TW201245382A - Photocurable adhesive, polarizing plate and laminated optical member - Google Patents

Abstract

Provided is a photocurable adhesive for laminating a protective film made of a transparent resin on a polarizer made of a polyvinyl alcohol resin film, including 100 parts by weight of a cationic photocurable component (A), and 1 to 10 parts by weight of a cationic photocurable component (B), wherein the cationic photocurable component (A) containing the following (A1) to (A3) based on a total amount thereof: 60 to 75% by weight of a cycloaliphatic diepoxy compound (A1) represented by formula (I), 5 to 35% by weight of a diglycidyl compound (A2) represented by formula (II), and 2 to 15% by weight of a monofunctional epoxy compound (A3) represented by formula (II).

Description

[Technical Field] The present invention relates to a light for bonding a polarizer composed of a polyvinyl alcohol-based resin film having a dichroic dye orientated and a protective film made of a transparent resin. A sclerosing adhesive, a polarizing plate comprising a protective film bonded to a polarizing plate using the photocurable adhesive, and a laminated optical member formed of another optical layer such as the polarizing film laminated retardation film. [Prior Art] The polarizing plate is used as one of the optical elements constituting the liquid crystal display device. The polarizing plate usually has a structure in which a protective film is formed on two areas of the polarizing plate, and the sweat is incorporated into the liquid crystal display I. Although it is known that the film is formed only on one side of the polarizer, in most cases, n is not a simple protective film rain and has a film of another optical layer. Further, the method for producing a polarizer is widely carried out by a uniaxially-stretched polyvinyl alcohol of the dichroic dye (four) color, which is treated by a liquid treatment, and then washed. Usually, the polarizer is adhered to the film immediately after being washed and dried as described above. The polarizer of this system is (4), the physical strength of the polarizer is weak, and the coiled polarizer has a problem that the rt has a tendency to crack. Therefore, the water-based adhesive agent of the aqueous solution of the polyvinyl alcohol-based resin is usually dried after drying.

" two (five) bonding protective film of the y Μ ώ iX π partial film simultaneously by the adhesive; Protect and hang the triethyl cellulose membrane with a thickness of 3〇 to just (4). Dance Ge 2: = excellent transparency, easy to form a variety of surface: or learn the functional layer 'at the same time moisture permeability, high degree, the use of the agent and attached to the partial ^Ujc 的 的 的 的 , , , , It has the other side of the film 324108 8 4 201245382 film which is different from the high moisture permeability. It is used as a protective film to bond the partial plate under wet heat, for example, the temperature is 7G ° C, and the relative humidity is 90%. Under the conditions, there are problems such as deterioration and deterioration. Here, the known ratio is such that the cellulose penetration rate of the cellulose fiber is low, and for example, a rare resin is used as the inert polyolefin system. Μ 曰曰 • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • ... an aqueous solution of a glycol-based resin as an adhesive, ! The resin film having insufficient strength of the contactor or the outer surface of the polarizing plate obtained is generally low in hydrophobicity and low in moisture permeability, and the water as a solvent cannot be sufficiently dried. On the other hand, it is known to apply different types of protective films to both sides of the polarizer. For example, a protective film made of a tree-like enamel having a low moisture permeability, such as an amorphous poly-saturated resin, is bonded to the other side, and the other side of the polarizer is bonded to a cellulose-based resin such as triethyl cellulose. The resin constitutes a protective 臈. Here, at the same time, a high adhesion force is applied to the permeable (4) phase and the =1, and the adhesive is also applied between the resin which is permeable to moisture such as a cellulose resin and the polyvinyl alcohol-based polarizer. A photocurable adhesive is used. For example, in JP-A-2004-245925 (Patent Document No.), the dioxane compound is used as an adhesive for the main component, and the ultraviolet ray is irradiated by the active energy ray = frequency. The cationic polymerization is carried out to homogenize, and the polarizer and the protective film are proposed. Further, Japanese Patent Publication No. 257199 (Patent Document 2) discloses an epoxy compound having an alicyclic epoxy group of alicyclic epoxy m 324108 201245382. Further, a photocurable adhesive having a photocationic polymerization initiator is used, and a technique for using a polarizer and a protective film is provided. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2004-245925 [Patent Document 2] JP-A-2008-257199 SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) However, the adhesive of the composition specifically disclosed in Patent Document 1 or Patent Document 2 is sufficiently low, It is not necessarily easy to form a film and a uniform adhesive layer by applying it to polarizing # or a film adhered thereto. Moreover, the adhesive layer after curing is not fixed to exhibit a sufficient storage modulus. The result is that when the polarizing plate obtained is subjected to intense temperature, for example, the thermal shock test of the low temperature holding and the high temperature maintaining is repeated, the polarizer may be broken. #再再,,,,,,,,,,,,,,, The bonding force is followed by the polarizing and the protective film, but the bonding force is not sufficient. For example, the polarizing plate and the protective film are bonded by using the photocurable adhesive to obtain the optical plate 1 in order to be applied to the liquid crystal display device. In the state in which the end portion is cut into a predetermined size and the end portion is polished, the end portion (4) is peeled off. The object of the present invention is to provide a photocurable adhesive which is imparted to the polarizer when the protective film is attached thereto. When it has a sufficiently low viscosity of 324108 6 201245382 which can be applied at room temperature, and exhibits sufficient storage modulus after hardening, the polarizer is not easily broken even when subjected to a severe temperature experience, and A polarizing plate in which the adhesion between the light sheet and the film is also improved. Another object of the present invention is to provide a photocurable adhesive for bonding a polarizer and a protective film, which are excellent in adhesion and are subjected to intense When the temperature is experienced, the polarizer is still less likely to cause cracking of the polarizing plate. Another object of the present invention is to provide an optical layer which is suitable for liquid crystal display by using other optical layers such as a retardation film laminated on the polarizing plate. In order to solve the problem, the present inventors have intensively studied the present invention, and as a result, have achieved the present invention. Specifically, it has been found that a photocationic curable component is formulated with a predetermined amount of a photocationic polymerization initiator. In the photocurable adhesive, it is effective to use the following composition as a photocationic curable component, wherein the composition is mainly composed of a specific alicyclic diepoxide compound and has an intramolecular compound therein. 2 epoxy-propyl compounds which are not bonded to the alicyclic ring and which are not aromatic, and which have a minor amount of one molecule Monofunctional epoxy compounds are epoxy groups bonded cyclic ring. That is, it has been found that the photocurable adhesive of the specific composition exhibits low viscosity at room temperature to impart good coating suitability, and at the same time exhibits a high storage modulus after hardening, and strongly follows the polarizer and the protective film. The invention includes the following. [1] A photocurable adhesive agent for bonding a protective film made of a transparent resin to at least one surface of a polarizing plate comprising a polyvinyl alcohol-based resin film having a dichroic dye orientated thereon, comprising light 100 parts by weight of the cation hardening component (Α) and 324108 7 201245382 Photocationic polymerization initiator (B), wherein the photocationic curable component (A) is contained based on the total amount thereof. The following amounts (A1), (A2), and (A3) are as follows. The alicyclic diepoxide (Ai) represented by the following formula (I) is 6 to 75 parts by weight

(I) wherein R and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may have an alicyclic structure when the carbon number is 3 or more; χ represents a gas atom and has a carbon number of 1 to 6 An alkanediyl group or a divalent group of any of the following formulas ([a) to (Id):

