TW201207060A - Adhesive composition for polarizer and polarizer using the same - Google Patents

Abstract

This invention provides an adhesive composition for a polarizer and a polarizer using the same with excellent adhesiveness and improved warm water tolerance under a wetted and heated condition and can inhibit generation of the breakage point. The adhesive composition for a polarizer comprises acetoacetyl-modified polyvinyl alcohol (PVA) resin, water, alcoholic solvent with a boiling point less than 100 DEG C, and glyoxylate represented by the formula as below. Based on 100 parts by weight of water, the composition comprises 1 to 8 parts by weight of acetoacetyl-modified polyvinyl alcohol resin, wherein the weight ratio between acetoacetyl-modified polyvinyl alcohol resin and glyoxylate solid content is 1:0.03 to 1:0.25, the weight ratio between water and alcoholic solvent is 99:1 to30:70, and pH is 4 to 10, wherein M represents alkali metal or alkaline earth metal and n is 1 or 2.

Description

201207060 VI. Description of the Invention: [Technical Field] The present invention relates to an adhesive composition for a polarizing plate and a polarizing plate using the same, and relates to an excellent adhesion and resistance under humidification and heating conditions. The adhesive composition for polarizing plates and the polarizing plate using the same can be used to suppress the occurrence of cracks (kmek). [Prior Art] In terms of the image forming method of the liquid crystal display device, it is necessary to arrange a polarizing element on both sides of the surface glass substrate on which the liquid crystal panel is formed. The polarizing element is obtained by dyeing the three-color material (four) poly (10) film, such as (4), and then cross-linking with a crosslinking agent and uniaxially stretching to form a film. Since the polarizing element is produced by stretching, it is easy to shrink. Further, since the polyethylene-based film is made of a hydrophilic polymer, it is easily deformed by non-invasiveness under humidification and heating conditions. Further, since the mechanical strength of the film white film itself is weak, there is a problem that the film is broken. Therefore, it is advantageous for the polarizing plate which is strong in strength and strong in strength on both sides of the transparent sighing member such as triacetonitrile cellulose or on one side. This kind of creation. ^The first 7" pieces and the transparent protective film are followed by two =) = two... end machines Each use forms its own specifications. ::= To be widely promoted' and based on the premise that the user carries the belt: the use of the opposite end. Because of KI, the requirement for durability is not a good name. 1 Q, the polarizing plate is required to have a temperature-resistant water content even if condensation or ° does not change. Characteristics under conditions of ～, , and , 〇 3 201207060 Polarized 7L parts are made of a polarizing plate by using a protective film to enhance the strength. The adhesive for polarizing plate used for the light 7L member and the protective film is preferably an adhesive, for example, a polyethylene glycol-based adhesive which is used in a polyvinyl alcohol aqueous solution mixed with a crosslinking agent. Among them, the polyvinyl alcohol-based adhesive may be peeled off at the interface between the polarized 7L member and the transparent protective film under humidification and heating conditions. It is considered that 2 is because the polyvinyl alcohol-based resin which is a main component of the adhesive is water-soluble and may cause dissolution of the adhesive when it is condensed. In order to solve the above problem, an adhesive for a polarizing plate containing an ethylene glycol-based modified polyvinyl alcohol-based resin and a parent-linked agent has been proposed. On the other hand, when a polarizing plate is produced, there is a problem that cracks occur when a polarizing element and a transparent protective film are passed through a polyvinyl alcohol-based adhesive. The crack point is a local unevenness defect generated at the interface between the polarizing π piece and the transparent protective film. The cracking point is particularly likely to occur in the case where an ethyl ethoxylate-modified polyvinyl alcohol-based resin is used as the polyvinyl alcohol-based adhesive. Therefore, it has been demanded to develop an adhesive composition for a polarizing plate which exhibits high adhesion and water resistance and can suppress the occurrence of cracks. SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide an adhesive for an polarizing plate which is excellent in adhesion and temperature resistance under humidification heating conditions and which can suppress generation of cracks. And a polarizing plate using the same. An adhesive composition for a polarizing plate according to one aspect of the invention of the present invention, which comprises an ethyl acetonitrile-modified polyvinyl alcohol-based resin, water, an alcohol-based solvent having a boiling point of less or less, and a chemical formula below The glyoxylic acid salt is represented, and comprises from 1 to 8 parts by weight of an ethylene acetylated modified polyvinyl alcohol-based resin relative to 100 parts by weight of water, and the acetylated group is modified.

S 201207060 The weight ratio of the solid content of vinyl alcohol resin and glyoxylate is i: 〇〇3 to 1. 0.25 'The weight ratio of water to alcohol solvent is 99 : 1 to 3 〇: 7 〇, yang is 4 To 10: 1/η Κ/Γ HCC-0-II II 0 〇 where 'Μ denotes an alkali metal or alkaline earth metal, η is 1 or 2. The polarizing plate was made of an adhesive composition at 2 Torr. (The viscosity is 3 to 25 mPa.seC. The alcohol solvent may be a lower alcohol having a carbon number of 1 to 3, especially ethanol. The weight of the water and the alcohol solvent is preferably 95: 5 to 50: 50. Another aspect of the present invention provides a polarizing plate comprising a polarizing element, and a protective film for an adhesive composition for a polarizing plate according to an aspect of the invention, which is followed by at least one side of the polarizing element. The protective film may comprise a cellulose selected from the group consisting of cellulose. At least one of a resin, a cycloolefm resin, a polyethylene terephthalate resin, and a (meth) acrylate resin. According to the present invention, the polarizing element and the protective film are Further, since the strength is excellent, it is excellent in the adhesiveness and the temperature-resistant water under the humidification heating condition, and since the alcohol-based solvent having a boiling point of 100 ° C or less is contained, the occurrence of cracks can be suppressed. Increasing the productivity of the step of producing a polarizing plate by using the composition for a weaving adhesive of the present invention, and improving the productivity. [Embodiment] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. The embodiment may be modified into various other forms, and the scope of the invention is

