt; The curable resin composition VI obtained in Production Example 7 was applied onto a polyethylene terephthalate (pet) film (ESTER FILM E7002, manufactured by Toyobo Co., Ltd.) using a bar coater. . Next, it was dried at 80 ° C for 3 minutes to remove the solvent. Next, a pET film in which two coating films formed of a curable resin composition are formed by using a bonding apparatus (manufactured by FUJIPLA Co., Ltd., LPA3301) is attached to the coating film side as a bonding surface. Both sides of the polarizing film obtained in Example i were produced. Then, the laminated body was irradiated with ultraviolet light at a cumulative light amount of 1,5 〇〇mJ/cm 2 by D Valve manufactured by Fusion UV Systems, and the coating films on both sides were cured. Finally, after peeling off the PET film on both sides, a polarizing plate having a protective layer on both surfaces of the polarizing film was obtained. &lt;Comparative Example 5&gt; A polarizing plate (TRW842A 'Sumitomo) having a protective film of 8 Å/m thick formed of triacetyl cellulose was bonded to both surfaces of a polarizing film having a polyvinyl alcohol film having adsorbed iodine. Chemical (stock) system) was used as Comparative Example 5. Table 1 shows the compositions of the compositions used in Examples 1 to 8 and Comparative Examples 1 to 5, respectively, 321008 48 200949317, the modulus of elasticity when these compositions were hardened, and only the (methyl group) blended therein. The elastic modulus of the cured product formed by the acrylic compound and the radical polymerization initiator (abbreviated as "acrylic acid" in the "elasticity"), and the hardened matter of each composition at 8 (the storage elasticity of TC) The elastic modulus and the storage elastic modulus can be obtained as follows. [Method for measuring elastic modulus]

A curable resin composition for forming a protective layer was coated on a polyethylene terephthalate (PET) film (ESTER FILM E7002, Toyobo Co., Ltd., using a coater (First Chemical Co., Ltd., Bar Coater). On one side of the (share) system, the curable resin composition was cured by irradiating ultraviolet rays with a cumulative light amount of 1,500 mJ/cm 2 by D Valve ' manufactured by Fusion UV Systems. Next, the cured product was cut into a length of 1 cm 寛 x 8 cm along with the PET film, and the sample was obtained after peeling off the PET film. Next, the upper and lower jaws of the AUTOGRAPH AG-1S tester manufactured by Shimadzu Corporation were clamped at a temperature of 23 ° C and 55% RH, and the long side portion of the sample was sandwiched at a clamping gap of 5 cm. . At temperature 23. (:, 〇 〇 〇 〇 〇 〇 TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA TRA The elastic modulus is calculated from the initial straight line of the obtained stress-strain curve, and the cured product composed of only the (meth)acrylic compound and the radical polymerization initiator is used for each of the curable resin compositions. After the same production, the measurement was carried out. [Method for Measuring the Elasticity at 80 ° C] The respective curable resin compositions were applied to a PET film in the same manner as described above, and then cured by irradiation with ultraviolet rays. Cut into 5mmx3Omm, 49 321008 200949317 After peeling off the PET film, 'the individual use of each curable resin composition is measured by the Π measurement control (strand) leg _22〇, with the long side being stretched by the way For the separate film, set the clamp interval to 2 coffee, frequency, and 幵/胤 speed to 3 C / min, and obtain the storage elastic modulus of got. In Table 1, 'is an epoxy-based cationic polymerizable compound, epoxy hospital. Cationic polymerization The product, the radical polymerizable compound, the cationic polymerization initiator, and the radical polymerization initiator are indicated by the symbol on the left side of the colon in each item in accordance with the trade name and the abbreviation shown above. And the same as the abbreviation, the following are all the nicknames in Table 1. [Epoxy-based cationically polymerizable compound] • CEL 2021P: Daicel Chemical Co., Ltd. CELLOXIDE 2021P, chemical name 3, 4-epoxy Cyclohexyl decyl 3, 4-epoxycyclohexane carboxylate. • YX8000: EPICOAT YX8000, manufactured by Nippon Epoxy Resin Co., Ltd., chemically called ML bis double A dehydroglycolide®.