A look - prepared. ί 〇 C C C 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 一 CH CH CH CH 』 』 』 』 』 』 』 ch ch ch ch ch ch ch ch ch ch ch ch ch ch ch ch ch The alkanediyl group of 20 may have an alicyclic structure when the carbon number is 3 or more; and a and b each represent an integer of q to Μ. The diepoxypropyl compound (Α2) represented by the following formula (11) is 5 to 35 wt%; —ch2, V γ (Π) where Z is a non-carbon number 1 to 9 alkyl group, carbon number 3 Or a subunit of 324108 201245382 alkyl, a divalent alicyclic hydrocarbon group, or a divalent group represented by the formula _CmH2m_zl_CnH2n_ where -Z1- represents -〇---C0-0---0-C0-- -s〇2___s〇... or -CO-, m and η each independently represent an integer of i or more, and two counts are 9 or less. '口 % The monofunctional epoxy compound (Α3) 2 to ΐ5 by the formula (in) R3—Ο—CH: (nr)

In the formula, 'R3' represents an alkyl group having 1 to 15 carbon atoms. [2] The photocurable adhesive according to [1], wherein R3 is an alkyl group having 6 to 1 carbon atoms in the formula (III) of the monofunctional epoxy compound (A3). [3] The photocurable adhesive according to [1] or [2], wherein the viscosity at 25 t is 100 mPa·sec or less. [4] The photocurable adhesive according to any one of [1] to [3] wherein the cured product exhibits a storage modulus of 1,000 MPa or more at 80 °C. [5] The polarizing plate is composed of a polarizer composed of a polyvinyl alcohol-based resin film having a dichroic dye adsorbed thereon, and is bonded to at least one surface of the polarizer via an adhesive. A cured film of a photocurable adhesive according to any one of [1] to [4], wherein the adhesive is a cured film of a photocurable adhesive. [6] The polarizing plate according to [5], wherein the protective film adhered to at least one surface of the polarizer comprises an acetaminophen-based resin formulated with an ultraviolet absorber. [A] The polarizing plate according to the above aspect, wherein the protective film bonded to at least one surface of the polarizer comprises an amorphous polyolefin resin, a polyester resin, and a chain polyglycol. A transparent resin in the group of resins. [8] The polarizing plate according to any one of [5] to [7] wherein the adhesive strength measured by a 180-degree peeling test between the polarizer and the protective film is N. 6N/25min or more. [9] A laminated optical member comprising the laminate of the polarizing plate and the other optical layer described in any one of [5] to [8]. [10] The laminated optical member according to [9], wherein the optical layer comprises a retardation film. (Effect of the Invention) The photocurable adhesive agent of the present invention is prepared as a photocationic curable component (A) by a predetermined amount of an alicyclic diepoxide (A1) or a diepoxypropyl compound (A2). And the monofunctional epoxy compound (A3), which can increase the storage modulus of the adhesive layer with low viscosity and hardening, and at the same time, improve the bonding strength between the polarizer and the protective film. Therefore, a polarizing plate in which a protective film made of a transparent resin is bonded to at least one surface of the polarizer via the adhesive is subjected to a severe temperature such as a thermal shock test, and the polarizer is less likely to be cracked and the thermal shock resistance is obtained. Excellent. The laminated optical member ′ having the other optical layers laminated on the polarizing plate also sufficiently exhibits the function of the polarizing plate and is excellent in thermal shock resistance. [Embodiment] Hereinafter, embodiments of the present invention will be described. The present invention provides a polarizing plate for a polarizing film consisting of a polyethylene photo-curable adhesive and a light-curing adhesive photocurable adhesive, which is composed of a transparent tree 324108 5 10 201245382 grease. member. Below you. Further, the present invention provides a method in which a protective film made of a transparent resin is bonded to the above, and a laminate of the other optical layers and a laminated optical member are laminated on the polarizing plate. [Photocurable adhesive] Next, a light hard adhesive, a polarizing plate, and a light for a protective film made of a polyvinyl alcohol resin film and a protective film made of a transparent resin are sequentially described in the present month. The curable adhesive contains the following two components (A) and (B): (A) a photocationic curable component, and (B) a photocationic polymerization initiator. (Photocation-curable component) The photocationic curable component (A) which imparts an adhesive force by polymerization hardening as a main component of the photocurable adhesive contains the following three compounds: (A1) An alicyclic diepoxide compound represented by the above formula (A2), a diepoxypropyl compound represented by the above formula (Π), and (A3) a monofunctional epoxy compound represented by the above formula (III). The amount of the alicyclic diepoxy compound (A1) in the photocationic curable component (A) is from 6 Å to 75% by weight based on the total amount of the photocationic curable component (A). By containing (9) by weight or more of the alicyclic diepoxy compound (A1) in the photocationic curable component, the storage modulus after curing of the photocurable adhesive containing the same can be improved, for example, 8〇 . The storage modulus in the crucible is above 1,0 MPa, and even if the polarizer is bonded to the polarizer with the adhesive and the polarizing plate of the protective film is subjected to intense temperature, the crack of the polarizer can be avoided. On the other hand, when the amount is more than 75% by weight, the amount of the following diepoxypropyl compound (A2) and monofunctional epoxy compound (A3) is relatively small, and it is difficult to obtain the light of the present invention. The low viscosity of the hardenable adhesive and the adhesion between the polarizing and the protective film are improved. The alicyclic diepoxy compound (Al) is more preferably contained in an amount of 7% by weight or more based on the total amount of the photocationic curable component (1). The amount of the di-epoxypropyl compound (10) engraved in the hardening component (A) is 5 to 35. By dispersing 5% by weight or more of the diepoxypropyl compound (A2) in the photocationic curable component (1), the storage modulus after hardening the photocurable adhesive containing the same can be kept high and polarized. The adhesion between the sheet and the protective film is increased. On the other hand, when the amount exceeds 35 weights, the adhesion between the partial sheet and the protective film is insufficient, and the storage modulus after curing the photocurable agent is also lowered. It is better to have a storage modulus after the polarizer and the protective force, and the photocurable adhesive is hardened. </ RTI> The bis-epoxypropylation of the D-A towel is preferred. The amount of the substance (A2) is 25% by weight or less. Further, the amount of the photocationic curable component (A) t^ monofunctional epoxy compound = 2 to 15% by weight. The monofunctional epoxy compound (10) having a photocationic curable component (1): or more than 2% by weight, in addition to lowering the viscosity of the light=adhesive agent, exhibits poor coating properties, and at the same time improves the adhesion between the films. On the other hand, the amount is more than eight resets, 'the storage modulus that cannot be cured by the photocurable adhesive is filled with the polarizer of the polarizer and the protective film. When subjected to intense temperature history of 324108 12 201245382, the polarizer is easily broken. In the above formula (I) representing the alicyclic diepoxide compound (A1), R1 and R2 are each independently a hydrogen atom or a carbon number of 1 to 6. The alkyl group may have an alicyclic structure when the carbon number of the alkyl group is 3 or more. When the position of the cyclohexane ring bonded to X in the formula (I) is taken as the 1-position (hence, in the two cyclohexane rings) The position of the epoxy group is 3,4-position), and the alkyl group may be bonded to any one of the 1-position to the 6-position. The alkyl group may of course be a linear chain, and may be classified when the carbon number is 3 or more. Further, as described above, the carbon number may be 3 or more, and may have an alicyclic structure. Typical examples of the alkyl group having an alicyclic structure are Also in the formula (I), an X-type oxygen atom of two 3,4-epoxycyclohexane rings, an alkanediyl group having 1 to 6 carbon atoms or the above formula (la) to The divalent group represented by any one of (Id), wherein the alkanediyl group has a concept of an alkylene group or an alkylene group, and the alkylene group may be a straight chain, and may be branched when the carbon number is 3 or more. Further, when X is a divalent group represented by any one of the above formulas (la) to (Id), each of the linking groups Υ\Υ2, Υ3, and Y4 is an alkanediyl group having 1 to 20 carbon atoms, respectively. The alkanediyl group may have an alicyclic structure when the carbon number is 3 or more. The alkanediyl group may of course be a straight chain, and may be branched when the carbon number is 3 or more. Further, as