S 201207060 is not limited to the embodiments described below. The embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art. The adhesive composition for a polarizing plate of the present invention, which comprises an ethylene acetylated modified polyvinyl alcohol resin, water, an alcohol solvent having a boiling point of 1 001 or less, and glyoxylate, and is relative to 100 parts by weight. The water 'containing 1 to 8 parts by weight of the ethyl acetonitrile-modified polyvinyl alcohol-based resin, and the weight ratio of the ethyl acetate-modified polyvinyl alcohol-based resin and the solid component of the glyoxylate is 1:0 03 to 1 : 〇25, the weight ratio of water to alcohol solvent is 99: 1 to 30: 70, and the pH is 4 to 1 〇. The adhesive composition for a polarizing plate of the present invention is used for a polarizing plate, and the polarizing plate-based polarizing element is produced by adhering a protective film to at least one surface of the polarizing element. At this time, the adhesive composition for a polarizing plate of the present invention is applied to either side of the polarizing element, followed by a protective film. The form of the adhesive composition for a polarizing plate is not particularly limited, and it is preferably used in a liquid form in order to form a uniform adhesive layer on the surface of the protective film of the adherend. Such a liquid adhesive may, for example, be a solution or a dispersion of various solvents. The coating property to the substrate is preferably a solution type, and in terms of safety, it is generally suitable to use water as a main component. Solution. The adhesive composition for a polarizing plate contains a resin, water, an alcohol solvent, and a crosslinking agent. The resin used in the adhesive composition for a polarizing plate of the present invention is an ethyl acetonitrile-modified polyethylene glycol-based resin. Since the ethyl hydrazide-based modified polyvinyl alcohol-based resin is a polyvinyl alcohol-based adhesive having a highly reactive functional group, when an ethylene-ethyl fluorene-modified polyvinyl alcohol-based resin is used, polarized light is used. The durability of the board is improved. The ethyl acetonitrile-modified polyvinyl alcohol-based resin is obtained by reacting a poly-S. 6 201207060 acetol-based resin with diketene by a known method. Examples of the polyethylene glycol-based resin include a polyethylidene alcohol obtained by saponifying polyvinyl acetate and a derivative thereof; a saponified product of a copolymer of vinyl acetate and a copolymerizable monomer, and a polycondensation A modified polyvinyl alcohol obtained by shrinking ethylene glycol, urethane, shouting, grafting or phosphating. The above monomers include unsaturated carboxylic acids such as cis-butyl dioxime (anhydride), anti-butyric acid, butyric acid, itaconic acid, (sub)acrylic acid, and esters thereof; Ethylene such as ethylene or propylene, (meth)allylsulfonic acid (sodium), sodium sulfonate (single alkyl maleate), sodium disulfonate maleate, hydrazine - Hydroxymercapto acrylamide, acrylamide alkyl sulfonate base salt, hydrazine-vinyl pyrrolidone or fluorenyl vinylpyrrolidone derivative, and the like. The polyethylene glycol-based resin may be used alone or in combination of two or more. The polyvinyl alcohol-based resin is not particularly limited, and in terms of adhesion, the average degree of polymerization is from 100 to 5,000, preferably from 1 to 4, and the average degree of saponification is from 85 to 1 Torr. %, preferably 9〇 to 1〇〇% by mole. It is obtained as described above using known ones.醯 醯 醯 醯 醯 制造 : : : : : : : : : : : : : : : : : : : : 预先 预先 预先 预先 预先Further, a method of making bis-sterol can also be used. If the degree of modification of the acetaminophen is less than 0.1 mol%, it is appropriate. Ethyl acetate-based modified polyvinyl alcohol-based resin method for reacting a polyvinyl alcohol-based resin with a diketene-modified polyvinyl alcohol-based resin, for example, by dispersing the following enol-based resin in acetic acid or the like In the solvent, a polyvinyl alcohol-based resin is dissolved in a dioxonium in advance, and a ketene gas or a liquid diketene is directly contacted with a polyvinylidene-based modified polyvinyl alcohol in a method in which a diketene is added thereto. The resin is not particularly limited as long as it is at least G] mol%, and the water resistance of the adhesive layer is insufficient, so that it is uncomfortable.

S 201207060 preferably has a quality of about 0.1 to 40 mol%, more preferably i to 2 mol%, and particularly preferably 2 to 7 mol%. If the degree of modification of the ethyl hydrazide group exceeds 40 mol%, the effect of improving the water resistance is small. The degree of modification of the B-brewed base is determined by the value measured by Li & The solvent-based water used in the adhesive composition for a polarizing plate of the present invention and an alcohol-based solvent having a boiling point of 100 C or less. In the present invention, since an alcohol-based solvent having a very low surface energy is used as a solvent in addition to water, the surface energy of the adhesive is lowered to suppress the occurrence of cracks. As the surface energy of the adhesive decreases, the local unevenness generated at the interface between the polarizing element and the protective film is buried, whereby the occurrence of cracks can be avoided. After the application to the adherend, in order to remove the solvent contained in the adhesive, a drying step is usually carried out. If the water is mixed with the alcohol in the adhesive solution as in the present invention, the drying step can be shortened. The alcohol solvent has a lower boiling point than water, that is, 1 point at 4 points. (The following, especially 80 ° C or less, may be 7 (rc or less. The alcohol solvent may be a lower alcohol having 1 to 3 carbon atoms. Specific examples of such an alcohol solvent include decyl alcohol 'ethanol, positive An alcohol having 1 to 4 carbon atoms such as propanol, isopropanol, i-butanol or 2-butanol. The alcohol-based solvent may especially be ethanol. The amount of the alcohol-based solvent is not particularly limited, and is in water and The ratio (weight ratio) of the two of the mixed solvents of the alcohol-based solvent is preferably in the following range: 9:1 to 30:70, preferably 95:5 to 50:50, more preferably 90: 10 to 80: 20. If the content of the alcohol-based solvent is too large, the solubility of the resin may decrease or the viscosity of the adhesive solution may decrease. If the amount is too small, the effect of suppressing the occurrence of cracks may not be obtained. The crosslinking agent used for the adhesive composition of the polarizing plate is the glyoxylate represented by the following Chemical Formula 1 of 201207060: H—C—C~0 Λ II II 1 /η Μ Ο Ο Metal or soil test metal, η is ι or 2. The acid salt is the metal salt or soil test metal salt of the acid. The metal and soil test metal It is an element with a lower anion property, and its carboxylic acid has similar chemical properties, so it exhibits excellent performance as a crosslinking agent of ethylene glycol-modified polyvinyl alcohol. Glyoxylic acid is presumed from the aldehyde portion of glyoxylate. The alkali metal salt and the alkaline earth metal salt are those having the same effect. The specific compound of the glyoxylate of the chemical formula 1, for example, if the ruthenium is an alkali metal, there are lithium glyoxylate, sodium glyoxylate and B. Potassium aldehyde or the like, if strontium is used as the soil for soil inspection, there are magnesium oxalate, sulphuric acid, acetic acid, and bismuth ethoxide. Among them, it is preferred to consider the viewpoint of being easily soluble in water. The alkali metal salt is preferably sodium glyoxylate. The method for producing the glyoxylate is not particularly limited, and a known method can be preferably used, and the method is preferably used, which is easy to manufacture and easy to purify. The aldehyde acid is neutralized and reacted with an alkali metal hydroxide or an alkaline earth metal hydroxide. The adhesive composition for a polarizing plate of the present invention is a mixed solution of a water/alcohol solvent, and an ethylene acetylated modified polyethylene is dissolved. The mixture of alcohol resin and glyoxylate In solution compositions, acetyl acetyl group modified polyvinyl alcohol-based material of the said month / e of water with respect to 1 part by weight may be in the range of 1 to 8 parts by weight.

