TW200909891A - Adhesive for polarizer, polarizer, and manufacture method thereof - Google Patents

Abstract

The invention provides an adhesive for polarizer with favorable adhesive strength, capable of obtaining complete adhesive power in short time and having favorable stability of the solution even when water/alcohol mixing solvent is used. The invention contains polyvinyl alcohol resin of structure unit represented by the general formula (1) (where R1, R2, and R3 represent hydrogen atom or alkyl independently and respectively, X represents alkylidene with 4 to 50 carbon atoms, and Y represents hydrogen atom or alkali metal.)

Description

In the manufacture of a polarizing plate in which a polarizing film and a protective film are used in a liquid crystal display device or the like, it is suitable as a polarizing film and a protective film. A polarizing plate for an adhesive for an adhesive, a polarizing plate obtained by using the polarizing agent, and a polarizing plate using the polarizing plate. <Prior Art Liquid crystal display devices are widely used as image display devices such as liquid crystal televisions, computer monitors, mobile phones, and digital cameras. In the liquid crystal display device, a polarizing film is disposed on both sides of a glass substrate sealed with a liquid crystal, and various optical elements such as a retardation film are laminated thereon as needed. The polarizing film is widely used in polyvinyl alcohol. In the resin (hereinafter referred to as "PVA"), a dichroic material such as a moth is dispersed and adsorbed, and a crosslinked uniaxially stretched film is applied by a crosslinking agent such as borazine. The uniaxially stretched film of the PVA + resin is more easily contracted under high humidity, and the film is adhered to the film or the like on one side or on one side to absorb moisture and strength. It can be used as a polarizing plate in combination. In the case of the adhesiveness of the polarizing film and the protective enamel, the affinity of the m-based resin is higher in the affinity of the m-based resin, and the moisture is higher. When the agent is applied, it also occurs at a high p degree, which is a shrinkage of the polarizing film for the polarizing plate, which causes the shrinkage of the polarizing film of the 97128578 200909891 end, and the durability of the white spot occurs. For the above problem, the proposal is to use a pVA-based February 含有 containing an acetamidine acetate group: a PVA-based adhesive, and to improve moisture resistance by using a crosslinking agent in combination, and to use the adhesive. A polarizing plate of the present invention (for example, refer to the patent document [Patent Document 1], Japanese Patent Laid-Open No. Hei. No. Hei. No. 2005-189.

(Problems to be Solved by the Invention) Refractive Film and Protective Film Requirement In recent years, a polarizing plate has been firmly adhered to with the increase in size of a liquid crystal display device. Furthermore, with the rapid expansion of demand for liquid crystal display devices, productivity improvement has become a major issue. In this step, for example, in the step of bonding the bias to the protective film during the production of the polarizing plate, an adhesive for obtaining sufficient adhesion for a short period of time b in the next step, and an adhesive are required. The enamel agent has a higher volatilization speed and can shorten the adhesive in the drying step. For example, in the case of the latter, in the case where only water is used as a solvent in the adhesive, a low-boiling solvent such as methanol is used in combination. In addition, the adhesives of the PVA-based sapphire containing the acetamidine acetate as the main component described in Patent Documents 1 and 2 were examined in detail by the present inventors, and it was found that the adhesion strength and the adhesive force were observed. There is still room for improvement in terms of speed. Further, in the adhesives described in Patent Documents i and 2, when a water/alcohol mixed solvent is used as the solvent, the solubility decreases as the alcohol content increases, and even if it is in a solution state, the stability is extremely low. Time and 97128578 6 200909891 In the case of white turbidity, thickening/gelling, it is difficult to mix alcohols that are sufficient to increase the volatilization rate. That is, the object of the present invention is to provide an adhesive for a polarizing plate which is used when the polarizing film and the protective film in the polarizing plate are attached to σ, and is excellent in adhesion strength, and can be obtained by transferring to the next step. Adequate adhesion required - an adhesive for polarizing plates which has excellent solution stability when using a water/alcohol mixed solvent.

〇 (the means to solve the problem) ^ Inventors have intensively studied in view of the above situation, and found that f is used to bond the bias region to the protective aid by using the pva containing the structural unit shown in (1). The resin-based polarizing plate is bonded: it can be used for the purpose of the invention, and the present invention has been completed. L1] R1 R3 (1) CC-

X-COOY (wherein, R1, R2, R3, you have eight mouths, tf', and the hydrogen atom or alkyl group which is independent of each other; X is the alkyl group with an inverse number of 4 to 50; γ bauxite, λ The buckle is the following, and the subject matter of the present invention is as follows. 蜀) Π An adhesive for a polarizing plate is a unit of a polyvinyl alcohol-based resin. There are eight types of structures shown in (1) [Chemical 2] 97128578 200909891

