JP2017032813A - Polarizing plate adhesive composition and polarizing plate produced using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polarizing plate adhesive composition which offers water resistant adhesivity that prevents elution of an adhesive layer even through prolonged immersion in water.SOLUTION: It has been discovered that a polarizing plate having superior water-resistant adhesivity can be achieved by adding a metallic cross-linker to a composition comprising a polyvinyl alcohol resin containing an active hydrogen-containing modified group and a glyoxylic acid salt. In other words, the polarizing plate adhesive composition comprises a modified group-containing polyvinyl alcohol resin (A) containing active hydrogen, glyoxylic acid salt (B), and metallic cross-linker (C).SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to a polarizing plate formed by bonding a polarizing film and a protective film, and to a polarizing plate adhesive composition used for the bonding and a polarizing plate using the polarizing plate adhesive composition. . More specifically, the present invention relates to an adhesive composition for a polarizing plate having water-resistant adhesion that does not elute the adhesive layer even when immersed in warm water for a long time.

Liquid crystal display devices are widely used as image display devices for liquid crystal televisions, computer displays, mobile phones, digital cameras, and the like. Such a liquid crystal display device has a configuration in which a polarizing film is laminated on both sides of a glass substrate in which liquid crystal is sealed, and various optical functional films such as a retardation plate are laminated on this as necessary.
As the polarizing film, a dichroic material such as iodine is dispersed and adsorbed in a highly saponified polyvinyl alcohol resin (hereinafter, polyvinyl alcohol may be abbreviated as PVA), and after stretching or simultaneously with stretching. A uniaxially stretched film crosslinked with a crosslinking agent such as boric acid is widely used.
A polarizing film using a uniaxially stretched film of this PVA resin tends to shrink under high humidity, and usually compensates for moisture resistance and strength by attaching a protective film on at least one side, preferably both sides. Are used as polarizing plates.

As the protective film, cellulose ester resins such as triacetyl cellulose are widely used because of their excellent transparency, mechanical strength, and moisture resistance.
Such a protective film is bonded to a polarizing film by an adhesive, and as an adhesive composition constituting such an adhesive, a PVA resin, particularly a polarizing film, is used from the viewpoint of adhesiveness to a polarizing film having a hydrophilic surface. Those mainly composed of a high saponification degree PVA-based resin are used.

  A polarizing plate with a protective film and a polarizing film bonded together is transported around the world through land, air and sea. In the process of transportation, it often passes through high-temperature and high-humidity areas, and in some cases it is stored in such areas, and at that time, the adhesive strength between the protective film and the polarizing film has been a problem. .

In order to solve this problem, for example, it has been proposed to use a crosslinked polymer obtained by crosslinking a polyvinyl alcohol-based resin containing an acetoacetyl group with glyoxylate as an adhesive layer (for example, see Patent Document 1). ).
In addition, in an adhesive containing an acetoacetyl group-containing polyvinyl alcohol resin and glyoxylate, it has also been proposed to further improve the adhesion by setting the concentration and pH to a specific value (see, for example, Patent Document 2). ).

JP 2010-077385 A JP 2010-191389 A

However, in the adhesives described in Patent Documents 1 and 2, the adhesive layer elutes when immersed in water for a long time, and in the recent increase in required performance, the water-resistant adhesion is still satisfactory. There is a need for further improvements.
Therefore, in the present invention, an object of the present invention is to provide an adhesive composition for polarizing plates that is excellent in water-resistant adhesion, such that the adhesive layer does not elute even when immersed in water for a long time. .

  However, as a result of intensive studies in view of the above circumstances, the present inventor has found that the composition of a polyvinyl alcohol-based resin having an active hydrogen-containing modifying group and a glyoxylate further contains a metal-based cross-linking agent, thereby providing water-resistant adhesion. The present invention was completed by finding that a polarizing plate having excellent properties can be obtained.

  That is, the gist of the present invention is an adhesive composition for a polarizing plate comprising a modified group-containing polyvinyl alcohol resin (A) containing active hydrogen, a glyoxylate (B), and a metal crosslinking agent (C). It is about.

  Furthermore, in this invention, the polarizing plate formed by adhere | attaching a polarizing film and a protective film using the said adhesive composition for polarizing plates is also provided.