9 S 201207060 When the concentration of the ethylene-based modified polyvinyl alcohol-based resin is less than 1 part by weight based on 100 parts by weight of the water/alcohol mixed solution, the adhesion tends to decrease, and When the concentration of the fluorene-modified polyvinyl alcohol-based resin exceeds 8 parts by weight based on 100 parts by weight of water, the optical characteristics of the polarizing plate tend to be lowered. The amount of the acetonitrile-modified polyvinyl alcohol-based resin to 100 parts by weight of the mixed solution of the water/alcohol-based solvent is preferably 5 parts by weight. The weight ratio of the ethyl acetate-modified polyvinyl alcohol-based resin to the solid content of the glyoxylate is in the range of 0.03 to 0.25 with respect to the ethyl acetylated modified polyvinyl alcohol-based resin 1. The reason is that when the weight ratio of the glyoxylate to the ethylene-vinyl modified resin is less than 〇〇3, the water resistance of the subsequent layer is difficult to be sufficiently expressed, and The weight ratio of the acid anhydride to the ethylene glycol modified polyethylene resin is more than that of the 〇·25, and the compatibility of the polarizing plate is liable to decrease. Further, in terms of the balance between water resistance and adhesion, the weight ratio of the ethyl phthalate-modified polyvinyl alcohol-based resin to the solid component of the glyoxylate in the adhesive composition is better. For 1 ·· 〇 still to the extent of 0.2. Further, the adhesive composition for a polarizing plate is used in a pH range of 4 to 1 Torr. The reason for this is that when the pH of the adhesive composition for a polarizing plate is less than 4, the water resistance in the state of the polarizing plate cannot be sufficiently exhibited, and when the pH of the adhesive composition for a polarizing plate exceeds 1 Torr, The polarizing plate is shortened by the pot life of the aqueous solution of the adhesive (poUife). From the viewpoint of the safety of the operation, it is preferable that the pH of the adhesive composition for a polarizing plate is 8 or less. The polarizer has an adhesive composition of 20. (The viscosity is preferably in the range of 3 to 25 mPa · sec. The reason is that when the viscosity of the adhesive composition 201207060 of the polarizing plate is less than 3 mPa·sec, the water resistance of the polarizing plate cannot be sufficiently exhibited. When the viscosity exceeds 25 mPa · sec, the optical properties of the polarizing plate are liable to decrease. The adhesive composition for a polarizing plate may further contain a water-soluble catalyst. The water-soluble catalyst which can be used in the present invention may, for example, be piped , pyrrolidine, zinc chloride, cobalt chloride, magnesium chloride, ammonium chloride, cerium oxide, alkyl iodide, etc. In the case of formulating a water-soluble catalyst, it is preferred to make the solid content of the catalyst relative to acetamidine The weight ratio of the acetyl group-modified polyvinyl alcohol-based resin i is in the range of 〇〇〇5 to 0.2. The adhesive composition for a polarizing plate of the present invention may contain, for example, a plasticizer insofar as the effect is not inhibited. An additive such as a decane coupling agent, an antistatic agent, or a leveling angent. According to another aspect of the present invention, an adhesive composition comprising a polarizing element and an adhesive composition using the polarizing plate according to an aspect of the present invention can be provided. The polarizing plate of the polarizing element of the present invention is produced by a protective film comprising a transparent tree or a two-layer layer of a polarizing element comprising a polyethylene glycol-based resin. After the electroconductive layer contains an aqueous solution of an ethylene glycol-based modified polyvinyl alcohol-based m曰 and a salt of a salt, that is, an adhesive composition, and the polarizing element film is bonded to the protective film, the film is dried to form a polarizing plate. The thickness of the layer is not particularly limited, and is usually 0 0015 #m, preferably 〇.〇12 (four) more = 0. 03 to 〇.5 core. When the thickness of the adhesive layer exceeds, the polarizing plate is easily generated. The polarizing element including the polyvinyl alcohol-based resin is specifically a one in which a uniaxially-stretched polyethylene resin film is adsorbed and aligned with a dichroic dye. The polyvinyl alcohol-based resin constituting the polarizing element 201207060 It is obtained by making poly(vinyl acetate) resin into a resin. The polyvinyl acetate resin 'except for the homopolymer of vinyl acetate, ie, 'B, vinyl vinegar' can also be exemplified by vinyl acetate. Polymerized other early copolymers, etc. Other monomers copolymerizable with vinyl acetate include, for example, saponification degree of a vinyl resin such as an unsaturated sulphuric acid-unsaturated acid, a rare hydrocarbon, an etherified ether, or a acrylamide having a recording group. 8 to (10) mol% or so, preferably 98 mol% or more. The above polyethylene glycol resin can be further modified, for example, it can also be modified to a polytype of polyformic acid or polyethylene. Further, the polymerization degree of the polyethylene (tetra) alcohol is usually from 1, _ to about 0,000, preferably from about 15 Å to about 5 Å. The obtained polyethylene (tetra) resin is obtained by film formation. The disk film of the polarizing element may be formed. The method of forming the polyvinyl alcohol-based resin is not particularly limited, and the film may be formed by a method known in A. The film thickness of the polyvinyl alcohol-based disk film is not particularly limited. For example, it is about 10 m to 150 # m. The polarizing element is usually manufactured by the following steps: the film f-axis is pulled by a dichroic dye to the polyethylene glycol::: the step of adsorbing the coloring pigment; a step of a polyethylene resin-based resin film of a pigment; and a step of washing with water after treatment with the erlot liquid. The early axial stretching can be carried out before the dyeing, or simultaneously with the dyeing, or the tingling is carried out in the case of uniaxial stretching after dyeing, and the uniaxial stretching can be carried out before the acid removal treatment. Can be carried out during meal processing. Of course, Tian is uniaxially stretched in several stages. The uniaxial stretching can be applied, for example, to a method in which the peripheral speed is different on the single axis (four). Moreover, it can be a method of stretching by uniaxial stretching using a hot roller of 12 201207060, or stretching, or stretching by a dry pull τ such as stretching in a hu-'milk of milk, which is a magnification of stretching by an agent. Usually about 3 to 8 times. Stretch wet stretching. The good dye is dyed with a poly(ethylene glycol) resin, for example, a medium color: an alcohol resin film is immersed in an aqueous solution containing a dichroic dye. In the case of using a dichroic dye in advance, and in the case of using a dichroic dye, the iodine content in the aqueous solution is usually 1 to 1 in which the polyvinyl alcohol (tetra) lipid film is impregnated with an aqueous solution containing angstrom. 〇〇 The weight of water is 〇〇... To ^* left ^8' left Γ 之 之 之 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 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 水溶液 5 Left and right, and the immersion time (dyeing time) in the aqueous solution is usually 20 to 1,80 sec. On the other hand, in the case of using a dichroic organic dye as a dichroic dye, a method of dyeing a polyvinyl alcohol-based resin film by an aqueous solution containing a water-soluble dichroic organic dye is generally employed. The content of the heterochromatic organic dye in the aqueous solution for dyeing is usually from 4 to 10 parts by weight, preferably parts by weight, per part by weight of the water. The above aqueous solution may also contain an inorganic salt such as sodium sulphate as a dyeing aid. The temperature of the dye aqueous solution used for dyeing is usually about 2G to (10), and the immersion time (dyeing time) in the aqueous solution is usually from 1 Torr to 00 sec. The boric acid treatment after dyeing with the dichroic dye is carried out by dipping the dyed polyvinyl alcohol resin film into an aqueous solution containing an acid. The amount of boric acid in the aqueous solution containing boron 13 201207060 is usually from 2 to 15 parts by weight, preferably from 5 to 12 parts by weight, per 100 parts by weight of water. When iodine is used as the clearing of the dichroic dye, the aqueous solution containing boric acid preferably contains potassium iodide. The amount of potassium iodide in the aqueous solution containing boric acid is usually from 1 to 15 weights per 100 parts by weight of water, preferably from 5 to 2 parts by weight. The impregnation time for the aqueous solution containing boric acid is usually from 60 to 1,200 seconds, preferably from 15 to 6 seconds, more preferably from 200 to 400 seconds. The temperature of the aqueous solution containing boric acid is usually 5 〇 β 〇 or more, preferably 50 to 85 ° C, more preferably 60 to 80 ° C. The polyvinyl alcohol-based resin film after the boric acid treatment is usually subjected to a water washing treatment. The washing treatment is carried out, for example, by impregnating a boric acid-treated polyvinyl alcohol-based resin film with water. The temperature of the water during the water washing treatment is usually 5 to 4 Torr, and the immersion time is usually 1 to 120 seconds. After washing with water, drying treatment was carried out to obtain a polarizing element. The drying treatment is usually carried out using a hot air dryer or a far infrared heater. The drying treatment temperature is usually from 30 to 100. (3, preferably 5 to 80 ° C. The drying treatment time is usually 60 to 600 seconds, preferably 12 to 6 seconds. In this way, the polyvinyl alcohol resin film is uniaxially stretched. A polarizing element is obtained by dyeing a dichroic dye and a boric acid treatment. The polarizing element has a thickness of 5 to 4 Å/zm. A material which forms a protective film attached to one or both sides of the polarizing element is preferably transparent. Properties, mechanical strength, and thermal stability. The moisture barrier property and the asymmetry are excellent. The protective film may be selected from the group consisting of cellulose resins, cycloolefin resins, dimethyl terephthalate resins, and (methyl). At least one of the acrylate-based resins. For example, the protective film 'is exemplified by polyethylene terephthalate or poly-Bin