(wherein R 1 , R 2 , R 3 are each independently a hydrogen atom or an alkyl group; hydrazine means an alkylene group having a carbon number of 4 to 50; γ means a hydrogen atom or an alkali metal) [2] as in [1] The adhesive for polarizing plates described above, wherein the polyvinyl alcohol-based resin having a unit of a general formula is a copolymer saponified product of a vinyl ester monomer and a compound represented by the general formula (2). (2) R\ /3 c ==cx - cooy (wherein R1, R2, R3 are each independently a hydrogen atom or an alkyl group; lanthanide is an alkyl group having 4 to 50 carbon atoms; The γ is a hydrogen atom or an alkali metal. [3] The adhesive for a polarizing plate according to [2], wherein the compound of the formula (2 系 is undecylenic acid. [4] as [1] The adhesive for a polarizing plate according to any one of the above [3], further comprising a mixed solvent of water and an alcohol solvent having a boiling point of 10 (rc or less) ([5] for the polarizing plate described in [4] Adhesive, wherein water and boiling black. mt: the following alcohol-containing solvent has a h匕 ratio of 99 Λ 30 30 70. [6] For the polarizing plate described in [4] or [5] An adhesive in which an alcohol-based solvent having a boiling black content of 100 C or less is a lower alcohol having a carbon number of 丨 〜3. [] [1] [6] </ RTI> Included in the adhesive for polarizing plates, is $97128578 200909891 A crosslinking agent for at least one selected from the group consisting of a methyl group-containing compound and a glycidyl group-containing compound. [2] The adhesive for polarizing plates described in [7], wherein the crosslinking agent is relatively adjusted. Polyvinyl alcohol resin 1 part by weight [10] The polarizing plate according to any one of [1], the polarizing plate and the protective film of the polarizing plate according to any one of the above [1H8]. The polarizing plate according to any one of [1] [8] is bonded to at least one of the protective films of the polarizing plate of the above-mentioned item. The state-of-the-art resin having the structural unit of the general formula (1) used in the present invention is used for the polarizing film, The protective film has a higher affinity for the rebel, and the bond is at a proper distance from the PVA main chain, so the degree of freedom is high, and the result is good adhesion strength, which is presumed to be fully adhered in a short time. Moreover, even if it is used to increase the water resistance of the adhesive layer and use various cross-linking agents, it is effective to judge the degree of freedom of the carboxyl group. Further, in the case of the PVA-based resin, the alcohol is a poor solvent, even if it is owed. This σ / 谷 卜 仍 仍 仍 仍 仍 仍 仍 仍 仍 仍 仍 仍 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随 随M-based resin with external gate % ratio The water/alcohol mixed solvent can still maintain the state of the stable solution. (Effect of the invention) The adhesive for a polarizing plate of the present invention is excellent even because the adhesion between the polarizing film in the polarizing plate and the protective film of 97128578 200909891 is excellent. In the case of the polarizing plate, good adhesion can be obtained over the entire surface. Furthermore, the adhesive for polarizing plate of the present invention can shorten the step because it can obtain sufficient adhesion in a short time, and even if the solvent is water/alcohol The mixed solvent B temple, because it can still maintain a stable 8-liquid state, can also shorten the drying step and contribute to industrial production. [Embodiment] The description of the constituent elements described below is only an example (representative example) of the embodiment of the present invention, and is not limited to the contents. The following is described in detail with respect to the present invention. The invention relates to a method for producing a polarizing plate for a polarizing plate, a method for producing a polarizing plate using the polarizing plate adhesive, and a polarizing plate obtained according to the manufacturing method. (PVA-based resin) First, the pVA-based resin 使用 used in the adhesive for polarizing plates of the present invention will be described. The PVA-based resin used in the present invention has a PVA-based resin having a unit of the following general formula (丨), and the structure and the production method thereof are, for example, in the Japanese Patent Laid-Open Publication No. 2006-152206. It has been disclosed and belongs to. It is well known, so I would like to make a summary here. [4] R1 R3 - f)- (1)