  The adhesive composition for polarizing plates of the present invention can provide a polarizing plate excellent in water-resistant adhesion, and the obtained polarizing plate can be applied to a display device used under particularly severe conditions. Is.

  In addition, such an effect is that the metal-based crosslinking agent (C) not only causes a crosslinking reaction with the modifying group having active hydrogen of the PVA-based resin, but also causes a crosslinking reaction with the hydroxyl group of the PVA-based resin or the hydroxyl group of the protective film. By this, it is estimated that the adhesiveness of PVA-type resin and a protective film improves, and the adhesive bond layer which is excellent in water-resistant adhesiveness is obtained.

The description of the constituent requirements described below is an example (representative example) of an embodiment of the present invention, and is not limited to these contents.
Hereinafter, the present invention will be described in detail.

[Modified group-containing polyvinyl alcohol resin having active hydrogen (A)]
First, the polyvinyl alcohol-based resin having an active hydrogen-containing modifying group (hereinafter sometimes abbreviated as an active hydrogen-containing PVA-based resin) (A) used in the present invention will be described.
The active hydrogen of the present invention indicates a proton on a methylene group with increased acidity, such as hydrogen of a methylene group adjacent to a carbonyl group. Such protons cause a crosslinking reaction in the resonance-stabilized portion.
Examples of the PVA resin (A) containing active hydrogen as described above include PVA resins having a modifying group such as ketone, carboxylic acid or carboxylic acid ester having such active hydrogen. Specifically, for example, a PVA resin having an acetoacetyl group or a diacetone group can be used. Among them, acetoacetyl group-containing PVA resin (hereinafter sometimes abbreviated as AA-PVA resin) (A1) and diacetone acrylamide structural unit-containing PVA resin are preferable, and in terms of water resistance. AA-PVA-based resin (A1) is preferable.

The average degree of polymerization of the active hydrogen-containing PVA resin (A) is usually 300 to 4000, particularly preferably 400 to 3000, and more preferably 800 to 2000. If the average degree of polymerization is too small, sufficient water resistance may not be obtained or sufficient crosslinking rate may not be obtained. On the other hand, if the degree of polymerization is too large, the viscosity of the adhesive composition becomes too high, and coating Tend to be difficult.
The average degree of polymerization is measured according to JIS K6726.

The saponification degree of the active hydrogen-containing PVA resin (A) is usually 80 to 100 mol%, more preferably 85 to 99.9 mol%, and particularly preferably 90 to 99.8 mol%. It is done. If the degree of saponification is too low, it tends to be difficult to make an aqueous solution, the stability of the aqueous solution decreases, and the water resistance of the resulting adhesive tends to decrease.
The degree of saponification is measured according to JIS K6726.

  The modification amount of the active hydrogen-containing PVA resin (A) is usually 0.1 to 20 mol%, more preferably 1 to 15 mol%, and particularly preferably 2 to 10 mol%. If the content is too small, the water resistance tends to decrease or a sufficient crosslinking rate cannot be obtained. Conversely, if the content is too large, the water solubility tends to decrease or the stability of the aqueous solution tends to decrease. .

[AA-modified PVA resin (A1)]
Next, the AA-PVA-based resin (A1) preferably used in the present invention will be described.
The AA-PVA-based resin (A1) used in the present invention has an acetoacetyl group (AA group) bonded to the main chain of the PVA-based resin directly or through an oxygen atom or a linking group. PVA-type resin containing the structural unit which has AA group represented by (1) is mentioned. In addition, this AA-ized PVA-type resin (A1) has a vinyl alcohol structural unit other than the structural unit which has AA group, and also has the vinyl ester structural unit of an unsaponified part as needed.

  Examples of the vinyl ester compounds include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, Examples thereof include vinyl stearate, vinyl benzoate, vinyl versatate, and vinyl acetate is preferably used from the viewpoint of economy.