14 201207060 Acidic acid II is a poly(tetra) polymer, a cellulose polymer such as diacetyl cellulose or triacetyl cellulose, a polyacrylic acid methyl acetonate or the like, and a poly Examples of the styrene-based polymer such as styrene or acrylonitrile-styrene copolymer (AS resin), and the β-formation of the transparent protective film such as a polycarboester polymer can also be exemplified by poly Ethylene polymer, nylon, aromatic polyamine, etc., such as polystyrene, ethylene-propylene copolymer, or the like, which is a ring-shaped or a reduced or ethylene-propylene copolymer. Amidoxime polymer: amine polymer, sulfone polymer 'polyether sulfone polymer, polyether ether hydrazine salt D, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride Rare polymer 'vinyl butyral polymer, aromatic vinegar poly eight 'polyoxymethylene polymer, epoxy polymer, or the above polymer: two substances, etc." α, polarizing element usually By means of an adhesive layer followed by a transparent protective film, transparent, protective film, (meth)acrylic, amine vinegar can be used Acrylic-based brewing amine, oxygen-containing soil, and other silicon-based thermosetting resin or an ultraviolet curing resin. Any suitable additive of any one or more may be contained in the transparent protective film. Additives, exemplified by: ultraviolet absorber, antioxidant, lubricant, plasticizer, degreasing agent, anti-coloring agent, flame retardant, nucleating agent, antistatic agent, pigment or coloring transparent protective film The content of the thermoplastic resin is preferably from 5 () to _% by weight, more preferably from 50 to 99% by weight. /〇, more preferably 6〇 to 98% by weight, especially: ~, to 9 7 weight 1%. The content of the thermoplastic resin in the transparent protective film is 5 ' '曰-〇/ 里里/. In the following cases, the high transparency and the like which the thermoplastic resin originally has cannot be sufficiently expressed. Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not