R2 X-COOY 97128578 10 200909891 In the above general formula (1), R1, R2, and R3 are each independently a hydrogen atom or an alkyl group, X is an alkylene group having a carbon number of 4 to 50, and Y is a hydrogen atom. Or alkali metal. Further, the carbon number of the X is preferably 6 to 3 Å, particularly preferably 6 to 2 Å. In addition, the PVA-based resin used in the present invention is obtained by subjecting a monomer mainly composed of a vinyl ester monomer represented by vinyl acetate to copolymerization, and obtaining a polyvinyl ester-based resin by saponification. (1) The part other than the structural unit shown is the same as the ordinary m-series tree, and the saponification yields the equivalent of the B-structural unit and the amount of the acetic acid-based structural unit. $ 舣8 (1) Μ η is preferably all hydrogen. ? It is also possible to use an organic group for substitution without a large amount of f and a resin property. The organic group is not particularly limited, and is preferably, for example, methylamine, isopropyl, n-butyl or the like. The base of the butyl group, the third butyl group, and the like; and the substituent base such as a 14-base group and a rhein acid group may be optionally used. Preferably, the X in the formula (1) is preferably an alkylene group having a carbon number of 4 to 50, particularly preferably a carbon number of 6, more preferably 6, a pit base. , = is linear, but does not significantly damage the norm m most branched. If the carbon number of the swell base is too small, the adhesion strength or the solubility of the water/alcohol mixed solvent may be reduced. If too much, the adhesion strength is lowered, and the obtained == direction is required. The water is dissolved in water alone, and the solubility of the solvent is lowered. Hand water/alcohol mixture 97128578 In addition, 'the wire is green, in the range of no damage _ characteristics 11 200909891, part of the hydrogen can also use halogen, hydroxyl, ester, carboxylic acid, sulfonic acid Wait for it to be replaced. In the PVA-based resin used in the present invention, the content of the structural unit represented by the general formula (1) is usually 0.1 to 20 mol%, particularly preferably 5 to 15 mol, more preferably 10 mol%. When the content of the structural unit shown in the above formula (1) is too large, the adhesive strength is not good, and when a water/alcohol solvent is used for the adhesive, solubility tends to be insufficient. Further, if the content is too large, the water resistance tends to decrease. (The average degree of polymerization of the PVA-based resin of the present invention (according to the test of the claw u726), the use of _~4, just 300 to 3000, more preferably 500 to 2000. If the degree of polymerization is too small, sufficient adhesion cannot be obtained. In order to improve the viscosity of the adhesive, the workability is lowered, and it is difficult to uniformly apply the substrate to the substrate. The t = the degree of the PVA resin (measured according to JIS K 6726), 98 = 80 Mo·, It is better to use C./ _ 9 mol%. If the saponification yields 彳. Insufficient tendency. 4 If the degree is too low, there is adhesiveness of the adhesive layer. The method for producing the resin, and the PVA-based monomer having no structural unit, and the following general formula (2) 最好 are preferably used in the method of ethylene vinegar. The copolymer of the large (2) non-compound is administered [Chemical 5] 97128578 12 (2) 200909891 R\ R〆

COOY is listed in the above general formula (2). R R , r and X are as in the above general formula (j). Further, γ in the general formula (2) is preferably a hydrogen atom, a metal test, or a burnt group, and particularly preferably a hydrogen atom or a metal test. When a ketone-based vinegar is used, p may undergo a transesterification reaction with a radical of the pvA primary bond in the saponification step in the production of the PVA oxime resin to form a crosslinked structure. In the case of a Y-based alkyl group, for example, an anthracenyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, an octyl group, etc., which are on the saponification reaction day The knot is cut to form a comparable alcohol, and γ is a hydrogen atom or a metal in an alkali metal oxychloride as a saponification catalyst. Therefore, as the base to be used for the hydrazine, it is preferred that the alcohol produced by the secondary production is a methyl group which is often used as a sterol solvent. Specific examples of the compound represented by the general formula (2) include, for example, undecylenic acid, oleic acid, elaidic acid, oleic acid, fennel acid, linoleic acid, linolenic acid, and the like. A derivative such as vinegar or a salt, wherein from the viewpoint of availability, and good copolymerizability, it is preferred that R1, r2, and r3 are gas-derived + enoic acid, and γ is hydrogen. x is a C8Hi6-tert-enoic acid or a metal salt thereof. Examples of the ethylene-based system include, for example, vinyl formate, vinyl acetate, ethyl acetate, ethylene glycol pentoxide, ethyl butyrate, and ethyl acetoacetate. Vinyl citrate, vinyl laurate, stearic acid