[Glycidyl-based cationically polymerizable compound] ^ • OXT-221: ARON OXETANE 0XT-221, manufactured by East Asia Synthetic Co., Ltd., chemical name: bis(3-ethyl~3-epoxypropyl fluorenyl) ether . • OXT-101: ARON ΟΧΕΤΑΝΕ 101-101, manufactured by East Asia Synthetic Co., Ltd., chemically named 3-ethyl-3-mercaptomethyl epoxicone. • 0XT-121: ARON ΟΧΕΤΑΝΕ 0ΧΤ-121 ′ of the East Asian Synthetic Co., Ltd. Chemical name: 1,4-bis[{(3-ethyl-3-epoxypropyl)methoxy}methyl] is stupid. [Radical Polymerizable Compound] • A-DCP: A-DCP manufactured by Shin-Nakamura Chemical Industry Co., Ltd., chemical name: Tricyclic 321008 50 200949317 decane dimethanol diacrylate. • A-D0G: A-DOG manufactured by Shin-Nakamura Chemical Industry Co., Ltd., a diacrylate of an acetal compound of the chemical name of hydroxytrimethyl acetaldehyde and trimethylolpropane [in the above formula (2), Q ! = propylene oxime oxime group, Q2 = 2-propenyloxy-1, 1-dimethylethyl, R = ethyl compound]. _ A-9300: A-9300, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., chemically named 1,3, 5-gin(2-hydroxyethyl)isocyanurate triacrylate. • A-TMMT: A-TMMT manufactured by Shin-Nakamura Chemical Industry Co., Ltd., chemically named pentaerythritol tetraacrylate. • M-210: Aronix M-210 from East Asia Synthetic Co., Ltd., chemically known as bisphenol A, ethylene oxide modified diacrylate. • ΊΈΡΤΑ: The chemical name is trimethylolpropane triacrylate. • 702A: 702A, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., chemical name 2-hydroxy-3-phenoxypropyl acrylate ❹ 51 321008 200949317 [Table 1] Hard (iv) tt 萍 性 2,000 at 80eC 2,000 ί 1,900 1- 2,400 2,600 2,800 2,500 ο § m 1 Mixed (183⁄4) I 1 Acrylic i 3,200 3,100 3,800 i 4,300 3,200 3,100 2,700 1 I i 1 Hard peak 3,700 1 3, Liu i- 3,700 4,000 i 5,500 5,600 2,800 uoo 1,500 o 1 ! i miscellaneous (solid part 30X) i 1 1 1 30 parts (73 parts relative to tree shrew) 30 parts (73 parts relative to W deer) i 1 1 1 1 starting street i free silk m ΙΑ c^i In CM' ΙΛ cm' tn c^i in ea =· i 1 ir&gt; 1 cations m CO· ΙΟ IA cj LA eg* LO csi m O CM* 40.0 40.0 to csi 1 Free radical polymerization (parts)乙Α) 702Α [ 1 1 1 1 1 1 1 1 g 1 mPTA ί 1 1 i 1 i c3 1 1 1 1 〇* ^ I 1 1 1 1 1 Wear tl [ A- rush 1 1 1 g 1 ! 1 1 i I 1 A- 9300 1 is 1 1 ! 1 ί 1 1 1 1 m ! 1 1 s 1 1 1 1 I gi 1 1 g 1 1 1 1 1 1 I 1 Ai. R Oxygen R | 1 ί 1 1 1 I 1 1 茺i 1 1 1 ii 1 1 1 LO 1 1 1 ! i舀LO tn LA s in 1C) 1 1 1 1ft i Ϊ 5 YX 8000 t 1 II 1 i 1 gol 1 § 2021P Aluminium 苈LA i 1 1 Coating layer of single fabric (&quot;η) osoooo O oooes Hard New Zealand reduction one t-( = three &gt 1 - 2 X (TAC) Remuneration 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 1 Example 2 Comparison Example 3 Example 4 -1 Example 5 52 321008 • 200949317 <Evaluation Test> • For the polarizing plates produced in Examples 1 to 8 and Comparative Examples 1 to 5, the following evaluation tests were carried out. The results are shown in Table 2. [1] Adhesion test (cross hatch test) The pressure-sensitive adhesive is applied to the surface of the protective layer on the side opposite to the glass surface by bonding the protective layer side of the polarizing plate to the glass. A cutter knife was engraved into 100 1 mm square checkerboards, and a cellophane tape was attached thereto, and a peeling test was performed to remove the checkers left in the 1 〇 0 checkerboard. The number of cells is evaluated for adhesion. The number of checkerboards left is evaluated as a at 95 to 100/100, B is evaluated at 50 to 95/100, and c is evaluated at 49/100. [2] Temperature resistance test The following temperature resistance test (warm water dipping test) was carried out to evaluate the water resistance of each polarizer. First, the polarizing plate was cut into a strip-shaped sample of 5 cm x 2 cm with the absorption axis (stretching direction) of the polarizing plate as the long side, and the dimension in the longitudinal direction was measured. The sample at this time exhibited a characteristic color uniformly and uniformly due to the moths adsorbed in the polyvinyl alcohol film. Fig. 1 is a schematic view showing a water resistance evaluation test method, wherein Fig. i (person) shows sample 1 before dipping warm water, and Fig. 1 (B) shows sample i after dipping warm water. As shown in Fig. 1(A), after the short side of the sample was held by the nip portion, about 80% of the long side direction was immersed in a water bath of 60 ° C for 4 hours. After that, the sample 1 was taken out from the water tank, and the water was wiped off. The polarizing film 4 constituting the polarizing plate is shrunk by the impregnation of warm water. That is, as shown in Fig. 1(B), the light film 4 