S 201207060 is limited to these embodiments. Hereinafter, the % and the part of the content or the amount used are based on the weight unless otherwise specified. [Example 1] (a) Production of a polarizing element A polyethylene film having an average degree of polymerization of about 2,400, a degree of saponification of 99.9 mol% or more and a thickness of 75/zm was uniaxially stretched to about 5 by dry method. In addition, the state of maintaining the stretched state is 60. (: After pure water was immersed for 1 minute, it was immersed in an aqueous solution of 28 ° 匚 iodine/potassium iodide/water at a weight ratio of /55/5/1 60 for 60 seconds. Thereafter, potassium iodide at 72 ° C / An aqueous solution having a boric acid/water weight ratio of 8.5/8.5/100 was impregnated for 3 sec. Then, it was washed with pure water for 20 seconds and then at 65. (: Drying) was produced by adsorption of polyvinyl alcohol film. A molybdenum polarizing element. (b) The manufacture of an adhesive composition is an ethylene glycol-based modified polyvinyl alcohol-based resin [trade name "G〇hsenol Z200"' Japan Synthetic Chemical Industry Co., Ltd., 4% The viscosity of the aqueous solution is 12.5 mPa·sec's degree of saponification is 99.5 mol%], and the solution is dissolved in pure water to prepare an aqueous solution having a concentration of 10%. The aqueous solution of the ethyl hydrazide-modified polyvinyl alcohol-based resin is used as a crosslinking agent. Sodium glyoxylate formerly: the latter has a solid content ratio of 1: 0.1. The use of ethanol as the alcohol solvent and the weight ratio of the water/alcohol mixed solvent is 9 〇: 1 〇 to 醯Ethyl hydrazine-modified polyvinyl alcohol-based resin is water/alcohol mixed with 00 parts of water/alcoholic mixed solvent. The solvent was diluted to prepare an adhesive composition. The composition had a pH of 5.7' and a viscosity of 35 mPa·sec. (c) Production of a polarizing plate 201207060 The two sides of the polarizing element fabricated in the step (a) were coated with ( After b) the adhesive composition of the step, the protective film is bonded. The polarizing plate is prepared by drying at 6 rc for 3 minutes (thickness of the adhesive layer: about 〇 1 [Example 2] in Example 1 In the step (b), the ethylene-baked polyglycol-based resin is diluted with water/alcoholic solvent in a ratio of 1 part by weight of the water/alcohol mixed solvent. An adhesive composition was produced in the same manner as in Example i. The composition had a pH of 5 6, and a viscosity of 7.5 mPa·sec. In addition to the use of the composition, it was the same as Example i. The polarizing plate was produced in the same manner. [Example 3] In the step (b) of Example 1, the ethoxylated polyvinyl alcohol-based resin was mixed with 301 parts of water/alcohol to form 5 parts. The method is diluted with a water/alcohol mixed solvent, except that it is the same as (b) of the embodiment i. A composition of the adhesive was prepared in the form of a composition having a pH of 5 6 and a viscosity of 17.0 mPa sec. A polarizing plate was produced in the same manner as in the procedure of Example (Example j) except that the composition was used. 4] In the step (1) of the first embodiment, the weight ratio of the solid component of the ethyl hydrazide-modified polyvinyl alcohol-based resin: sodium glyoxylate is 1: 〇〇5, which is modified with acetamidine. The adhesive composition was produced in the same manner as in the embodiment (b) except that the polyvinyl alcohol-based resin was diluted with water/alcohol mixed solvent in a ratio of 3 parts by weight of the water/alcohol mixed solvent. The composition ρ Ή # is 7.4 mPa · sec. In addition to the use of components, and implementation

17 S 201207060 Example 1 The same procedure was used to make a polarizing plate. [Example 5] In the fh of the first embodiment, in the step of the first half (1), the weight ratio of the solid component of the sodium acetylate modified polyvinyl alcohol to the sodium dimethicone was 1: 〇'2 In the case of a B-B- 2 ethyl alcohol-based resin with respect to a water/alcohol mixed solvent-parts; and dilution with a water/alcohol mixed solvent, and other implementations