  Further, a saponified product of a copolymer of a vinyl ester compound and a copolymerizable compound can be used. Examples of the copolymerizable compound include ethylene, propylene, isobutylene, α-octene, and α-dodecene. Olefins such as α-octadecene; hydroxy-containing α-olefins such as 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, and 3,4-dihydroxy-1-butene And derivatives thereof such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, undecylenic acid, salts, monoesters or dialkyl esters thereof; acrylonitrile, methacrylonitrile Nitriles such as diacetone acrylamide, acrylamide, Amides such as Luamide; Olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid or salts thereof; alkyl vinyl ethers, dimethylallyl vinyl ketone, N-vinyl pyrrolidone, vinyl chloride, vinyl ethylene carbonate, 2, Vinyl compounds such as 2-dialkyl-4-vinyl-1,3-dioxolane and glycerol monoallyl ether; substituted vinyl acetates such as isopropenyl acetate and 1-methoxyvinyl acetate; vinylidene chloride, 1,4-diacetoxy-2 -Butene, 1,4-dihydroxy-2-butene, vinylene carbonate and the like.

  The amount of the copolymerizable compound to be introduced varies depending on the type of the compound and cannot be generally specified, but is usually 10 mol% or less, particularly 5 mol% or less of the total structural unit. In some cases, the compatibility with the crosslinking agent may be reduced.

The average degree of polymerization of the AA-PVA-based resin (A1) may be appropriately selected depending on the application, but is usually 300 to 4000, particularly 400 to 3000, and more preferably 800 to 2000. If the average degree of polymerization is too small, sufficient water resistance may not be obtained or sufficient crosslinking rate may not be obtained. On the other hand, if the degree of polymerization is too large, the viscosity of the adhesive composition becomes too high, and coating Tend to be difficult.
The average degree of polymerization is measured according to JIS K6726.

The saponification degree of the AA-modified PVA resin (A1) is usually 80 to 100 mol%, more preferably 85 to 99.9 mol%, particularly 90 to 99.8 mol%, 95 to 99.8 mol% is preferably used. If the degree of saponification is too low, it tends to be difficult to make an aqueous solution, the stability of the aqueous solution decreases, and the water resistance of the resulting adhesive tends to decrease.
The degree of saponification is measured according to JIS K6726.

  Moreover, AA group content (Hereinafter, it may be abbreviated as AA conversion degree.) In AA-ized PVA-type resin (A1) is 0.1-20 mol% normally, Furthermore, 1-15 mol. %, Particularly 3 to 10 mol% is preferred. If the content is too small, the water resistance tends to decrease or a sufficient crosslinking rate cannot be obtained. Conversely, if the content is too large, the water solubility tends to decrease or the stability of the aqueous solution tends to decrease. .

In the present invention, it is preferable that all of the PVA resins used are AA-PVA resins (A1), but PVA resins other than AA-PVA resins (A1) may be used in combination. The content is usually 20% by weight or less, particularly 10% by weight or less, more preferably 5% by weight or less, based on the AA-PVA-based resin (A1).
Examples of PVA resins other than the AA-modified PVA resin (A1) include unmodified PVA resins and various modified PVA resins obtained by copolymerizing various monomers having a copolymerization property with vinyl ester monomers. Can be mentioned.

  The AA-PVA-based resin (A1) used in the present invention includes an alkali metal acetate such as sodium acetate used or produced as a by-product in the production process (mainly an alkali metal hydroxide used as a saponification catalyst). Organic acids such as acetic acid (derived from a reaction product with acetic acid produced by saponification of polyvinyl acetate) (organics occluded in PVA during reaction with diketene when introducing acetoacetate groups into PVA resin) Part of organic solvent (derived from reaction solvent of PVA resin, cleaning solvent at the time of production of AA-modified PVA resin, etc.) such as methanol and methyl acetate may remain.

  As a method for producing the AA-PVA-based resin (A1), it can be produced according to the methods described in paragraphs [0059] to [0065] of JP-A-2010-077385.

[Glyoxylate (B)]
The glyoxylate (B) of the present invention will be described. The glyoxylate (B) of the present invention undergoes a crosslinking reaction with the active hydrogen-containing PVA resin (A).
Examples of the glyoxylate (B) include glyoxylic acid metal salts and amine salts. Examples of the metal salts include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, Transition metals such as titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper, other metals such as zinc and aluminum, and metal salts of glyoxylic acid, and amine salts include ammonia, monomethylamine, dimethylamine, Examples include salts of amines such as trimethylamine and glyoxylic acid.
In particular, a metal salt, particularly an alkali metal or alkaline earth metal salt is preferably used from the viewpoint of obtaining an adhesive having excellent water resistance, and an alkali metal salt (B1) is particularly preferable from the viewpoint of water resistance.