described above, when the carbon number is 3 or more It may have an alicyclic structure. Typical examples of the alkanediyl group having an alicyclic structure are a cyclopentylene group and a cyclohexylene group. Specifically, the alicyclic diepoxide compound (Α1) represented by the formula (I), X in the formula I) is a divalent group represented by the above formula (la), and the compound in which a is 0 is 3, 4-epoxycyclohexyldecyl alcohol (the cyclohexane ring may be compared with the carbon number) 1 to 6 alkyl groups) and 3,4-epoxycyclohexanecarboxylic acid (this An esterified product of a hexane ring which may be bonded to an alkyl group having 1 to 6 carbon atoms. Specific examples thereof are 324108 13 201245382: 3,4-epoxy ring of 3,4-epoxycyclohexanecarboxylic acid Hexyl ketone [Formula (1) (except that the divalent group represented by the formula (la) of the X system a = 0), the compound of Ri = R2 = h], 3, 4-epoxy-6-oxime 3,4-epoxy-methylcyclohexyl decyl ester of the same ring as the above, [i.e., a compound having the formula (I), ri=6-methyl and R2=6-methyl], 3 , 4-epoxy-1-indenylcyclohexane decanoic acid 3, 4__ epoxy-1-indenylcyclohexyl decyl ester [Iso, in the formula X, R1 = methyl group and R2 = compound of diterpenoid] , 3, 4-epoxy-3-indolylcyclohexane tracing 3, 4-epoxy-3-indolylcyclohexylmethyl g | Same as above, with X formula (! ) ' ί ^ = 3-mercapto group and R 2 = 3-methyl compound] and the like. The compound of the formula (I) wherein X is a divalent group represented by the formula (lb) is a alkylene group and a 3, 4-epoxycyclohexanecarboxylic acid (the cyclohexane ring may have a carbon number of 1 to An ester of 6 alkyl groups). The compound of the formula (I) wherein X is a divalent group represented by the formula (Ic) is an aliphatic dicarboxylic acid and 3, 4-epoxycyclohexyl decyl alcohol (the cyclohexane ring may have a carbon number of 1 to 6) An ester of an alkyl group). Further, X of the formula ο) is a compound of the divalent group represented by the formula (Id), which is a test of 3, 4-epoxycyclohexylmethanol (the ring hexane ring can be combined with a carbon number of 1 to 6) a body (b = 〇) 'also' alkyl diols or polyalkylene glycols and 3, 4-epoxy nuclear hexanol (the cyclohexane ring can be with carbon number 1 to 6) Ether grouping of alkyl group) (b&gt; 〇). In the above formula (II) representing the diepoxypropyl compound (A2), Z is an alkylene group having 1 to 9 carbon atoms, an alkylene group having 3 or 4 carbon atoms, a divalent alicyclic group, or a formula The divalent group shown here, -Z1-system '° C0~°---〇-C〇---S〇2---SO- or -CO-,m and η are each independently 1 The integer above is a total of 9 or less. Divalent fat 324108 14 5 201245382 Typical examples of the cyclic hydrocarbon group are a cyclopentyl group and a cyclohexyl group. In the formula (Π), Z is an alkylene group compound which is a dicyclooxypropyl ether of an alkylene glycol. Specific examples thereof include: ethylene glycol diepoxypropyl mystery, monopropanediol diepoxypropyl ether, hydrazine, 4-butanediol diepoxypropyl ether, hydrazine, 6-hexane Glycol diglycidyl ether and the like. Further, in the formula (II), when Z is a divalent group represented by the formula -CmHwZi-Cnlhn-, Z is a stretching group having a carbon number of 2 or more, '〇-, -C0-0-, -0-C0- -s〇 corresponds to the CC bond of the alkylene group blocked by 2~, -so-, or -C0-. In the above formula (ΙΠ) representing a monofunctional epoxy compound, R3 is an alkyl group having a carbon number of i to 15. The alkyl group may of course be a straight chain and may be branched when the carbon number is 3 or more. The alkyl group is preferably a carbon number which is relatively large, for example, 6 or more, more preferably a carbon number of 6 to 10. Among them, it is difficult to branch the base. In a typical example of the monofunctional epoxy compound represented by the formula (1), 2-ethylhexyl epoxypropyl hydrazine is exemplified, and a photocationic curable component constituting the photocurable adhesive (A) The ratios described above include the above-described alicyclic diepoxide compound=Al)-%oxypropyl compound (A2) and a monofunctional epoxy compound (μ). ^It is expected that the photocurable adhesive before curing is more effective, the lower viscosity of the photocurable adhesive, the hard = the storage modulus of the object, and the dense tongue between the polarizer and the protective film, and the total amount of the photocurable adhesive. In view of the above, the total amount of the diepoxypropane compound (10) and the monofunctional epoxy compound (10) is preferably 25% by weight or more. (A photocationic curable component (A) is obtained by making the alicyclic diepoxide oxime, the diepoxypropyl compound (A2), and the monofunctional epoxy compound (A3) into 3241〇8 15 201245382 as the amount described above. In the range of the above, other cationically polymerizable compounds may be contained. (Photocationic polymerization initiator) In the present invention, the photocationic curable component is cured by cationic polymerization by irradiation of an active energy ray to form an adhesive layer. The photocationic polymerization initiator (B) is formulated in the photocurable adhesive composition. The photocationic polymerization initiator generates a cationic species by irradiating an active energy ray such as visible light, ultraviolet light, X-ray or electron beam. Or a Lewis acid, and a polymerization reaction of the photocationic hardening component (A) is started. The photocationic polymerization initiator is photocatalytic, so even if it is mixed with a photocationic cation formation component (A) It is excellent in preservative stability and workability. A compound of a cationic species or a Lewis acid is produced by irradiating an active energy ray, and it is exemplified as an aromatic m aromatic. a salt of rust such as salt; an iron-allene complex, etc. The aromatic diazonium salt may, for example, be a compound of the following: hexafluorocarbonate, diazobenzene, hexafluorophosphate, hexafluorobenzene, hexafluorobenzene The acid diazonium benzene, etc. The aromatic sulfonium salt may, for example, be a compound such as diphenyl sulfonium tetrakis(pentafluorophenyl)borate, diphenyl sulfonium hexafluoroantimonate or diphenyl hexafluoroantimonate.錤, bis(4-mercaptophenyl)phosphonium hexafluorophosphate, etc. The aromatic salt is exemplified by the following compounds: 324108 201245382 * Triphenyl sulfonium hexafluorophosphate, triphenyl sulfonium hexahydrate, four (Pentafluorophenyl)boronic acid triphenylsulfonium, • 4,4′-bis[diphenyldiarthyl]diphenyl sulfide dihexafluorophosphate, 4,4′-bis[di(yS-) Hydroxyethoxy)phenyldihydrothio]diphenyl sulfide dihexafluoroantimonate, 4,4'-bis[bis(wan-hydroxyethoxy)phenyldihydrothio]diphenyl Sulfide bishexafluorophosphate, 7-[bis(p-indolyl)dihydrothio]-2-isopropylthioxanthone hexafluoroantimonate, 7-[di(p-anthracene) Benzoyl)dihydrothio]-2-isopropylthioxanthone four (five Phenyl)borate, 4-phenylmethyl-4'-diphenyldihydrothio-diphenyl sulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4' -diphenyldihydrothio-diphenyl sulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-bis(p-nonylbenzylidene) dihydrogen Base-diphenyl sulfide tetrakis(pentafluorophenyl)borate, etc. The iron-heavy olefin complex can be exemplified by the following compounds: Diphenylbenzene-cyclopentadienyl iron (II) hexafluoroantimonic acid Salt, cumene-cyclopentadienyl iron(II) hexafluorophosphate, diterpene benzene-cyclopentadienyl iron(II) tris(trifluoromethylsulfonyl) fluorenyl (xylene-cyclopentadieneiron) (II) tris 324108 17 201245382 (trimethylsulfonyl)methanide). These photocationic polymerization initiators may be used alone or in combination of two or more. Among these, in particular, the aromatic sulfonium salt has ultraviolet absorbing properties in a wavelength region of around 3 〇〇 nm, and therefore is excellent in curability, and can be used as a cured product having good mechanical strength and adhesion strength. The compounding amount of the photocationic polymerization initiator (B) is 丨 to 1 part by weight based on 1 part by weight of the entire photocationic curable component (A). When the photocationic curable component (A) is used in an amount of 1 part by weight or more by weight of the photocationic polymerization initiator, the photocationic curable component (A) can be sufficiently cured, and the obtained polarizing plate can be provided high. Mechanical strength and strength. On the other hand, when the amount is too large, the increase in the ionic substance in the hardened material increases the hygroscopicity of the cured product, and the durability of the polarizing plate is lowered, so that the amount of photocationic polymerization is started. The photocationic curable component (1) is 10 parts by weight or less per 100 parts by weight. The compounding amount of the photocationic polymerization initiator (B) is preferably a photocationic curable component (...more than 2 parts by weight per 1 part by weight, more preferably 6 parts by weight or less. (Adjustable to photohardening) Other components of the adhesive agent) The photocurable adhesive of the present invention may be additionally contained in addition to the photocationic curable component (1) and the photocationic polymerization initiator (8) containing