Or in the same manner to make an adhesive composition. The composition has a pH t viscosity of 7.5 Å. A polarizing plate was produced in the same manner as in the step (e) of Practical Example 1, except that the composition was used. [Example 6] [" In the step (b), the ethoxylated polyvinyl alcohol resin was added to the water/alcohol mixed solvent with respect to the water/alcohol mixed solvent. Dilution ' At this time, the weight ratio of the water/alcohol mixed solvent was adjusted to 99: 1, and the adhesive composition was produced in the same manner as in the first embodiment (1) except that the viscosity was (10) ^ coffee. A polarizing plate was produced in the same manner as in the step (c) of Example 1, except that the composition was used. [Example 7] In the step (1) of Example 1 alone, the water-alcohol-modified glycerin-based resin was chilled with water/alcohol in a manner of 3 parts by weight of the water/alcohol mixed solvent. The adhesive composition was prepared in the same manner as in the above (1) of Example i except that the weight ratio of the water/alcohol mixed solvent was adjusted to 30:70. The composition had a pH of 5 and a viscosity of 7 7 mPa.sec. A polarizing plate was produced in the same manner as in the procedure of Example i < (c) except that the composition was used. [Example 8] In the step (b) of Example 1, the ethyl acetonitrile-modified polyvinyl alcohol-based resin was changed to "Gohsenol Z100j [trade name, Nippon Synthetic Chemical Co., Ltd., 4% aqueous solution The viscosity is 5 2 mPa · sec, and the degree of saponification is 99.2 mol%.] The aqueous solution having a concentration of 5% is prepared. The aqueous solution of the ethyl hydrazide-modified polyethylene resin is mixed with the ethyl acetate as a crosslinking agent. The former of the sodium sulphate: the weight ratio of the solid component of the latter is 1:1. The weight ratio of the water/alcoholic mixed solvent is 9 〇: 1 〇, U 醯 醯 醯 改 modified polyvinyl alcohol The resin was diluted with a water/alcohol mixed solvent in a ratio of 3 parts by weight of the water/alcohol-based mixed solvent to prepare an adhesive composition. The composition had a pH of 5.6 and a viscosity of 3.2 mPa·sec. Example 9] In the step (1) of Example 1, the ethyl hydrazide-based modified polyvinyl alcohol-based resin was changed to "Gohsenol Z3〇〇j [trade name, Nippon Synthetic Chemical Industry Co., Ltd., 4% The viscosity of the aqueous solution is 27.9mpa •like, the degree of recombination is 98·5 mol%]] An aqueous solution having a concentration of 5% is mixed with the aqueous solution of the ethylene-based modified polyethylene-based resin and the former (B) as a crosslinking agent: the weight ratio of the latter solid component is 1:1. The weight ratio of the water/alcohol mixed solvent is 9 〇: 1 〇, 卩 酿 醯 改 改 = = = = = = = = = = = = = = = The solvent is fed into the rod: μ, and the dilution is made to produce an adhesive composition. The composition has a ΡΗ5_6 and a viscosity of 12 〇ηιρ&·^. [Comparative Example 1] 201207060 / Only % of Example 1 (b In the step, the ethyl hydrazine-modified polyvinyl alcohol-based tree sorghum is added to the water/alcohol-mixed 丨i (9) portion to form a dilution of 3 parts by water/alcoholic co-agents. The weight ratio of the /alcoholic mixed solvent was adjusted to 20.80', and the same procedure as in the example (b) was carried out, followed by hydrazine, and the composition was obtained. The pH of the composition was 5 5, and the viscosity was 7 8 mPa·sec. A polarizing plate was produced in the same manner as in the procedure of Example (i) except that it was used as a composition. [Comparative Example 2] In the step (b), the ethylene glycol-based modified polyvinyl alcohol-based resin is diluted with water/alcohol mixed solvent in a manner that the water/alcohol mixed solvent 1GG is 3 parts. The weight ratio of the mixed solvent was adjusted to 99·5: 〇·5′, except that the adhesive composition was produced in the same manner as in the embodiment (b) of Example 1. The composition had a pH of 5 5 and a viscosity of 7 8 mPa. Separation A polarizing plate was produced in the same manner as in the procedure of Example i (c) except that the composition was used. [Comparative Example 3] In the step (b) of Example 1, a water/alcohol mixed agent was used in an amount of 3 parts by weight of the ethylene glycol-based modified polyvinyl alcohol-based resin with respect to 100 parts of the water/alcohol mixed solvent. An adhesive composition was produced in the same manner as in the first embodiment (b) except that the dilution was carried out and the preparation was carried out by using sodium hydroxide as an additive. The composition was pH η·0, and the viscosity was 7.8 mPa·sey. A polarizing plate was produced in the same manner as in the step (C) of Example 1 except that the composition was cited. [Comparative Example 4] 20 201207060 In the step (b) of Example 1, the polyvinyl alcohol-based tree ruthenium was modified with a water/alcohol mixed solvent by 7 Å, i + ^ with acetamidine. The method of making the scar into 3 parts is diluted with water/alcohol-mixed S solvent, and the pH is adjusted to 3 by using B and the additive, and otherwise P Μ with the example i is 3 Λ, > ΛΓ Δ The method of making an adhesive composition. The 忒 composition has a pH of 3 〇 and is 7.8 mPa·. A polarizing plate was produced in the same manner as in the step V of Example 1 except that the composition was used. [Comparative Example 5] In the step (b) of Example 1, the weight of the solid component of the sodium sulphate was changed in the 冉 冉 t t t t Ribbi is 1·0.5, and the 7-meryl modified polyvinyl alcohol is used to make the resin. The phenol/b f (4) is diluted with the water/alcohol mixture by the 1/g alcohol mixed solvent. 'Other than this, manufactured in the same manner as (b) of Example 1.

., 7 Λ I ^ connector composition. The composition has a pH of 7 5 5 mPa·sec. A polarizing plate was produced in the same manner as in the step (1) of Example 1, except that the composition was used. 4 [Comparative Example 6] In the step of taking the tree r~1:1 U), the weight ratio of the solid component of the ethyl acetonitrile modified polyvinyl alcohol ethyl sulphate is "0.02, The base-modified polyvinyl alcohol (IV) is used in the same manner as in the case of (b) of Example 1 in addition to the dilution of the water/alcohol mixed solvent of 100 parts. c ^ Flying I & splicer composition "This composition is: 7.5 mPa at 4 degrees. See. In addition to using the composition, a polarizing plate was produced in the same manner as in the procedure of (1) of Example 1. Example 7]