  Further, the solubility of glyoxylate (B) used in the present invention in water is 0.01 to 100%, particularly 0.1 to 50%, more preferably 0.5 to 20 in water at 23 ° C. % Is preferably used. If the solubility is too small, it tends to be difficult to obtain an aqueous solution.

  As a method for producing glyoxylate (B), a known method can be used. For example, (1) a method based on a neutralization reaction of glyoxylic acid, (2) an acid whose glyoxylic acid and acid dissociation constant are larger than glyoxylic acid. And (3) a method by alkaline hydrolysis of glyoxylic acid ester (see, for example, JP-A No. 2003-300926). In particular, when the alkaline compound used for the neutralization reaction with glyoxylic acid is highly water-soluble, the method of (1) is a salt of an acid whose glyoxylate salt is low in water solubility and has an acid dissociation constant greater than glyoxylic acid. When the water solubility of is high, the method (2) is preferably used.

The method (1) is usually carried out using water as a medium, glyoxylic acid and an alkaline compound, for example, various metal hydroxides or amine compounds are reacted in water, and the precipitated glyoxylate is filtered off. It can be produced by drying.
The method (2) is also generally carried out in water, and glyoxylate can be obtained in the same manner as the method (1). Examples of the acid salt having a larger dissociation constant than glyoxylic acid used in the method (2) include, for example, alkali metal or alkaline earth metal salts of aliphatic carboxylic acids such as sodium acetate, calcium acetate, and calcium propionate. Can be mentioned.

[Metal-based crosslinking agent (C)]
Next, the metal-based crosslinking agent (C) used in the present invention is not limited as long as it is a metal compound having the ability to crosslink PVA-based resins. As a metal type crosslinking agent, the metal compound containing metals, such as Ti, Zr, Al, V, Mo, Ce, La, Cr, W, is mentioned, for example, These 1 type or 2 types or more are used. . Although it does not specifically limit as a metal compound, For example, the oxide, hydroxide, complex compound, organometallic compound, metal alkoxide, organic acid salt, inorganic acid salt, etc. of these metals are mentioned.
Among these, preferred is a water-soluble metal-based crosslinking agent in terms of reactivity with PVA, particularly preferred is an inorganic acid salt (C1), and more preferred is a zirconium compound in terms of water-resistant adhesion. Inorganic acid salt (C1-1).

  Specifically, examples of the complex compound include titanium compounds such as titanium diisopropoxybis (triethanolaminate), titanium lactate, titanium tetrakisacetonate, ammonium bis (oxalato) oxotitanate, zirconium tetrakisacetylacetonate, Zirconium compounds such as zirconium tributoxy monoacetylacetonate, zirconium acetylacetonate, tetrakisdimethylaminozirconium, aminocarboxylic acid-based zirconium, aluminum compounds such as aluminum trisacetylacetonate, vanadium compounds such as vanadylacetylacetate and vanadiumacetylacetate, Molybdenum compounds such as molybdenum dioxide acetylacetonate, lanthanum acetylacetonate What lanthanum compound, cerium acetylacetonate, ammonium penta nitrate Lato cerate, cerium compounds such as ammonium hexane Sanitora preparative cerate, tungsten acetylacetonate, tungsten compounds such as tungsten hexacarbonyl and the like.

  Examples of organometallic compounds include titanium compounds such as tetraisopropyl titanate and tetrabutyl titanate, zirconium compounds such as tetrapropyl zirconate and tetrabutyl zirconate, aluminum compounds such as triisobutylaluminum, and tungsten compounds such as tungsten hexacarbonyl. Can be mentioned.

  Examples of the metal alkoxide include titanium compounds such as titanium methoxide, titanium ethoxide, titanium propoxide, and titanium butoxide, zirconium compounds such as zirconium methoxide, zirconium ethoxide, zirconium butoxide, and zirconium propoxide, aluminum ethoxide, and aluminum butoxide. Aluminum compounds such as vanadium methoxide, vanadium ethoxide, vanadium propoxide, vanadium butoxide, vanadium aluminum propoxide, etc., molybdenum methoxide, molybdenum ethoxide, molybdenum isopropoxide, molybdenum butoxide, molybdenum phenoxide, molybdenum phenyl Molybdenum compounds such as ethoxide and molybdenum phenoxyethoxide Cerium compounds such as cerium methoxide, cerium ethoxide, cerium isopropoxide, cerium butoxide, lanthanum methoxide, lanthanum ethoxide, lanthanum isopropoxide, lanthanum compounds such as lanthanum butoxide, tungsten methoxide, tungsten ethoxide, tungsten iso Examples thereof include tungsten compounds such as propoxide and tungsten butoxide.