97128578 13 200909891 Dilute bismuth citrate, sulphuric acid, vinegar, etc. Among them, from the viewpoint of economy, it is preferred to use vinyl acetate. Further, in the present invention, in addition to the above-mentioned copolymerization component, it is also possible to use a copolymerization of other monomers in such a manner that the other monomers are not inhibited within the range which does not inhibit the object of the present invention. 'Other single systems include, for example, olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, α-octadecene, etc.; 3-butene-bupropanol, 4-pentene 1 Known, 5-hexene-bupropanol, 3,4-dihydroxy-1-butene and other hydroxyl-containing α-olefins and derivatives thereof; acrylic acid, methyl propyl acid, crotonic acid, Maleic acid, maleic acid, itaconic acid, etc., and acids, salts, monoesters, oxime-albufos. κ early 曰Α-alkyl hydrazine, acrylonitrile, methacrylonitrile Acetone, such as acetone acrylamide, acrylamide, methacrylamide, etc., olefins such as ethylene phosphite, allyl tartaric acid, methyl hydrazine, propyl sulfonate, etc.: : its salt; alkyl methallyl ethyl sulphate _, N: vinyl ketone ketone, ethylene ethoxide, ethylene carbonate ethyl thiophene, t: base 4-vinyl ί # burning, glycerin Monomers such as monopropyl propylene m = base + butene; isopropyl acrylate, acetic acid: vinyl acetate, vinyl acetate, etc.; vinylidene chloride gamma lactyl-2-butene, ethylene carbonate, etc. . Further, in the present invention, a mixture of two or more kinds of sin (1) different in polymerization degree, degree of liberation, and content of the structural unit shown may be used. Further, in the range which does not impair the object of the present invention, the side chain to be used for the resin has a PVA resin in combination with the PVA system of the present invention. 97128578 14 200909891 (adhesive for polarizing plate) of J s moon base. Eight persons are described with respect to the adhesive for polarizing plates of the present invention. The adhesive for polarizing plate of the present invention is mainly composed of a PVA-based resin having f per unit represented by the above formula (1), and the content thereof is usually 80% by weight or more of the total solid content, preferably 90% by weight or more. . If the content is too small, there is a case where the adhesion is insufficient. &quot;The sorrow of the adhesive is not particularly limited, but in order to be able to form a uniform adhesion on the surface of the adherend or on the surface of the film, it is preferable to use the liquid-like adhesive in liquid form. In the case of a solution or a dispersion of various solvents, it is preferably a solution type from the viewpoint of coatability to a substrate, and it is generally preferred to use a water-based solution from the viewpoint of safety. Furthermore, after the polarizing plate (four) agent is applied to the adherend, in order to remove the solvent contained in the adhesive agent, a drying step is usually provided, and the adhesive is used for the purpose of shortening the drying step. a solvent which can be easily mixed with water in a solution, and also an alcohol solvent which is formulated to have a lower boiling point than water (i.e., at a point of 1 〇〇C, preferably 80 ° C or less, more preferably 70 or less) A water/alcohol mixed solvent is a preferred embodiment. Specific examples of the alcohol-based solvent include a lower alcohol having a carbon number of 3 such as decyl alcohol, ethanol, n-propanol or .isopropanol. The use of a lower boiling point sterol - the amount of the alcohol solvent is not particularly limited, as long as The drying conditions and the type of the alcohol to be used may be appropriately selected, and usually water has a ratio of two::9/:, two... (weight: two, 99.99/〇.〇i.2〇/8〇, preferably 99/1~3〇/7〇, 97128578 15 200909891 ', the range of ~5〇/5〇. If the amount of the alcohol is too late, there is a tendency for the viscosity stability of the adhesive solution to decrease, if too little, However, there is a case where the effect of shortening the drying step cannot be obtained. Conversely, the solid concentration of the adhesive solution for the polarizing plate varies depending on the + coating, the coating = characteristics, but it is generally preferred. Use 0.5 30% by weight, Tejiab 2〇% by weight, and more preferably i 5~1(10). If the concentration is too low, it will take a long time to dry, so if the damage is too high, the viscosity will increase. Difficult to apply the tendency of uniform sentence coating 0:: The adhesive for the polarizer is 'adhesive force between the polarizing film and the protective film, and the adhesive strength of = can obtain good adhesion in a short time, Soaring adhesion, especially for improving the water-resistance and using various cross-linking agents is also a preferred embodiment. There is a known product which can use a crosslinking agent of m-type wax, or a compound which has a functional group for the reaction of the operator, for example, for example, formic acid, Ethene; urea resin, decylamine, and sulphate compound; amine resin, water 223: cyanamide and other methyl group-containing epoxy group-containing compound, polyamine amine polyamine Alcohol, etc. 1 miscellaneous, ethylamine, hexamethylenediamine, m-xylenediamine, hexanylamine, hexamethylenediamine, hexamethylenediamine, hexamethylenediamine, hexamethylenediamine, hexamethylenediamine, hexamethylenediamine An isobaric compound; a sulphuric acid sulphuric acid or the like; a bismuth compound, and a heat exchanger cross-linking agent, for example, a saponin such as a sphagic acid or a stone sand, 97128578 16 200909891 Zirconium compound such as chlorinated hydroxy hydrazine ("zircosol ZC-2" manufactured by First Least Element Chemical Co., Ltd.) and cerium nitrate ("Zirc〇s〇i 烈" manufactured by First Least Element Chemical Co., Ltd.); tetraalkoxy Titanium compound such as titanate, water-soluble titanium compound ("TC-310" "TC-400" manufactured by Matsumoto Pharmaceutical Co., Ltd.); aluminum sulfate, chlorination , An aluminum compound such as aluminum nitrate; phosphites, bisphenol A modified polyphosphate like filling compound; ketone having a reactive functional group burning compound, glycidyl like. Among them, from the viewpoint of high reactivity and excellent water resistance even in a small amount, it is preferred to use a compound containing a glycidyl group and a compound having a methyl group. The amount of the crosslinking agent to be added is not particularly limited, and may be selected from the desired water resistance and the like. However, it is usually used in an amount of less than 100 parts by weight, preferably 100 parts by weight or less. 5〜50重量份的范围内。 1~1〇〇 parts by weight, more preferably 0. 5~50 parts by weight. If the amount of the crosslinking agent is too large, the viscosity stability of the adhesive solution tends to be deteriorated. Further, within the scope of not impairing the object of the present invention, it is usually 3%, preferably 2. 