the epoxy compound described above. Other components of the curable resin or the adhesive. Suitable examples of other components are exemplified by light-enriching and photo-sensitizing assistants. The light-increasing amount of the maximum absorption wavelength of the tb photocationic polymerization initiator (8) is longer. The wavelength shows the maximum absorption and promotes the compound which initiates the reaction by the polymerization of the photocationic polymerization initiator (8). Further, the photo sensitization aid is incorporated into 324108 18 201245382 The type of compound 1 which promotes the action of the photosensitizer in one step Preferably, the light sensitizer is compounded, and the light sensitizing aid is adjusted. The light sensitizer is preferably a compound exhibiting a maximum wavelength of light longer than 380 nm, and the photocationic polymerization initiator ( )) in 3 A wavelength near or shorter than 〇nm indicates maximum absorption, and light of a wavelength near it is induced to generate a cationic species or Lewis acid, and cationic polymerization of the photocationic hardening component (A) is started, and if the photosensitizer is as described above, Then, it becomes possible to induce a longer wavelength, especially a wavelength longer than 380 nm. The photo sensitizer is suitable for using a lanthanoid compound. Specific examples of the lanthanide sensitizer may be exemplified by the following compounds d 9, 10-dimethoxy hydrazine, 9, 10-diethoxy hydrazine, 9, 10-dipropoxy fluorene, 9, 10-diisopropoxy hydrazine, 9, 10-dibutoxy蒽, 9, 10-dipentyloxy oxime, 9.10-dihexyloxy, €, 9.10-bis(2-decyloxyethoxy) ruthenium, 9,10 bis (2-ethoxy ethoxylate) , 9,, 9,10-bis(2-butoxyethoxy)anthracene, 9,10-bis(3-butoxypropoxy)anthracene, 2-indenyl- or 2-ethylidene-MO -dimethoxy hydrazine, 2-mercapto- or 2-~ethyl·_9,10-ethoxylated onion, 2~mercapto- or 2-~ethyl-9,--propoxy side, 324108 19 201245382 2 - Mercapto- or 2-ethyl-9,10-diisopropoxy fluorene, 2-mercapto- or 2-ethyl-9, 10- Butoxy oxime, 2-mercapto- or 2-ethyl-9,1 fluorene-dipentyloxy, 2-mercapto- or 2-ethyl-9,10-dihexyloxy onion, and the like. When the photo-sensitizing agent is blended with the photo-sensitizing agent as described above, the curability of the adhesive is improved as compared with the case where the photo-curable component (A) is used in an amount of 100 parts by weight. On the other hand, when the amount of the photosensitizer is increased, there is a problem such as precipitation during storage at a low temperature, and therefore the amount is preferably relative to the photocationic curable component. (A) 100 parts by weight or less is 2 parts by weight or less. From the viewpoint of maintaining the neutral gray of the polarizing plate, it is advantageous to reduce the amount of the light sensitizing agent in a range in which the adhesion between the polarizer and the protective film is moderately maintained, for example, relative to photocationic hardenability. 5重量份范围内。 The component (A) 100 parts by weight, preferably the amount of the light sensitizer is 0. 1 to 0. 5 parts by weight, more preferably from 0.1 to 0.3 parts by weight. Next, the photosensitization aid will be described. Although various light sensitizing aids are available, naphthalene-based compounds are advantageous for use. Specific examples of the naphthalene-based photosensitizer include the following compounds. 4-decyloxy-1-naphthol, 4-ethoxy-1-naphthyl, 4-propoxy-1-naphthalene, 4-butoxy-1-naphthol, 4-hexyloxy- 1-naphthene, 1,4-dimethoxynaphthalene, 324108 20 201245382 ethoxyethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dipropoxynaphthalene, 1,4-Dibutoxynaphthalene or the like. By blending a naphthalene-based photo sensitizer in the photocurable adhesive, the hardenability of the adhesive is improved as compared with the case where the photo-curable adhesive is not blended. The effect is exhibited by blending a naphthalene-based photo sensitizer 〇. 1 part by weight or more with respect to the photocationic curable component (Α). On the other hand, when there is an increase in the blending of the naphthalene-based photo sensitizer, there is a problem that precipitation occurs during storage at a low temperature. Therefore, the weight of the vehicle is preferably 5 parts by weight relative to the photocationic curable component (A). The injury is preferably set to be less than 3 parts by weight. (Physical properties of photocurable adhesive) The I-level adhesive is used as described above for bonding a protective sheet to a polarizer composed of a polyvinyl alcohol-based tree. After the adhesive is applied to the bonding surface of the polarizing stones, the two adhesives are cured. Then, in order to make its *viscosity==coating suitability improve, it is preferred that the compound of the specific three types of the tenderness is shortened by a predetermined two-stage sclerosing contact, (4) 4: the photocurable adhesive is in the _ The viscosity becomes again, and the adhesion between the polarizer and the protective film is increased. The adhesive layer of the subsequent suppressive layer has a higher modulus. The preferred one is 324108. The same as the photocation. The curable component (A) can be prepared by mixing the above-mentioned two types of three kinds of compounds in a predetermined ratio, and maintaining the coating suitability while maintaining the coating viscosity at a low value as described above. The modulus is increased. Specifically, the cured product of the photocurable adhesive can exhibit a storage modulus of 10,000 MPa or more at 80 °C. [Polarizing Plate] In the present invention, the at least one surface of the polarizer composed of the polyethylene resin film is bonded to the ray lion which is made of a transparent resin through the photocurable adhesive described above. The hardenability is then slated as a polarizing plate. According to the present invention, as described above, the storage modulus of the adhesive layer of the cured product of the photocurable adhesive can be improved, and the adhesion between the polarized light and the protective film can be improved. Therefore, the bonding strength of the (10) peeling test between the polarizer and the protective film can be made G. 6M/25 mm or more. Here, the (10) peeling test was carried out in accordance with JIS K 6854-2 M999 "Adhesive-peeling strength test method - Part 2: 180 degree peeling". Hereinafter, the polarizer and the protective film constituting the polarizing plate of the present invention will be described, and a method of manufacturing the polarizing plate will be briefly described. (Polarizing Sheet) The polarizing film is composed of a polyethylene glycol-based resin film in which a dichroic dye is adsorbed in an oriented manner. The polyethylidene alcohol-based resin constituting the polarizer can be obtained by saponifying a polyethylene acetate vinegar resin. The polyacetic acid ethyl-based resin may be a copolymer of ethylene acetate vinegar and other monomers copolymerizable therewith, in addition to the polyacetate of the homopolymer of acetic acid. The other monomer copolymerized with ethyl acetate vinegar may, for example, be an unsaturated carboxylic acid or an olefin, or a 324108 22 201245382% olefinic vinegar or an unsaturated sulfonic acid. The degree of saponification of the polyvinyl alcohol-based resin is usually from 85 to 1% by mole, preferably from 98 to 1% by mole. The polyvinyl alcohol-based resin can be further modified. For example, the degree of polymerization of the 4-ethylenic resin such as polyethylene, polyethylene, and the like which is modified by a genus can be used, usually from 1, to 10,000. , preferably the range of 500 to 5, 〇〇〇. The polarizer is produced by a step of uniaxially stretching such a polyvinyl alcohol-based resin film, and a step of adsorbing the polyvinyl alcohol-based resin film with a dichroic dye to adsorb the dichroic dye; The polyvinyl alcohol-based resin film having the dichroic dye adsorbed thereon is treated with an aqueous solution of boric acid. The uniaxial stretching can be carried out before the dyeing by the dichroic dye, at the same time as the dyeing with the one-color pigment, or after the dyeing with the dichroic dye. The uniaxial extension is carried out after the dichromatic color money color, and the single 2 extension can be performed in the processing of the money, or in the food. It is of course also possible to carry out a uniaxial extension in the plural phases of these. The uniaxial extension can be carried out by uniaxial stretching between rolls having different circumferential speeds, or by using a hot roll for stretching of the bicycle I, stretching in the atmosphere, or by swelling with a solvent. Extended wet stretch. The stretching ratio is usually about 4 to 8 times. When the polyacetate-based resin film is dyed with a dichroic dye, for example, the poly(enyl alcohol) resin film may be impregnated into an aqueous solution containing a dichroic dye. For the dichroic color, "specifically, iodine or dichroic organic dye can be used. When π/^ is used as a dichroic dye, it is usually used to make a polyethylene chain tree = Mann: in an aqueous solution containing moths and moths. The method of dyeing. The content of strontium in the liquid is generally 0.01 to 324,108 with respect to 100 parts by weight of water.