  Examples of organic acid salts include titanium compounds such as titanium acetate, titanium citrate, titanium oxalate, ammonium oxydioxalate, titanium tetraoleate, zirconium octoate, zirconium acetate, zirconyl acetate, zirconium octylate, octylic acid Zirconyl compounds such as zirconyl, aluminum oxalate, aluminum tartrate, aluminum benzoate, aluminum oleate, aluminum citrate, aluminum gluconate, aluminum stearate, aluminum lactate, aluminum butyrate, vanadium acetate, vanadium oxyoxalate , Vanadium compounds such as vanadium octoate and vanadium naphthenate, molybdenum compounds such as molybdenum acetate and molybdenum butyrate, octanoic acid Lanthanum, lanthanum formate, lanthanum acetate, lanthanum oxalate, lanthanum compounds, such as stearic acid lanthanum, cerium acetate, cerium oxalate, cerium compounds such as cerium stearate.

Examples of the inorganic acid salt (C1) include titanium compounds such as titanium chloride, titanium hydrofluoric acid, titanium nitrate, and titanium oxynitrate, zirconium chloride, zircon hydrofluoric acid, zirconium chloride oxide, zirconium phosphate, and zirconium carbonate hydroxide. Zirconium compounds such as ammonium, ammonium zirconium carbonate, zirconium silicate, zirconium nitrate, zirconium sulfate, zirconium titanate, aluminum compounds such as aluminum chloride, aluminum phosphate, aluminum sulfate, aluminum nitrate, aluminum perchlorate, aluminum titanate, Vanadium chloride, vanadium dichloride oxide, vanadium trichloride oxide, vanadium compounds such as ammonium metavanadate, vanadyl sulfate, vanadium titanate, molybdenum chloride, Molybdenum compounds such as molybdenum oxide, molybdenum nitrate, molybdenum phosphate, molybdic acid, ammonium molybdate, lanthanum compounds such as lanthanum chloride, lanthanum perchlorate, lanthanum dititanate, lanthanum sulfate, lanthanum phosphate, cerium chloride, perchlorine Examples thereof include cerium compounds such as cerium acid, cerium nitrate, cerium sulfate, and cerium phosphate, and tungsten compounds such as tungsten chloride, tungsten dichloride dioxide, tungsten carbonate, sodium tungstate, ammonium tungstate, and ammonium phosphotungstate.
Among the above, a preferable metal-based crosslinking agent (C) is an inorganic acid salt, and among them, an inorganic acid salt (C1-1) of a zirconium compound is preferable, and ammonium carbonate is particularly preferable in terms of water-resistant adhesion. .

[Other cross-linking agents]
In addition to the glyoxylate (B) and the metal-based crosslinking agent (C), other crosslinking agents may be blended in the adhesive composition for polarizing plates of the present invention. For example, boron compounds (for example, boric acid) , Borax, etc.), amine compounds (eg, diamine compounds, polyamine compounds, polyallylamine, etc.), silane compounds, aldehyde group-containing compounds (eg, dimethoxyethanal, glutaraldehyde, glyoxylic acid and its hemiacetal and acetal forms) Derivatives), thiol compounds, isocyanate compounds, polyisocyanate compounds (for example, “Hydran Assist C1” manufactured by Dainippon Ink & Chemicals, Inc.), block isocyanate compounds (for example, ketoxime block products or phenol block products), Water-soluble or water-dispersible epoxy resin or Compound (for example, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, diglycerin diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1 , 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, resorcin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol Polyglycidyl ether, sorbitol polyglycidyl ester Ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, etc.), water-soluble or water-dispersible oxetane resins or compounds, polyethyleneimine, and the like. These may be used alone or in combination of two or more.