5% by weight or less and other tree waxes, for example: Dian powder, and, vitamins, glutinous rice; polyethylene glycol, polyvinylpyrrolidine _, polycarbazole:: watery polyamine, water-soluble polyester , a water-soluble resin such as polyacrylamide or polyamine; and an amine formic acid agent. ... 曰糸 者 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Agent, antistatic agent, = 97128578 17 200909891 Surfactant, desiccant, deodorant, antibacterial agent, preservative, defoamer, etc. (Polarizing Plate) Next, the polarizing plate of the present invention will be described. The polarizing film used in the polarizing plate of the present invention is not particularly limited, and known materials can be used. For example, (i) in a vinyl alcohol resin film such as a pVA film, a partially formalized PVA film, or an ethylene-vinyl alcohol resin film, C adsorbs a dichroic material such as iodine or a dichroic dye, and (a) a vinyl alcohol resin film having one of (i) a color material and having a liquid crystal property, for example, a uniaxially-extended product is disclosed in the Japanese Patent Laid-Open Publication No. 2001-296427 For the birefringent material (for example, refer to Japanese Patent Laid-Open Publication No. 2007-72203); (iii) applying a uniaxially stretched thermoplastic resin film containing a dichroic material to a uniaxially stretched product (for example, (i) a polyene-based film obtained by subjecting a PVA-based tree, an ethylene-vinyl alcohol resin to dehydration or deacetation, and introducing a continuous fluorene structure and then extending it ( For example, Japanese Patent Laid-Open Publication No. 20-7-17845, and the like. "In view of the above, from the viewpoint of excellent polarization characteristics, it is preferable to form a polarizing film which is composed of an m-based film and a dichroic material, and which is uniaxially stretched. = The thickness of the film is usually. .w..heart, especially good., better 1~60/zm. It is laminated with the protective film through the adhesive layer. The residence of the film is not particularly limited, but it is usually thicker than Polarizing film 97128578 18 200909891 , 'The substrate of polarizing film has the function of strength, usually 10 100/zm, preferably 20~80#m. This material is good for use and is excellent in durability. The limitation of the most suitable product is, for example, a vitamin ester resin film or a cyclic olefin resin film, a resin film, etc. (meth)acrylic acid is used for the cellulose I resin film. Cellulose § is intended to be resinous, such as triethyl fluorenyl cellulose, diethyl hydrazine cellulose, etc., but other uses such as: low-grade fatty acids of cellulose @,, cellulose acetate acetaminophen or Mixed fatty acid ester of cellulose acetate butyrate, etc. In order to improve the affinity between the polarizing film and the m-type resin used in the seventh embodiment, the I-based resin thin-film system is subjected to a deuteration treatment using an aqueous solution or the like, but is not limited thereto. The electrostatic agent is applied to the surface or is contained in the film. 代表 A representative example of the cyclic vodonic resin used in the above-mentioned cyclic olefin-based resin film is a resin based on a _-based resin. For example, a ring-opening (co)polymer of a pentene-based monomer, a pentene monomer, a polymerization, a resin, and a distillate of a tetrabasic monomer or ethylene or a "sparse hydrocarbon" A resin in which a monomer is subjected to addition copolymerization or the like. Specific examples of the norbornene-based monomer include dimers such as rifene and phenanthrene; tricyclic compounds such as dicyclopentene-i-pentylene; and seven rings such as tetracyclopentadiene And an alkyl group such as a mercapto group such as a thiol group, an ethyl group, a propyl group or a butyl group; an alkylene group such as an ethyl bromide group; an aryl group such as a phenyl group, a phenyl group or a naphthyl group; Substituent; having such hydroxy, scaly, cyano, _, alkoxy, pyridyl, hydroxy, carboxylic acid, amine, anhydride, decane 97128578 19 200909891, epoxy, A substituent containing a group other than carbon or hydrogen, such as an acrylonitrile group or a methacrylium group. The commercially available product of the cyclic olefin-based tree (four) film is, for example, "ART0N" manufactured by the company, "ZE〇N〇R" manufactured by Nippon Paint Co., Ltd., "ΖΕ〇ΝΕχ", and "0PT0REZ" manufactured by Hitachi Chemical Co., Ltd. Mitsui Chemical Co., Ltd. made "ship" and so on. Further, the (meth)acrylic resin used in the (meth)acrylic resin film may, for example, be a poly(meth)acrylate such as polymethyl propyl ketone or methacrylate; Ester-(meth)acrylic acid copolymerized human body, methyl methacrylate-(meth)acrylic acid oxime copolymer, methyl propyl acrylate-acrylate-(fluorenyl) acrylate copolymer, (A Methyl acrylate-styrene copolymer, polymer having an alicyclic hydrocarbon group (for example, methyl methacrylate-mercapto acrylate ring copolymer, methyl propyl methyl sulfonate) acrylic acid An alkyl ester copolymer, such as an alkyl ester copolymer or the like, or a ruthenium Tg (methyl) propyl benzoate, a rubber-acrylic acid graft type core-shell polymer obtained by intramolecular crosslinking or intramolecular cyclization. . For example, "Acrypet VRL20A" manufactured by Mitsubishi Rayon Co., Ltd., "Acrypet IRD-70", "MUX-60" manufactured by UMGABS Co., Ltd., and the like are commercially available. In addition to these protective films, polyester resin films such as polyethylene terephthalate or polyethylene naphthalate; polystyrene, acrylonitrile and styrene copolymers; Polystyrene resin film such as a composite; polyolefin resin such as polypropylene; polyaromatic resin film, water-soluble polyether sulfone resin film, polycarbonate resin film, vinyl chloride resin film, nylon, aromatic A phthalamide-based resin film such as a polyamine or a fluorene-based resin film; (fluorinated) poly phthalimide 97128578 20 200909891 A resin film, a polyetheretherketone resin film, a polyphenylene sulfide resin film, a vinyl alcohol resin film, and a second A polyvinyl acetal resin film such as a vinyl chloride resin film or a polyethylene condensate; a poly aryl vine resin film, a polycondensation resin film, or an epoxy resin film. Further, as the protective film, for example, a thermosetting type such as a propylene glycol-based, an urethane-based, an urethane-based urethane, an epoxy-based or an anthraquinone-based, or an ultraviolet-curable resin can be used. * or a polymerization film as described in Japanese Patent Laid-Open Publication No. Hei No. 343529, which specifically comprises a mixture of isobutylene and N-methylmaleimide, and a copolymer of acrylonitrile. Resin film of phenethyl ether copolymer). In the protective film, it is preferable to use a total hydrocarbon cellulose resin film or a cyclic olefinic product from the viewpoints of transparency, heat resistance, mechanical strength, durability, and the like. , 曰 /, 'especially with diethyl phthalocyanine, or