About 0.5 weight loss, the potassium iodide content is usually about 5 to 10 parts by weight based on 1 part by weight of water. The temperature of the aqueous solution is usually about 20 to 40 ° C. The dipping time (dyeing time) of the aqueous solution is usually about 30 to 300 seconds. On the other hand, when a dichroic organic dye is used as the dichroic dye, a method in which a polyvinyl alcohol-based resin film is impregnated into an aqueous solution containing a water-soluble dichroic organic dye and dyed is usually used. The content of the dichroic organic dye in the aqueous solution is usually from about 1 part by weight to about 1 part by weight of the xxio-3 to lxiir2. The aqueous solution may contain an inorganic salt such as sodium sulfate. The temperature of the aqueous solution is usually about 20 to 8 (about TC, and the impregnation time (dyeing time) of the aqueous solution is usually about 30 to 3 sec. The boric acid treatment after dyeing with the dichroic dye will be The dyed polyvinyl alcohol resin film is impregnated in an aqueous solution of boric acid. The boric acid content in the aqueous boric acid solution is usually about 2 to 15 parts by weight with respect to 100 parts by weight of water, preferably about 5 to 12 parts by weight. When the moth is used as the dichroic dye, the aqueous solution of the humic acid solution preferably contains potassium carbonate. The potassium moth content in the aqueous boric acid solution is usually about 2 to 20 parts by weight based on 100 parts by weight of water, preferably 5 to 15 parts by weight. The impregnation time in the aqueous boric acid solution is usually from 1 Torr to about 200 seconds, preferably from about 150 to 601 sec., more preferably from about 200 to about sec. The temperature of the aqueous boric acid solution is usually 5 〇°c or more, preferably 50 to 853⁄4. The polyvinyl alcohol-based resin film after the rotten acid treatment is usually subjected to a water washing treatment. The water-washing treatment is immersed, for example, by dipping the acid-treated polyethtyl alcohol resin film. Performed in water. Washed and dried. The polarizer is obtained. Water 324108 24 201245382 The temperature of the water to be treated is usually about 5 to 攸, and the immersion time is usually 2 to 12 G. The left 纟 仃 仃 仃 通常 通常 通常 通常 通常 通常 通常 通常 通常 通常 通常 通常 通常 通常 通常 通常 通常 通常 通常 通常 通常 通常 通常The drying temperature is usually from 4 Torr to C. Further, the drying treatment time is usually from about 12 Torr to about _ second. The thickness of the polarizer composed of the polyethylene glycol-based resin film thus obtained can be 10 to (a protective film) The polarizer composed of the polyethylene glycol-based resin film described above is bonded to the protective film by the photocurable adhesive described above to harden the photocurable carrier. As a polarizing plate, the protective film is the most widely used acetaminophen-based resin film, which is the most widely used as the protective film of the polarizing plate, or which is lower in moisture permeability than triethylene fluorene cellulose. It is composed of a resin film. The moisture permeability of triacetyl cellulose is about 4 〇〇g/mV24 hr. - In a preferred embodiment, the protective film bonded to at least one surface of the polarizer is made of acetaminocellulose resin. Is in the polarizer The surface-bonded protective film 4 can be composed of an acetaminophen-based resin blended with a UV absorber. In another preferred embodiment, the protective film attached to at least one side of the polarizer is more transparent than the trimethylcellulose. The low resin film is made of, for example, a resin film having a moisture permeability of 300 g/m 2 /24 hr or less. The resin which has such a low moisture permeability resin film may, for example, be an amorphous polyolefin resin, a polyester resin or an acrylic resin. A resin, a polycarbonate resin, a chain polyolefin wax, etc. Among these, an amorphous polyolefin resin, a polyester resin, and a chain polyolefin resin are preferably used. In a preferred embodiment, the adhesive layer is made of the acetonitrile cellulose tree 324108 25 201245382 grease on one side of the polarizer, and is bonded to the polarizer (four)-surface (4) the adhesive layer. A protective film composed of a transparent resin having a low moisture permeability as described above. The at least a portion of the acetaminophen-based resin of the acetaminophen-based resin-based cellulose may be partially mixed with acetic acid and partially mixed with other acid. Specific examples of the acetaminophen-based resin may, for example, be triethylcellulose, diacetin, cellulose acetate propionate or cellulose acetate butyrate. The amorphous polyolefin resin has a polymerized unit of a cyclic hydrocarbon such as a rare, tetracyclic, or dicyclic, or a compound having a cyclic aliphatic hydrocarbon such as a compound having a substituent bonded thereto. The polymer 'may also be a copolymer which copolymerizes a cyclic hydrocarbon with a bond hydrocarbon and/or an aromatic ethide. In the case of a homopolymer of a cyclic hydrocarbon or a copolymer of two or more kinds of cyclic olefins, a double bond is left by ring-opening polymerization. Therefore, it is generally used as an amorphous polyalkylene resin. Among them, a thermoplasticity-reducing olefinic resin is representative. The vinegar-based resin is a polymer obtained by condensation polymerization of a dibasic acid and a diol, and is made of polyethylene terephthalate. The acrylic resin is a polymer mainly composed of thioglycolic acid vinegar as a main monomer, and may be f-based acid gg| and yttrium acid vinegar, in addition to the homopolymer of mercapto-acrylic acid methyl vinegar. A copolymer of acrylic acid acrylate or a fragrant aromatic ethylenic compound. The polycarbonate resin-based main chain has a polymer of a carbonate bond (_〇_C〇_〇_), and is represented by a condensation polymerization of bisphenol A and carbon dichloride. The chain polyolefin resin is a polymer having a chain olefin such as ethylene or propylene as a main monomer, and may be a homopolymer or a copolymer. Among them, a homopolymer of propylene, a copolymer of propylene and a small amount of ethylene is represented. 324108 26 201245382 Such a protective film may be on the opposite side to the surface to which the polarizer is attached, such as a hard coat layer, an antireflection layer, an antiglare layer, or an antistatic layer: The protection includes a case where such a surface treatment layer is formed, and the degree may be about 5 to 150 mm. The thickness is preferably 1 () or more and 12 〇 or less, and more preferably 1 〇 (^m or less. (Manufacturing method of polarizing plate). For the manufacture of a polarizing plate, the photocurable adhesive described above is used. The coating layer is formed on the bonding surface of the polarizer and the protective film, or both of them are bonded to the polarizer and the protective film via the coating layer, thereby forming an unhardened photocurable adhesive. The coating layer is cured by irradiation with an active energy ray, and the protective film is fixed to the polarizer. The coating layer of the photocurable adhesive can be formed on the bonding surface of the polarizer, or can be formed on the bonding surface of the protective film. The formation of the layer can be carried out, for example, by using a doctor blade (e.g., in various coating methods such as a sinker (je), a wire bar, a die coater, a comma coater, a gravure coater, etc.) By using the side so that the bonding surface of the protective film and the protective film are continuously supplied inwardly, and the adhesive is cast between them, each coating method has its optimum viscosity range, so The use of solvents for viscosity adjustment is a useful technique. In the case where the optical performance of the polarizer is not lowered and the photo-curing agent is dissolved, the type of the adhesive is not particularly limited. For example, a tobacco represented by toluene or an ester represented by ethyl acetate can be used. The organic solvent. The thickness of the adhesive layer is usually 20 Mm or less, preferably less than 1 m, more preferably 5 # m or less. If the adhesive layer is thick, the reaction rate of the adhesive is lowered, and there is a polarizing plate. The tendency to deteriorate the moist heat resistance 324108 27 201245382 When the polarizer and the protective film are subsequently attached, a corona discharge treatment or a plasma treatment may be performed before the coating layer of the adhesive is formed on one or both of the bonding surfaces of the two bonding surfaces. The flame treatment, primer treatment, or anchor coating treatment is easy to handle. The light source for applying the active energy ray to the coating layer of the photocurable adhesive is as long as it generates ultraviolet rays, electron beams, and krypton. For example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, or the like having a light-emitting distribution at a wavelength of 400 nm or less can be suitably used. A black light, a microwave-excited mercury lamp, a metal dentate lamp, etc. The intensity of the active energy ray of the photocurable adhesive depends on the intended composition, and is not particularly limited, but is preferably a photocationic polymerization initiator. The irradiation intensity in the wavelength region in which the activation is effective is 〇.丨 to 100 mW/cm 2 . If the light irradiation intensity to the photocurable adhesive is too small, the reaction time becomes too long, and if the light irradiation intensity is too large, It is possible to generate light from the heat generated during the polymerization of the lamp and the heat generated by the photocurable adhesive. The yellowing of the chemical binder and the deterioration of the polarizer are hard. The light irradiation time of the photocurable adhesive is hardened. The composition is individually controlled, and the same is particularly limited, but it is preferable to set the amount of the accumulated light expressed by the product of the irradiation intensity and the irradiation time to 10 to 5, 〇〇〇mj/cm2. If the total amount of light to the photocurable adhesive is too small, the production of the active species derived from the photocationic polymerization initiator may be insufficient. The resulting adhesive-like hardening may not be sufficient. On the other hand, if the cumulative amount of light is to be increased, The irradiation time becomes very long, which is not conducive to the improvement of productivity. When the protective film is attached to both sides of the polarizer, the active energy ray is irradiated from 324108 28