S 21 201207060 In the step (1) of the example, the water is diluted with a water/alcohol mixed solvent in such a manner that the PEG-based modified polyvinyl alcohol-based resin is made up of 5 parts of the water/alcohol mixed solvent. An adhesive composition was produced in the same manner as in Example i except the above. The composition had a pH of 5 and a viscosity of 2.5 mPa · sec. A polarizing plate was produced in the same manner as in Example 1 except that the composition was used. [Comparative Example 8] In the step (b) of Example 1, the polymerization was modified with an acetamidine group. An adhesive composition was produced in the same manner as in the example (b) except that the vinyl alcohol-based resin was diluted with water/alcohol mixed solvent in an amount of 1 part by weight with respect to 100 parts of the water/alcohol mixed solvent. The composition had a pH of 5, and a viscosity of 2.5 mPa. Sey. A polarizing plate was produced in the same manner as in the step [c] except that the composition was used. [Comparative Example 9] The crosslinking agent was changed to B. The weight ratio of aldehyde acid's modified polyethylene glycol resin (Gohsenol Z200) to the solid content of glyoxylic acid is j. 〇·2, modified with polyvinyl hydrazine An adhesive composition was prepared in the same manner as in the example (b) of Example i except that the resin was diluted with water/alcohol mixed solvent in a ratio of 100 parts by weight of the water/alcohol mixed solvent. 5.3, the viscosity is 7.6 mPa · sec. In addition to using the composition, it is the same as in Example 1. (c) A polarizing plate was produced in the same manner as in the step. [Comparative Example 10] The weight ratio of the crosslinking agent to boric acid, and the weight ratio of the ethyl phthalate-modified polyethylene resin (Gohsenol Z200) to the solid content of boric acid Is: 22 201207060 Ethyl acetate-based modified polyvinyl alcohol 100 parts into 3 parts by water;: broadly relative to the water/alcohol mixed solvent in the same way as in the example i (b): The solvent was diluted, except that the composition had a pH of 5.3 and a viscosity of 76 p followed by #1 composition. The outside of the group, and, 'mPa·sec. In addition to using the composition in the form of A polarizing plate was produced in the same manner as in the steps of 1 (, , , and L). The resins, crosslinking agents, solvents, and additives used in Examples 1 to 9 and Comparative Examples i to 1 are shown in Table 1 below. The content of the material, and the physical properties of the adhesive composition for the polarizing electrode produced.

23 S 201207060

I I

201207060 [Evaluation Test] Each of the polarizing plates obtained in Examples 1 to 10 and Comparative Examples 1 to 10 was subjected to the following evaluation test. [1] Adhesiveness (cutting evaluation) After each polarizing plate was allowed to stand at room temperature for 1 hour, a cutting blade was inserted between the films of the polarizing plate (between the polarizing element and the protective film A and between the polarizing element and the protective film B). According to the following criteria, the way of entering the knife when pushing the knife is evaluated. 〇_Cutting knife does not enter between any of the membranes. △. When pushing the knife, the knife stops when it enters 4 to 5 mm between at least one of the films. X · When pushing the knife, the knife smoothly enters between at least one of the membranes (if the knife smoothly enters between any of the membranes, it also includes the case where the knife does not enter the remaining membrane or stops when entering 4 to 5 mm) . [2] Temperature and water resistance For 23 C, relative humidity 55 ° /. The polarizing plates placed in the environment for 24 hours were subjected to the following temperature resistance test (warm water dipping test) to evaluate the water resistance. First, a sample was prepared by cutting a polarizing plate into a rectangle of 5 c m X 2 c m with the absorption axis (stretching direction) of the polarizing plate as a long side, and accurately measuring the size of the long side direction. Here, the sample uniformly displays the characteristic color throughout the entire surface due to the iodine adsorbed on the polarizing element. Figure 1 a is a diagram of a polarizing plate before the temperature is impregnated by the method of Example 3 of the present invention, and the ib is a polarizing plate after warm water immersion. Figure. As shown in Fig. u, one of the short sides of the sample was held by the grip portion (2), and about 8 〇 in the longitudinal direction was immersed at 6 〇. The sink is kept for 4 hours. Thereafter, the polarizing plate (1) is taken out from the water tank t, and rubbed

25 S 201207060 Dehydrated. The polarizing element (5) of the polarizing plate which is shrunk by warm water immersion is shown in Fig. ib. The polarizing element (5) is evaluated by measuring the distance from the end (the end of the protective film) of the polarizing plate at the center of the short side of the polarizing plate (1) to the end of the contracted polarizing element (5). The degree of shrinkage is set to the contraction length. Further, as shown in FIG. 2b, since the polarizing element (5) located at the center of the polarizing plate is shrunk by warm water immersion, a region where the polarizing element (5) is not formed between the protective films, that is, the non-polarizing element region is formed between the protective films. (3). Further, the iodine is immersed in warm water and is exposed to the periphery of the polarizing element (5) which is heated with water, and the area where the color is detached is generated in the peripheral portion of the polarizing plate (1) (4). By measuring the distance from the end of the contracting polarizing element (5) from the center of the short side of the polarizing plate (1) to the region of the color unique to the residual polarizing plate, the degree of discoloration is evaluated as Iodine shedding length. The total length of the shrinkage and the length of the iodine shedding are the total length of the erosion (X). That is, the total length (X) of the erosion refers to the end of the polarizing plate (1) from the center of the short side of the polarizing plate (1). (1) The distance from the end of the protective film to the area of the color unique to the residual polarizing plate. It can be judged that the smaller the shrinkage length, the iodine shedding length, and the total length (X) of the erosion, the higher the adhesion (water resistance) in the presence of water. The criteria for its judgment are as follows. ◎ · The total length (X) of the known surname is less than 2mm. 〇. The total length (X) of the rice is 2mm or more and less than 3mm. △. The total length (X) of the knowledge is 3 mm or more and less than 5 mm. x : The total length (X) of the intrusion is 5 mm or more. [3] Appearance evaluation (defective cracking point) 26 201207060 A polarizing plate was produced by cutting a polarizing plate to a size of 1000 mm x 1000 mm. Place the sample polarizer on the fluorescent lamp. Another polarizing plate is disposed on the light source side of the sample polarizing plate in such a manner that each absorption axis is orthogonal, and the number of leaks (cracking defects) is counted in this state. ◎: The number of crack defects is less than three. The number of 〇·cracking defects is three or more, and it is less than one. △. The number of crack point defects is 1 or more and less than 2. x : The number of crack defects is 2 or more. [4] Polarization degree of polarization (Py) is determined by using an ultraviolet-visible spectrophotometer [manufactured by Sakamoto Seiki Co., Ltd., trade name "v-7100/VAP-7〇7〇"] to measure the parallel penetration of polarized parts. The rate (Hg) and the orthogonal transmittance (h9()) were calculated from the degree of polarization (/〇) - { ( Η〇 - η90) / ( Η〇 + Η 90) } 1/2 χ 100. The transmittance is a γ value obtained by performing visibility correction by a 2 degree field of view (C light source) prescribed by JIS Z 8701 (1982 edition). The evaluation results are carried out as follows. 〇::^ is 99.996% or more. △ . Py is over 99.993% and is less than 99.996%. x ·· Py is 99.993% or less. The results of the evaluation test are shown in Table 2.