[Adhesive composition]
Next, the adhesive composition for polarizing plates of the present invention will be described. Such an adhesive composition is interposed between the polarizing film and the protective film, and the adhesive composition is crosslinked to form an adhesive layer.

The adhesive composition for polarizing plates of the present invention comprises an active hydrogen-containing PVA resin (A), a glyoxylate (B), and a metal crosslinking agent (C), and contains an active hydrogen-containing PVA resin ( A) The content of glyoxylate (B) is 0.1 to 20 parts by weight, particularly 1 to 10 parts by weight, and further 2 to 8 parts by weight with respect to 100 parts by weight. If the content of the glyoxylate (B) is too much or too little, the water-resistant adhesion tends to be lowered.
Moreover, content of a metal type crosslinking agent (C) is 0.001-20 weight part. If the content of the metal-based crosslinking agent (C) is too much or too little, the water-resistant adhesion tends to be lowered.

  Moreover, a metal type crosslinking agent (C) is 0.001-10 weight part with respect to 1 weight part of glyoxylate (B). If the content is too small or too large, the water-resistant adhesion tends to decrease.

  Further, when the metal-based crosslinking agent (C) is a zirconium compound inorganic acid salt (C1-1), the zirconium compound inorganic acid salt (C) is used with respect to 100 parts by weight of the active hydrogen-containing PVA resin (A). The content of C1-1) is preferably 0.001 to 1 part by weight, particularly 0.01 to 0.1 part by weight, and more preferably 0.03 to 0.08 part by weight. When the content is too large, the viscosity tends to increase, and when the content is too small, the water-resistant adhesion property tends to decrease.

  Further, the content of the inorganic acid salt (C1-1) of the zirconium compound is 0.001 to 1 part by weight, particularly 0.005 to 0.1 part by weight with respect to 1 part by weight of the glyoxylate (B). Furthermore, it is preferable that it is 0.01-0.08 weight part.

In the present invention, the form of the adhesive composition is not particularly limited, but it is preferably used as a liquid in order to form a uniform adhesive composition layer on the surface of the polarizing film or the protective film as the adherend. .
Examples of such a liquid adhesive composition include solutions and dispersions of various solvents, but it is preferably a solution type from the viewpoint of coating property to a polarizing film or a protective film, and water is usually used from the viewpoint of safety. A main solution is preferably used.

Furthermore, after applying the adhesive composition to the adherend, a drying step is usually provided to remove the solvent contained in the adhesive composition. For the purpose of shortening the drying step, the adhesive composition Water / alcohol mixed solvent, which is a solvent that is easily miscible with water in a solution and has a lower boiling point than water, that is, an alcohol solvent having a boiling point of 100 ° C. or lower, particularly 80 ° C. or lower, and further 70 ° C. Using is also a preferred embodiment.
Specific examples of the alcohol solvent include lower alcohols having 1 to 3 carbon atoms such as methanol, ethanol, n-propanol, and isopropanol, and methanol having the lowest boiling point is preferably used.

  The blending amount of the alcohol solvent may be appropriately selected depending on the drying conditions and the type of alcohol used. Usually, the content ratio (weight ratio) of both in the mixed solvent of water and alcohol is 99.99 / 0. A range of 0.01 to 20/80, preferably 99/1 to 30/70, particularly 90/10 to 40/60, more preferably 80/20 to 50/50 is preferably used. If the amount of such alcohol is too large, the viscosity stability of the adhesive composition solution tends to decrease, and if it is too small, the effect of shortening the drying process tends not to be obtained.

  The solid content concentration of the adhesive composition solution cannot be generally specified depending on the desired coating amount and the characteristics of the coating apparatus, but is usually 0.5 to 30% by weight, particularly 1 to 20% by weight, A range of 1.5 to 15% is preferably used. If the concentration is too low, drying takes a long time, so that productivity is impaired. On the other hand, if the concentration is too high, the viscosity tends to be high, and uniform coating tends to be difficult.