I 201245382 can be carried out on either side of the protective film. For example, if one side of the protective film contains an ultraviolet absorber' and the other side of the protective film does not contain an ultraviolet absorber, the active energy line is irradiated from the side of the protective film containing no ultraviolet absorber. It is preferable to use the active energy ray of the irradiation to increase the hardening speed. [Laminated optical member] The polarizing plate of the present invention can be used as a laminated optical member by laminating an optical layer having an optical function other than a polarizing plate. Typically, the optical layer is laminated as a laminated optical member by a protective film of a polarizing plate via an adhesive or an adhesive, and further, for example, a photocurable adhesive may be applied to one side of the polarizer according to the present invention. The protective film is attached, and the optical layer is laminated on the other side of the polarizer via an adhesive or an adhesive. In the latter case, in the case of attaching a polarizer and an optical layer, if the photocurable adhesive according to the present invention is used, the optical layer can simultaneously serve as a protective film specified in the present invention. In the example of the optical layer laminated on the polarizing plate, there is a polarizing plate disposed on the back side of the liquid crystal cell, and a reflective layer laminated on the opposite side of the side of the polarizing plate facing the liquid crystal cell. , a semi-transmissive reflective layer, a light diffusing layer, a light collecting plate, a brightness increasing film, and the like. In addition, any of the polarizing plate disposed on the front side of the liquid crystal cell and the polarizing plate disposed on the back side of the liquid crystal cell may have a retardation film laminated on the side of the polarizing plate facing the liquid crystal cell. . The reflective layer, the semi-transmissive reflective layer, or the light-diffusing layer are provided as a reflective polarizing plate (optical member), a transflective polarizing plate (optical member), or a diffusing polarizing plate (optical member), respectively. The reflective polarizing plate is used to reduce the thickness of the liquid crystal display device by 324108 29 201245382 (a liquid crystal display device of a type that is reflected from the incident side of the identification side, because the light source such as a backlight can be omitted.) The plate is used as a reflective type in a bright place and a liquid crystal display device in a dark place by light of a backlight. As an optical member of a reflective plastic polarizing plate, for example, a metal such as aluminum may be attached to a protective film on a polarizing plate. Forming a foil or a vapor-deposited film to form a reflective layer. The optical member as a semi-transmissive polarizing plate can be made into a half mirror by using the reflective layer; or it can contain a pearl pigment or the like and exhibit light penetration. The reflective plate is formed on the polarizing plate. On the other hand, as the optical member of the diffused plastic polarizing plate, for example, a method of applying a resin containing fine particles by a method of performing a matting treatment on a protective film on a polarizing plate Then, various methods such as a method of containing fine particles are used to form a fine uneven structure on the surface. Further, 'can also be formed as a reflection diffusion. In this case, for example, an optical member that acts as a polarizing plate for both uses can be used, for example, a method in which a fine uneven structure surface of a diffusing type polarizing plate is provided with a reflecting layer reflecting the uneven structure. A reflective layer of a fine uneven structure is used to diffuse incident light. It is reflected and diffused, and has the advantages of preventing directivity, glare, and suppressing unevenness of light and darkness. Further, the resin layer or film containing fine particles diffuses light and diffuses when penetrating the layer containing fine particles, thereby suppressing unevenness in brightness and darkness. Advantages: The reflective layer reflecting the fine uneven structure of the surface can be formed, for example, by directly attaching a metal to the surface of the fine concavo-convex structure by vapor deposition or coating such as vacuum evaporation, ion plating, or sputtering. The fine particles which are formed by forming the surface fine concavo-convex structure may be, for example, an average particle diameter of 〇·1 to 30/zra such as oxidized second, oxidized, titanium oxide, 324108 30 201245382, tin oxide, indium oxide, oxidized crane, cerium oxide. Inorganic microparticles such as organic microparticles of crosslinked or non-crosslinked polymers, etc. = (4) silk (4) purpose twirling, can be used as prism t-column (prism An array sheet), a lens array sheet, or a sheet with a dot (d〇t), etc. The brightness enhancement film is exemplified for the purpose of improving the brightness of the liquid crystal display device. A reflective sheet designed to form an anisotropic manner in which the reflectance can produce anisotropy, an oriented film having a cholesteric liquid crystal polymer, and an oriented liquid layer thereof supported on the film base Further, the above-mentioned retardation film which functions as an optical layer is used for the purpose of compensating for the phase difference of the liquid crystal, etc. As an example, a second example of a plastic film may be used. The birefringent film is oriented with dlscotic liquid crystal or nematic liquid crystal. When a liquid crystal layer is formed on the ruthenium substrate on the film substrate and the liquid crystal layer is formed on the film substrate, a cellulose resin film such as triacetonitrile cellulose is preferably used as the film substrate. t = plastic of a refraction film, for example, an amorphous polyolefin tree, a polycarbonate resin, an acrylic resin, a chain-like polystyrene resin such as polypropylene, and a polyethylene Alcohol, polystyrene, polyarylamine, polyamine, and the like. The stretch film can be treated in a suitable manner such as uniaxial or biaxial. Further, the retardation film can be used in combination of two or more for the purpose of controlling optical characteristics such as wide band. Among the laminated optical members, a retardation film is included as the light other than the polarizing plate. 324108 31 201245382 The layered film is suitable for use in a liquid crystal display device because it is effectively optically protected. The phase difference (in-plane and thickness direction) of the retardation film can be selected according to the applicable liquid crystal cell. The laminated optical member is selected from the group consisting of a polarizing plate and one or more layers of the above various optical layers for the purpose of use, and may be a laminated body of two or more layers. In this case, the various optical layers forming the laminated optical member are integrated with the polarizing plate using an adhesive or an adhesive, and the adhesive or adhesive used for this purpose is not particularly good as long as the adhesive layer or the adhesive layer is formed well. limited. Adhesives (also known as pressure-sensitive adhesives) are preferred from the standpoint of ease of handling, prevention of occurrence of silk strain, and the like. As the adhesive, an acrylic polymer, a poly-molecular polymer, a polyester vinegar, a polyacetal, a polyether or the like can be used as a matrix polymer ("adherent." Use light such as B-when acid-based adhesives [excellent, maintain moderate (4) wetness or cohesiveness, benevolent, and have weather resistance or heat, etc., in heating or humidifying conditions For the problem of peeling off, the propionate-based adhesive is produced so that the glass transition temperature is preferably below the muscle, and more preferably, it is used in the formula: having a carbon number of 2{) or less (4) such as a base group, an ethyl group, or a butyl group. Acrylic acid-based acetonitrile, and an acrylic copolymer having a molecular weight of H or more from a fluorinated rare earth (methyl ethyl vinegar or the like containing a functional group-containing acryl-based monomeric acid) As a matrix, the formation of an adhesive layer on the polarizing plate, for example, an object. Disperse in an organic solvent such as methyl bromide or ethyl acetate to prepare a solution of no heavy weight (iv), by directly coating it on a polarizing plate. Up to 40 2141OR, or 32 201245382 &gt; pre-formed on the protective film The thickness of the adhesive layer is determined by the method of attaching the layer to the polarizing plate, etc. The thickness of the adhesive layer is determined by the adhesion force, etc., and is suitably in the range of about 1 to 50/zm. Need to be formulated with glass fiber or glass bead, resin beads, metal powder or other inorganic powder to constitute a historical filler, pigment or colorant, antioxidant, UV absorber, etc. UV absorber with salicylic acid An ester compound, a diphenyl sulfonium compound, a triterpenoid compound, a cyanoacrylate vine compound, a nickel stear salt compound, etc. The laminated optical member can be disposed on one side or both sides of the liquid crystal cell. The cell is arbitrary, and for example, an active matrix drive type represented by a thin film transistor type or a liquid crystal cell of a simple matrix drive type represented by a super twisted neinat iq can be used to form a liquid crystal display device. The lamination of the laminated optical member and the liquid crystal cell can generally be carried out using the same adhesive as above. (Embodiment) Hereinafter, the embodiment will be more specifically described to explain the present invention. The invention is not limited to the examples. In the examples, 'the content or the amount used and the parts are based on weight when not specifically noted. Further, the photocationic curable component and the photocationic polymerization initiator used in the following examples. As described below, the following is a list of the respective symbols &gt; y% ° (A) Photocationic curable component (al) 3, 4-epoxycyclohexanone 3, 4-epoxycyclohexyl decyl ester [previously RkRkH, compound of formula X=-C00CH2- in formula (I), 324108 33 201245382 (a2) 1,4-butanediol diepoxypropyl ether [z=-(CH2)4 in the above formula (π) - compound], (a3) 2-. ethylhexylepoxypropyl ether [R3=CH3(CH2)3-CH(CH2CH3)-CH2- compound in the above formula (ΠΙ)] 〇(B) photocation Polymerization initiator (abbreviated as "starter" in the table) (bl) triaryl sulphate. [Examples 1 and 2 and Comparative Examples 1 to 9] (1) Preparation of Photocurable Adhesive Agent The components were mixed at a mixing ratio (unit: part) shown in Table 1, and then defoamed to prepare a photocurable adhesive liquid. . Further, a photocationic polymerization initiator (bl;) was formulated as a 50% propylene carbonate solution, and the solid content thereof is shown in Table 1. [Table 1]