a slightly lowering of the resin for the purpose of improving the affinity with the polarizing film or as an adhesive to make ϋ ^, / can also be applied to various surface treatments In addition, in addition, in addition to the polyester I-based resin film, the latex-based cattle are listed on the surface of the protective film, containing (meth) acrylate, B. An imine, a polyurethane condensate/polymerization method, an ion-assisted method (for example, a layer method, a method using a method of imparting hydrophilicity to a surface of a corona discharge surface), and the like, and a surface method at the surface of the surface. Further, the above-mentioned respective 97128578 21 200909891 may be used in combination, and the protective film may be provided with a hard coat layer on one side not provided with the polarized light absorbing layer, or various treatments such as anti-sticking, anti-reflection, and anti-glare. Further, various optical functional films such as a retardation film and a viewing angle expansion film may be laminated on one surface which is not laminated with the polarizing film. In the polarizing plate of the present invention, at least one of the polarizing films (preferably on both sides, the transparent protective film is bonded by the adhesive for polarizing plates of the present invention, and thus the polarizing plate adhesive of the present invention is usually uniformly coated. After being coated on a polarizing film or a preservative film or on the other side, the two are bonded together and then crimped and formed by heating and drying. ' When the polarizing plate is coated with an adhesive on a polarizing film or a protective enamel , such as: 軚 coating method, pneumatic knife coating method, knife coating method, spray method, dipping method, or just before the polarizing film and the protective film are bonded, = should be and flow into the thin raft. The known method of laminating the two is as follows: The coating amount of the aqueous adhesive is dry (four), usually from 0.01 to 1 〇 / zm, particularly good n ^ a and degree Ο the thickness is too thin, then If there is a sticking force, it is not fixed. If the tendency of the male is insufficient, if it is too thick, it will be difficult to send T unevenness and the appearance will be worse. In the fitting and C picking up... use For example, the roll laminator and so on are selected within 0.1-... In addition, the tender; the force 5~air, the special good Qin boots, according to _ points ^ = The condition of the score of 20 points is divided into 30 minutes. [Embodiment] The following is a description of the embodiment of the present invention. The more the subject matter is, the more the handle is not the handle. Guardian is not limited to the description of the application. 97128578 22 200909891 In addition, in the examples, 'parts' and '%' refer to the weight basis without any special statement. ' [Example 1] (l) PVA Production of a resin in a reaction tank having a reflux condenser, a dropping funnel, and a stirrer, and loading 100 g of vinyl acetate, 5 g of decyl alcohol, and undecylenic acid (in general formula (2), R, R, R is hydrogen, X-C8Hi6-, Y-hydrogen) 85.6 g (4 mol/〇), and is charged with azobisisobutyronitrile. 1 mol% (relative to the charged vinyl acetate single) The mixture was heated under a nitrogen stream while stirring = polymerization was carried out. After 2 hours from the start of the polymerization, azobisisobutyronitrile was added to 1 mol% (relative to the initial loading of vinyl acetate). Then, the polymerization is continued. Then, when the polymerization rate of vinyl acetate reaches 62.5%, it is filled into the polymerization end. The polymerization was terminated with a stopper. Then, the unreacted vinyl acetate monomer was removed to the outside of the system by a method of blowing methanol vapor to obtain a methanol solution of the total solution. Next, the solution was adjusted with methanol to adjust to The concentration was 30% and charged in a kneader. In the case where the temperature of the solution was maintained at 40, a 2% methanol solution of sodium hydroxide was added, and the molar unit of vinyl acetate in the copolymer was 8 m. The saponification is carried out in the amount of the molar amount, and the saponified product is precipitated and finally becomes a particulate form. The produced pvA is filtered, thoroughly washed with methanol, and dried in a hot air dryer. The saponification degree of the obtained PVA-based resin (1) was analyzed by the amount of alkali consumption required for the hydrolysis of the residual vinyl acetate unit, and the result was 99 97128578 23 200909891 mole %' polymerization degree was JISK6726 performed the analysis and the result was 1〇〇〇. Further, the modified mass of the PVA-based resin (1) was calculated by NMR measurement and found to be 4 mol%. (2) Preparation of an adhesive for a polarizing plate: (1) A 6.55% aqueous solution of a PM resin obtained in (1), 52 parts of methanol, 47.5 parts, and a polyamine amine polyamine gas as a crosslinking agent The parts were mixed to prepare an adhesive solution having a solid moisture content of 5% by weight and a hydroalcohol ratio to weight ratio. (3) Production of evaluation sample = Membrane 3 is a biaxially stretched film of PVA ("Ship (10)", thickness 25 (four)), which is obtained by Sakamoto Synthetic Industrial Co., Ltd., and the adhesive liquid material obtained in 1 The surface of G8g/m2 is then laminated as the surface of the protective film by deuteration treatment dimension = thickness 8 a), and the lamination machine _: = calendar - 65GY", laminating light pressure G lMPa) is applied, and then Execute the (4) Jane for 5 minutes in the dryer. The thickness of the dry layer is 0. 8 /Z m. Adhesive agent for T (4) Evaluation For the adhesive sample for polarizing plate obtained in (7), the following evaluation was carried out. The results are shown in Table i. Also in Pingping [adhesive stability] 'The adhesive is stored at room temperature, and the time until gelation is visually observed and evaluated as follows: See white turbidity or condensation A · · · - Week above 97128578 24 200909891 5 days or more, less than 7 days C. · · 3 days or more, less than 5 days D · · · less than 3曰 [adhesive strength] = After the evaluation sample is prepared, in the environment of 23〇C, 60% RH After storage for 24 hours, the sample was cut to a width of 25 mm, and a _ peeling test (test speed 300 mm/^7) was performed. The same test was carried out for 1 ,, and the number of places where the material broke due to the biaxially stretched film was evaluated as follows. Further, the term "material breaking rate" as used herein means the ratio at which the PVA biaxially stretched film is cracked in the strength measurement. A · · · Material breaking rate is 90% or more B · · · Material breaking rate is 80% or more, less than 9〇% C · · · Material breaking rate is 70% or more, less than 80% D · · · Material breaking rate is not full 7〇% [adhesive performance time]