Further, the adhesive composition of the present invention is usually 30% by weight or less, particularly 20% by weight or less of other resins, for example, polysaccharides such as starch and cellulose, polyethylene glycol, and the like within the range not impairing the object of the present invention. Water-soluble resins such as polyvinylpyrrolidone, polyoxazoline, water-soluble polyamide, water-soluble polyester, polyacrylamide, and polyethyleneimine, and urethane adhesives and emulsion adhesives can be used in combination.
Similarly, as various additives, antifoaming agents, leveling agents, colorants, dyes, pigments, fluorescent brighteners, pigments, UV absorbers, antioxidants, fillers, plasticizers, antistatic agents, thermal stability Agents, surfactants, desiccants, deodorants, antibacterial agents, preservatives, antifoaming agents, and the like can be included.

In the present invention, the adhesive composition of the present invention is uniformly applied to a polarizing film and / or a protective film, and after both are bonded, they are pressure-bonded and heat-dried.
In applying such an adhesive composition on a polarizing film or a protective film, a roll coater method, an air doctor method, a blade coater method, a spray method, a dipping method, or just before bonding the polarizing film and the protective film, A known method such as laminating the two can be used after supplying and pouring an appropriate amount between the films.
For laminating and pressure bonding, for example, a roll laminator or the like can be used, and the pressure is selected from the range of 0.1 to 10 MPa. The heating and drying conditions are usually 5 to 150 ° C., particularly 30 to 120 ° C., for 10 to 60 minutes, further 30 seconds to 30 minutes, particularly 1 to 20 minutes.

  In the present invention, the adhesive composition is crosslinked to form an adhesive layer. The thickness of the adhesive layer is usually 0.01 to 10 μm, particularly preferably 0.05 to 5 μm. If the thickness is too thin, the adhesive force tends to be insufficient. If the thickness is too thick, uniform coating tends to be difficult, or thickness unevenness tends to occur and the appearance tends to deteriorate.

(Polarizing film)
The polarizing plate adhesive composition of the present invention is used for bonding a polarizing film and a protective film.
There is no restriction | limiting in particular as a polarizing film used by this invention, A well-known thing can be used.
For example, (i) A dichroic material such as iodine or a dichroic dye is adsorbed on a vinyl alcohol resin film such as a PVA film, a partially formalized PVA film, or an ethylene-vinyl alcohol resin film. Stretched (for example, see JP-A-2001-296427, JP-A-7-333426), (ii) a birefringent material having liquid crystallinity together with a dichroic material in the above (i) is a vinyl alcohol resin What is contained in the film (for example, see JP-A-2007-72203), (iii) A uniaxially stretched thermoplastic norbornene resin film containing a dichroic material (for example, JP-A-2001-356213) (Iv) PVA resin or ethylene-vinyl alcohol resin is dehydrated or deaceticated. Introducing a polyene structure continue, polyene-based film obtained by stretching them (e.g., see JP Patent 2007-17845.), And the like.
Among these, a uniaxially stretched film in which iodine is adsorbed on a PVA-based film is preferable because of excellent polarization characteristics.

The thickness of such a polarizer is usually 0.1 to 100 μm, particularly 0.5 to 80 μm, more preferably 1 to 60 μm.
The moisture content of the polarizer is usually 15% by weight or less, preferably 14% by weight or less, and particularly preferably 0.2 to 13% by weight.

(Protective film)
The protective film used in the present invention can make up for the lack of durability under high humidity, which is a problem of polarizers, by bonding to at least one surface, preferably both surfaces, of the polarizer.
Such a protective film compensates for the lack of durability under high humidity, which is a problem of the polarizing film, by adhering to at least one surface of the polarizing film, preferably both surfaces. The contact surface is hydrophobic, and the contact angle of water on the bonding surface is in the range of 5 to 90 degrees. Further, the contact angle is preferably 6 to 50 degrees, particularly 10 to 30 degrees. The contact angle on the surface of the protective film was measured by the droplet method in an atmosphere of 23 ° C. and 50% RH. When the contact angle of water is too small or too large, the adhesion with the polarizing film tends to be insufficient.
Furthermore, the properties required for the protective film used in the present invention include transparency, mechanical strength, thermal stability, moisture shielding properties, optical isotropy, and the like.