(2) Viscosity measurement of the adhesive liquid at 25 ° C For the respective adhesive liquid prepared above, a rotary viscoelasticity measuring device "Physica MCR301" manufactured by Anton Paar Co., Ltd. was used to measure 324108 34 201245382 when the temperature was 25 C. Viscosity. The results are shown in Table 2. (3) Measurement of the storage modulus of the cured product at 8 (TC) using a coater [bar coater, manufactured by First Chemicals Co., Ltd.], and the respective adhesive liquid prepared in the above (1) is hardened. The film thickness is about 3 〇. It is applied to a single side of a polyparaphenylene n film [trade name "Toyobo FELLME 7002" - Toyo Textile Co., Ltd.). Then, Fusi〇n UV Systems The "D bulb," is irradiated with ultraviolet rays in such a manner that the cumulative amount of light becomes 3, OOOmJ/cm2, and the adhesive is hardened. The film is cut into a size of 5 mm x 3 0 to peel off the polyethylene terephthalate film. A cured film of the adhesive is obtained. The cured film has a long side as a stretching direction, and the dynamic viscoelasticity measuring device "DVA_22" made by the IT measurement system is gripped at a distance of 2 cm by the holder. The frequency of stretching and contraction was set to 1 Hz, the temperature rising rate was set to 3 ° C / min, and the storage modulus at a temperature of 8 ° C was obtained. The results are shown in Table 2. (4) Preparation of polarizing plate for absorption of rabbit-containing external line The thickness of the agent is 8〇_ of the triacetyl cellulose film [trade name "K0NICATACKC8UX2MW", K〇nica Minolta 0ptics ( The surface of the system was subjected to a corona discharge treatment, and each of the above-described adhesive liquids prepared above was applied to the corona discharge treated surface by a bar coater so that the film thickness after hardening became about 2/Zm. The agent layer is laminated with a polyetheryl alcohol-filled polarizer having a thickness of 28 (10), and a retardation film having a thickness of 40 #m composed of an acetaminocellulose-based resin [trade name "N_TACKC4FR_r, K〇nica"