Q After the evaluation sample is prepared, the time for peeling off by hand is performed at intervals, and evaluation is performed as follows. A · · · β 〇 within 23 ° C, 60% RH environment, every 'measurement until the material breaks β · · · more than 60 minutes, but within 90 minutes C •• more than 90 minutes, but 12 〇 In the case of the yoke example 1, except for the amount of methanol in the preparation of the PVA-based resin, 9712,285,78, 2009, 2009, 891, 20,0Og, the use amount of the eleven acid was changed to the polymerization. The rest are as shown in Fig. 1 (1). The structure of the single (four) is a pVA-based resin having a content of 2%, a general formula of -76, a degree of polymerization, and a degree of polymerization of 99%. Next, an adhesive for a polarizing plate was obtained as in Example i except that it was used as a crosslinked-substituted (tetra)amine polyamine epichlorohydrin, methylated melamine was used, and the water/methanol ratio was changed to &amp; , the same S flat evaluation. The results are shown in Table 1. [Example 3] Except that in Example i, the amount of methanol in the production of the PVA-based resin was changed to 85.6%, and the structural unit shown in the general formula U) was obtained as in the embodiment. A PVA-based resin having a content of 4 mol%, a degree of polymerization of 500, and a degree of saponification of 9 9 mol%. Then, except that the substituted methanol was changed to 47 5 Torr of water, and it was not blended with the polyvinyl alcohol, the same evaluation was carried out as an adhesive for a polarizing ruthenium plate. The results are shown in Table 2. [Comparative Example 1] In the first embodiment, a PVA-based resin containing an acetamethylene acetate* ester group was used as the PVA-based resin (acetamidine acetate group content: 5 mol %, polymerization degree • 1100, saponification degree) The same evaluation was carried out as the adhesive for the polarizing plate was obtained as in Example i except that the ratio of the crosslinking agent was glyoxal and the ratio of the diterpene alcohol was set to 8/2. The results are shown in the table. [Comparative Example 2] In the first embodiment, as the PVA-based resin, maleic acid was used, and all of the polymerized PVA-based resin (the maleic acid structural unit content was 2 mol %, the combined degree was 1200, and the saponification was used). Degrees 99. 2 Mo Er Xi Sun, Li Cong, ^ 杲 Fight, the rest of the same as in Example 1, obtained the adhesive for polarizing plates, the same evaluation was carried out. The results are as shown. ... [Table 1]