which is positioned in the center of the polarizing plate is shrunk by the immersion of warm water, and the region 2 where the non-polarizing film 4 exists is formed between the protective films. Then, the distance from the end side la of the sample 1 in the center of the short side (the end side of the protective film) to the end side of the contracted polarizing film 4 is taken as the contraction length. At the same time, iodine is eluted from the peripheral portion of the polarizing film 4 which is in contact with warm water due to the impregnation of warm water, and the fading portion 3 is formed on the peripheral portion of the sample 1. The length of this fading portion is taken as the detached length of iodine. The total length of these shrinkage lengths and the length of iodine peeling off is taken as the total erosion length X. In other words, the total erosion length X is the distance from the end side la of the sample 1 (the edge of the protective film) to the region where the polarizing plate has a characteristic color in the center of the short side of the sample 1. It can be judged that the smaller the total corrosion length X, that is, the higher the adhesion (water resistance) in the presence of water. It is evaluated as A when the erosion distance is less than 1 000 # m, B when it is 1 000 # m to 3 000 // m, and C when it is above 3,000 /z m. [3] Dimensional stability test After each polarizing plate was placed in a dry environment at 85 ° C for 120 hours, the dimensional change was measured. First, the polarizing plate was cut into a size of 8 cm x 8 cm, and bonded to the glass through a pressure-sensitive adhesive as a measurement sample. The sample was subjected to autoclave treatment at a temperature of 50 ° C and a pressure of 5 kg / cm 2 (490.3 kPa) for 1 hour, and then left to stand in an environment of a temperature of 23 ° C and a relative humidity of 55% for 24 hours. The size of this state was taken as the initial size, and after standing still in a dry environment of 85 ° C for 120 hours, the machine direction (MD) and the transverse direction were measured using a binary size measuring device (manufactured by Nikon, NEXIV VMR-12072). After the size of (TD), the dimensional change rate is calculated by the following formula.

Dimensional change rate (%) = {(size after test - initial size) / initial size 丨 xlOO 54 321008 9 200949317 Table 2 shows the dimensional change rate in the MD direction (since the symbols are negative, - it is shrinkage Meaning). When the absolute value of the dimensional change rate is less than 0.7%, it is evaluated as A, 0.7% or more, and when it is less than 1.0%, it is B, 1.0% or more, and when it is less than 1.3%, it is C, and when it is 1.3% or more, it is D. . [4] Optical durability test Each of the polarizing plates was statically placed at 85 ° C or at 60 ° C and a relative humidity of 90 % to determine the optical properties as a function of time. That is, first, the polarizing plate was cut into a size of 3 cm x 3 cm, and bonded to a glass through a pressure-sensitive adhesive, as a measurement sample. The sample was subjected to high-pressure treatment for 1 hour at a temperature of 50 ° C and a pressure of 5 kg/cm 2 (490. 3 kPa), and then placed in an environment of a temperature of 23 ° C and a relative humidity of 55% for 24 hours. After attaching the accessory "film holder with a polarizing film" to an ultraviolet-visible spectrophotometer (UV2450, manufactured by Shimadzu Corporation), the sample was measured for the wear of the polarizing plate in the wavelength range of 380 to 700 nm. The transmission spectrum of the direction of the through-axis and the direction of the absorption axis, and the polarization degree Py (unit: %) and the transmittance of the monomer permeation Ty (unit: %) are obtained, and the monomer of the monomer hue is obtained in accordance with JIS Z 8729. No unit). The optical performance of this state was taken as the initial optical performance, and the optical performance after drying at 85 ° C or 60 ° C and a relative humidity of 90% was measured, and the change in polarization degree Δ Ρ γ was calculated from the following formula. The monomer permeability changes ΔΤγ and the hue change Ab*. △ Py = Py-initial Py after test y Ty = Ty-phase period Ty △ after test 1) 51: = 135|! - initial 1) after test * Moreover, for APy, the change in the degree of polarization expressed in % Not up to 55 321008 200949317 At 1 o'clock, it is evaluated as A, i is above the point, but when it is less than 5 o'clock, it is b, and when it is 5 or more, it is C. For ATy, the change in the penetration rate expressed in % is less than 3 points. The ping is estimated to be A ′ at 3 or more points and B at 5 points, and C at 5 points or more. For △!;)*, it is evaluated as a, 3 or more when the amount of change is less than 3, and B when it is less than 5, and 〇5 in the case of 5 or more, indicating ΔΡγ and Ab after standing still under dryness. *Evaluation results, evaluation results of Δ Py and Δ Ty after standing at 6 〇 and a relative humidity of 9 环. [4] Film thickness measurement The film thickness of the entire polarizing plate (the laminated body of the upper and lower protective film and the polarizing film) was measured by a film thickness measuring instrument (ZC-101' (manufactured by Nikon). [Table 2]

As is apparent from Table 2, in the examples, a polarizing plate having a film which is excellent in water resistance, dimensional stability, and optical durability at the same time as the film 4 of the polarizing film and having excellent optical durability, 321008 56 200949317 was obtained. The embodiments and examples disclosed in the present disclosure are merely illustrative and not limiting. The scope of the present invention is to be construed as being limited by the scope of the claims and the scope of the claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1(A) shows a sample 1 before warm water immersion, and FIG. 1(B) shows a warm water® immersion. FIG. After the sample material [Description of the main components] 1 sample la end 2 area between the protective film without polarizing film 3 polarized plate peripheral portion faded portion 4 contracted polarizing film ^ 5 clamping portion 57 321008

Claims (1)

200949317 VII. Application for Patent Park: 1 · A polarizing plate with a value of s ^ white, /, and prepared. It has been adsorbed in a polyethylene resin film. a partial region of the pigment; and a layer formed on at least one side of the polarizing film. The layer is formed of a cured product of a hardened eucalyptus composition containing an active energy ray-curable compound, wherein the active energy ray The curable compound contains: a compound having up to 9 epoxy groups in the molecule; and a (meth)acrylic compound having at least one (meth) acryloxy group in the molecule, and the modulus of elasticity of the layer It is 3, 3 〇〇 to 1 〇, 〇〇〇 MPa. 2. The polarizing plate of the invention of claim 1, wherein the (meth)acrylic acid compound is contained in an amount of from 丨〇 to 7 parts by weight based on 1 part by weight of the active energy ray-curable compound. 3. The polarizing plate of claim 2, wherein the (meth)acrylic compound is provided as a hardened product formed only from the (fluorenyl)acrylic compound and a polymerization initiator; The elastic modulus of 〇 MPa or more. 4. The polarizing plate of claim i, wherein the (mercapto)acrylic compound is at least one compound represented by the following formulas (1) to (4): 58 321008 200949317 (1) (2) CH2*CHCO-CH2-C-CH2-〇CCH=CH2 iH2-〇CCH*CH2 (In the above formulas (1) and (2), 'Qi and Q2 independently of each other mean (meth) propylene oxime or (meth) propylene decyloxyalkyl group, at this time alkyl Carbon number is 1 to 10; '&quot;, In the above formula (2), R represents argon or a hydrocarbon group having 1 to 10 carbon atoms; in the above formula (3), τ, T2 and T3 are independent of each other (methyl propylene oxy group; earth) In Shen; 1: 2: 4), τ represents hydroxy or (meth) propylene oxime: The polarizing plate of claim 6 is characterized in that t' is relative to the aforementioned: 321008 59 200949317, and the curable composition contains 5 to 250 parts by weight of fine particles. The polarizing plate of the sixth aspect of the invention is the cerium oxide particle having a particle diameter of 100 nm or less. 9. The polarizing plate of claim 8, wherein the dioxic microparticles have a group selected from the group consisting of a hydroxyl group, an epoxy group, a (meth) propoxy group, and a vinyl group. The above functional groups. 10. For the polarizing plate of the patent application, the (4) soil layer is 1 to 35 #01. Further, an optical component is formed by a laminate of a polarizing plate and an optical functional layer according to any one of the above claims. 12. The optical component of claim U, wherein the optical functional layer is any one of a phase difference layer, a brightness enhancement film, and a surface treatment layer, and the liquid crystal display device is the subject of the patent application. The polarizing plate of any one of the above items, or the optical component of the U or U of the patent application, is formed on one or both sides of the liquid crystal cell. 321008 60