The surface of Minolta Optics Co., Ltd. was subjected to a corona discharge treatment, and the same adhesive liquid as described above was used in such a manner that the film thickness after hardening was about 324108 35 201245382 = coater was applied to the corona discharge treatment surface. . The polarizer side of the polarizer of the triacetonitrile cellulose film which was produced by one side was bonded to the adhesive layer to prepare a laminate. From the acetamethylene fiber of the laminate, the phase is replaced by: :,, using the ultraviolet ray irradiation device with the belt conveyor (light system makes ^

Fus wears "D·," manufactured by UVSmems Co., Ltd. to irradiate ultraviolet rays to accumulate the light to make the adhesive harden. Thus, two (4) W polarizing plates with a protective film are provided. (5) 180-degree peeling test The polarizing plate produced in the above (4) is cut to a length of 2 mm. The width of the polarizing plate is 2 mm. The thickness of the polarizing plate produced by the above (4) is Μ ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί = test piece of strength, in addition, the thickness of 8 〇 _ of triethylene fluorene =: = acid adhesive layer, as the thickness of 80 &quot; m between the 醯 cellulose film and the peeling strength between the polarizer The layer of the agent layer is placed between the polarizer and the adhesive side of the "cellulose-based retardation film or the thickness of the 8 〇 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The peeling portion was peeled from the side end by 30 mm'. The peeling portion was sandwiched by the clamping portion of the testing machine. The 4 sheets in this state were in the environment of temperature 231 and relative humidity, according to JIS K 6854-2. 1999 "Adhesive-stripping Then the strength test method _ second part: 180 degree peeling" 'to clamp the moving speed 3 〇〇 mm / The average peeling force of the length of 170 mm other than the 30 mm of the nip portion was taken by the ι8 twist peeling 4 test. The results are shown in Table 2. In the 180 degree peel strength item of Table 2, "N-TAC/PVA" The column indicates the peel strength between the above-mentioned acetonitrile-based retardation film and the polyethylene-324108 36 8 201245382 dilute-barrier polarizer, and the column "TAC/PVA" indicates the above-mentioned thickness of 80//m of triethylene fluorene fiber. The peeling strength between the plain film and the polyvinyl alcohol-iodine-based polarizer. (6) Evaluation of the durability of the polarizing plate by the thermal shock test The polarizing plate produced in the above (4) was cut into the size of i7〇mmxii〇mm. An acrylic pressure-sensitive adhesive layer was provided on the side of the acetonitrile-based retardation film, and the pressure-sensitive adhesive layer was applied to a glass plate to perform a thermal shock test (heat shock test). The thermal shock test was performed by the thermal shock test. The polarizing plate sample on the glass plate was kept at -35 ° C for 1 hour, and then the temperature was raised to 70 ° C for 1 hour. This was repeated for 3 cycles. This was carried out separately for each of the 6 polarized plate samples. The test was observed in the polarizer after the test The proportion of the total number of samples (6) was evaluated by the rupture. The results are shown in Table 2 〇 [Table 2]

As is apparent from Tables 1 and 2, in Comparative Examples 1 to 2 in which the photocationic curable component (A) is a two-component system of (al) and (a2), the protective film and the polarizing film were between 324108 37 201245382. The peel strength cannot be greater than 0·6Ν/25ιηιη between N-TAC/PVA and TAC/ΡνΛ. Further, in Comparative Example 3, the elastic modulus of the cured product of the adhesive was low, and the polarizer was cracked in the thermal shock test. In Comparative Examples 4 and 5 in which the photo-cation hardenability was not obtained as the two-component system of (al) and (a3), the elastic modulus of the cured product of the adhesive was low, and the polarizer was cracked in the thermal shock test. When the photocationic curable component (A) is used as the ternary system of (al) and (a2) and (&amp; 3), 20 parts of (a3) are prepared (2 in the photocationic curable component (A)) %) In Comparative Examples 8 and 9, since the elastic modulus of the cured product of the adhesive was low, the polarizer was broken in the thermal shock test, and the amount of (al) was 80 parts or more. [Photocation-curable component ( In Comparative Examples 6 and 7 in which A) is 8 or more, the peeling strength between the protective film and the PVA cannot be as high as 6 N/25 mm or more. In contrast to this, as in Examples 1 and 2, the adhesives of (al) and (a2) and (a3) are formulated in a predetermined ratio to have a low viscosity, and the cured product imparts a high modulus of elasticity, thereby providing a polarizer which is not easily broken and adhered. High polarizing plate. [Simple description of the diagram] None [Key component symbol description] None 324108 38 8

Claims (1)

201245382 VII. Patent application scope: 1 . A photocurable adhesive for adhering to at least one surface of a polarizer composed of a polyvinyl alcohol-based resin film having a dichroic dye attached thereto, and laminated with a transparent resin. The protective layer contains a photocationic curable component (A) in an amount by weight and a photocationic polymerization initiator (Β) from 1 to 1 part by weight, wherein the photocationic curable component (A) is used. The alicyclic diepoxide (A1) represented by the following formula (I) is contained in an amount of from 6 〇 to 75 wt% based on the total amount thereof: (wherein R and R each independently represent a hydrogen atom or an alkyl group having a carbon number of 丨6, and an alkyl group may have an alicyclic structure when the carbon number is 3 or more; X represents an oxygen atom and an alkyl group having 1 to 6 carbon atoms; Divalent or divalent groups of any of the following formulas (ia) to (Id): 〇\ Ο / 0-CH2—(la) 1 (lb) Ο c—o—ch2 - (Ic) “o —ch2— (Id) Here, each of Y1 to Y4 represents an alkanediyl group having a carbon number of 丨 to 20, and the carbon number—C—^*0—Y1—I 0 II 324108 1 201245382 3 or more may have an alicyclic structure; And b each represents an integer of 〇 to 2〇); the diepoxypropyl compound (A2) represented by the following formula (II) is 5 to 35 parts by weight H2 to 0~Z-〇-C H2 (Π) (wherein ' Ζ represents an alkylene group having 1 to 9 carbon atoms, an isomorphic group having 3 or 4 carbon atoms, a divalent alicyclic hydrocarbon group, or a 2 fluorenyl group represented by s_CmH2n_zl_CnH2n_, where -Z1- represents -〇-, _c 〇_〇-, -〇_c〇_, _s〇2_, _s〇_, or -CO-, m and n each independently represent an integer of 1 or more, and the sum of the two is 9 or less); III) a monofunctional epoxy compound (Α3) 2 to 15% by weight: r3-o-ch2 απ) (wherein, R3 is The photocurable adhesive according to the above aspect of the invention, wherein the R3 based carbon in the formula (III) representing the monofunctional epoxy compound (A3) 3. A photocurable adhesive according to the first aspect of the invention, wherein the viscosity at 25 ° C is less than i 〇〇 mPa sec. 4_ as claimed in the patent scope The photocurable adhesive according to the item 1, wherein the cured product exhibits a storage modulus of 〇〇〇 MPa or more at 80 ° C. 5. The polarizing plate is composed of: a polarizer composed of a polyvinyl alcohol resin film of a dichroic dye, and a protective film made of a transparent resin bonded to at least one surface of the polarizer via an adhesive 324108 8 2 201245382, wherein the adhesive The polarizing plate of the photocurable adhesive according to claim 5, wherein the polarizing plate according to claim 5, wherein the polarizing plate is bonded to at least one side of the polarizing film. The film system contains an ethyl cellulose resin formulated with a UV absorber. The polarizing plate according to claim 5, wherein the protective film bonded to at least one surface of the polarizer comprises a non-crystalline polyolefin resin, a polyester resin, and a chain polyolefin resin. 6N/25毫米以上。 The polarizing plate of the polarizing plate and the protective film measured by the 180 degree peeling test measured by the thickness of 0. 6N / 25mm or more. A laminated optical member comprising a laminate of a polarizing plate and another optical layer described in claim 5 of the patent application. 10. The laminated optical member according to claim 9, wherein the optical layer comprises a retardation film. 324108 3 201245382 IV. Designated representative map: (1) The representative representative of the case is: (). (There is no picture in this case) (2) The symbol of the symbol of this representative figure is simple: (none) 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 〇 __^ch2—0_Z—0—ch2 R3-o-ch2 (Π) (m) 324108 3