Embodiment 1 Embodiment 2 Embodiment 3

A A A

A A B

AA Comparative Example 1 1) (gelation) Comparative Example 2 D (gelation) Various modifications and corrections can be made to the present invention without departing from the spirit and scope of the present invention. Those who are familiar with this technology can easily think about it. This case is a Japanese patent application filed on July 30, 2007.

Based on the case (Japanese Patent Application No. 2007-1 96959), the contents of which are cited as references: (industrial availability) ^ The adhesive for polarizing plates of the present invention is excellent in adhesion strength, and thus the polarizing film and the protective film are difficult to be used. |彳_, it is possible to obtain sufficient adhesion in M time, thus shortening the manufacturing steps. Further, even when a water/alcohol mixed solvent is used, since the stability is excellent, the drying step after the application of the adhesive can be shortened. 97128578 27

Claims (1)

200909891 X. Patent application scope: It contains a structure represented by the general formula (1). 1. A polyvinyl alcohol-based resin for a polarizing plate; a unit of a polyvinyl alcohol-based resin; [Chemical 1] rr (1) C--c X -COOY wherein R1, R2, and R3 are each independently a hydrogen atom or an alkyl group; x is an alkylene group having a stone-penetration number of 4 to 50; and γ is a hydrogen atom or an alkali metal). The adhesive for a polarizing plate according to the first aspect of the patent specification, wherein the polyvinyl alcohol-based resin having a structural unit represented by / buckled () is a copolymerized product of a vinyl ester fit sheet and a compound represented by the general formula. Compound R1\ C = C R2〆/3 \ x—cooy (2) Work, R, R are independent hydrogen atoms or alkyl groups; they are alkyl groups with a carbon number of 4 to 50; γ is a hydrogen atom or The alkali metal 3. The adhesive for polarizing plates of claim 2, wherein the compound represented by the general formula (2) is undecylenic acid. 4. If you apply for a patent scope! The adhesive for the polarizing plate of the item is a mixed solvent of the alcohol solvent of the coffee or the following. 5. The adhesive for polarizing plates according to item 4 of the patent application, wherein the content ratio of the alcohol solvent below 1 g of water is 99128578 28 200909891 is 99/1 to 30/70. 6. The adhesive for polarizing plates according to item 4 of the patent application, wherein the alcohol solvent of the following point is a lower alcohol of carbon number 3. 7. For example, apply for a patent (4)! The polarizing plate of the present invention is characterized in that the adhesive (four) contains at least one selected from the group consisting of a methyl group-containing compound and a glycidyl group-containing compound. 8. For the adhesive for polarizing plates of claim 7 of the patent application, The blending amount is 0.1 to 100 parts by weight based on 1 part by weight of the polyvinyl alcohol-based resin. Any one of the first to eighth films is a polarizing plate for at least one of the polarizing plates, and is an adhesive for a polarizing plate, a polarizing film, and a protective film according to the scope of the patent application. 10. A method of producing a polarizing plate, which is applied to a polarizing film by using any of the applicants in the scope of the patents No. 8 to 8. U 97128578 29 200909891 VII. Designated representative map: (1) The representative representative of the case is: No (2) The symbol of the representative figure is simple: No C 8. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: [Chemical 1] R1 R3 —(-C—C-)— (1) \ | I 1 R2 X-COOY 97128578 4