S 27 201207060 [Table 2] Subsequent temperature-resistant water f-polarity cracking point defect Other physical properties Example 1 〇 ◎ 施 施 Example 2 〇 ◎ 〇〇 - Example 3 〇 ◎ 〇〇 Example 4 〇〇〇〇 _ Example 5 〇〇〇 Example 6 〇 ◎ 〇〇 _ Λ Example 7 〇 ◎ 〇〇 _ poor example 8 ◎ 〇〇 - Example 9 〇 ◎ 〇〇 _ Comparative Example 1 - 〇 phase separation comparative example 2 〇 ◎ "〇~~~Δ~ Comparative Example 3 ◎ 〇〇Potlife X Comparative Example 4 〇Δ 〇◎ Comparative Example 5 △ Γ ◎ △ 〇 a comparative example 6 ό Δ 〇〇 a comparative example 7 〇 △ 〇 △ Comparative Example 8 〇 ◎ Δ Δ A Comparative Example 9 Δ Δ Δ 〇 - Comparative Example 10 〇X 〇〇 - Referring to Table 2, a comparative example in which the weight ratio of the alcohol-based solvent in the mixed solvent was too high in the adhesive composition (1) The polarizing plate of Comparative Example 2 in which the compatibility of the ethylene-acetylated modified polyvinyl alcohol-based resin is decreased and the weight ratio of the alcohol is too low, and the effect of improving the crack defect is low. Comparative Example 3 with higher pH of the substance, which is applicable (Lifetime which can be used as an adhesive) is short, and Comparative Example 4 having a low pH cannot exhibit sufficient water resistance. Comparative Example 5 which increases the ratio of the crosslinking agent cannot exhibit sufficient degree of polarization to reduce the ratio of the crosslinking agent. Comparative Example 6 did not exhibit sufficient water resistance. In the adhesive composition, Comparative Example 7 in which the concentration of the ethyl acetylated modified polyvinyl alcohol-based resin was low was insufficient, and the polyvinyl alcohol-based resin was insufficient. Concentration 28 201207060 X 'Comparative Example 8 in which any of the well-known ones is not sufficiently high does not exhibit sufficient degree of polarization. Comparative Examples 9 and 1 of the crosslinking agent have a degree of polarization and adhesion. The performance of the polarizing plate of the comparative example 丨 to 1〇 which is higher or lower than the content of the alcohol solvent, the pH of the composition, the type and content ratio of the crosslinking agent, and the content of the resin is poor, and it can be confirmed that it is different from the above. The polarizing plates of Examples 1 to 9 which were invented by the invention exhibited excellent properties of adhesion, temperature resistance, polarization, cracking defect, and other physical properties. The present invention is not subject to the above embodiment and the accompanying drawings. The pattern is limited and must The scope of the invention is explained in the appended claims. Further, it will be apparent to those skilled in the art that the present invention can be modified and modified in various forms without departing from the scope of the technical spirit of the invention as set forth in the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1a is a diagram showing a polarizing plate before warm water immersion in a test method for dialysis resistance of a polarizing plate manufactured according to an embodiment of the present invention. Fig. 1b shows a diagram of a polarizing plate after warm water immersion. [Description of main component symbols] 1 Polarizer Γ End of polarizer 2 Grip 3 Non-polarizing element area 4 Color shedding area 5 Polarized element X Total length of erosion

S 29

Claims (1)

201207060 VII. Scope of application for patents: 1. A composition for an adhesive for polarizing plates, which contains an ethyl hydrazine-modified I ethyl amide resin, water, and an alcoholic point of 10 0 C or less. And the glyoxylate represented by the chemical formula below, and the water is contained in parts by weight relative to H), and the ethylene-based modified polyvinyl alcohol-based resin is added in parts by weight. The weight ratio of the vinyl alcohol resin and the solid component of the ethylene salt is 1: 〇.〇3 to i: 〇25, and the weight ratio of water saving to the alcohol solvent is 99:1 to 30:70, and the pH is 4 to 1〇: η* 1/n Μ H«, CT II II 〇Ο δ In the abbreviated form, 'μ denotes a metal or alkaline earth metal, η is 1 or 2. 2. The adhesive composition for a polarizing plate according to the first aspect of the invention, wherein the adhesive composition for the polarizing plate has a viscosity at 20 ° C of 3 to 25 mPa · sec ° 3 as claimed in claim 1 The polarizing plate is composed of an adhesive composition, wherein 'the alcohol solvent is a lower alcohol having a carbon number of 丨 to 4. 4. The adhesive composition for a polarizing plate according to the first aspect of the invention, wherein the '5-thyl alcohol solvent is ethanol. 5. The adhesive composition for a polarizing plate according to the first aspect of the invention, wherein the weight ratio of the water to the alcohol solvent is 95:5 to 50:50. 6 _ A polarizing plate comprising a polarizing element ′ and a protective film for bonding an adhesive composition for a polarizing plate according to any one of claims 1 to 5 to at least one surface of the polarizing element. The polarizing plate of claim 6, wherein the protective film comprises a cellulose resin, a cycloolefin resin, a polyethylene terephthalate resin, and (a) At least one of a acrylate resin.