As a material for such a protective film, a cellulose ester resin, a cyclic olefin resin, and a (meth) acrylic resin are preferably used from the viewpoints of optical properties and durability.
Other materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polystyrene resins such as polystyrene and acrylonitrile / styrene copolymers, polyolefin resins such as polyethylene and polypropylene, polyarylate resins, and polycarbonate resins. , Vinyl chloride resins, amide resins such as nylon and aromatic polyamide, (fluorine-containing) polyimide resins, polyether ether ketone resins, polyphenylene sulfide resins, vinylidene chloride resins, polyvinyl acetal resins such as polyvinyl butyral And polyoxymethylene resins and epoxy resins. These may be used alone or in combination of two or more.

  Typical examples of the cellulose ester resin used in the cellulose ester resin film include triacetyl cellulose and diacetyl cellulose, but other lower fatty acid esters of cellulose, cellulose acetate propionate, cellulose acetate butyrate, and the like. The mixed fatty acid ester can be used.

  Examples of the cyclic olefin resin used in the cyclic olefin resin film include norbornene resins. Such norbornene resins include, for example, ring-opening (co) polymers of norbornene monomers, addition-polymerized norbornene monomers, addition-copolymerized norbornene monomers and olefin monomers such as ethylene and α-olefins. Resin etc. are included.

  Specific examples of norbornene-based monomers include dimers such as norbornene and norbornadiene; tricyclics such as dicyclopentadiene and dihydroxypentadiene; heptacyclics such as tetracyclopentadiene; these methyl, ethyl, propyl and butyl Substituents such as alkyl, alkenyl such as vinyl, alkylidene such as ethylidene, aryl such as phenyl, tolyl, and naphthyl; and ester groups, ether groups, cyano groups, halogens, alkoxycarbonyl groups, pyridyl groups, hydroxyl groups, carvone Examples include substituents having groups containing elements other than carbon and hydrogen, such as acid groups, amino groups, hydroxyl-free groups, silyl groups, epoxy groups, acryloyl groups, and methacryloyl groups.

  Examples of commercially available cyclic olefin-based resin films include “ARTON” manufactured by JSR, “ZEONOR”, “ZEONEX” manufactured by ZEON Corporation, “OPTOREZ” manufactured by Hitachi Chemical, “APEL” manufactured by Mitsui Chemicals, and the like. it can.

  Examples of the (meth) acrylic resin used in the (meth) acrylic resin film include poly (meth) acrylic acid esters such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, and methyl methacrylate. -(Meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid ester- (meth) acrylic acid copolymer, (meth) acrylic acid methyl-styrene copolymer, polymer having alicyclic hydrocarbon group (For example, methyl methacrylate-cyclohexyl methacrylate copolymer, methyl methacrylate- (meth) acrylate norbornyl copolymer, etc.), (meth) having a high glass transition temperature obtained by intramolecular crosslinking or intramolecular cyclization reaction Acrylic resins, rubber-acrylic graft type core-shell polymers, and the like can be mentioned.

  Examples of such commercially available (meth) acrylic resin films include “Acrypet VRL20A”, “Acrypet IRD-70” manufactured by Mitsubishi Rayon Co., Ltd., “MUX-60” manufactured by UMGABS, and the like.

  In addition, the protective film is subjected to surface hydrophilization treatment such as saponification treatment with an alkali solution for a film made of a cellulose ester resin or corona discharge treatment or plasma treatment for a film made of a cyclic olefin resin, as necessary. It may be what you did.

In addition, in order to improve the affinity with the adhesive on the surface of the protective film, it is possible to perform various surface treatments other than hydrophilization, and (meth) acrylic acid ester latex or styrene latex on the surface of the protective film, Examples thereof include an easy-adhesion layer and an anchor coat layer containing polyethyleneimine, polyurethane / polyester copolymer, etc., and a surface treatment method using a coupling agent such as a silane coupling agent and a titanium coupling agent.
In addition, it is also possible to use together the above-mentioned various surface treatment methods.
Moreover, what coated the antistatic agent on the surface of the protective film or contained it in the film is also preferably used.

  Although the thickness of such a protective film is not particularly limited, a film thicker than the polarizer is usually used, and has a function of imparting strength as a base material of the polarizer, and is usually 10 to 100 μm, preferably 20 to 80 μm. is there.

In addition, such a protective film can be provided with a hard coat layer on a surface that is not laminated with a polarizer, or can be subjected to various treatments such as anti-sticking, anti-reflection, and anti-glare.
Furthermore, various optical functional films such as a phase difference plate and a viewing angle widening film can be laminated.

(Polarizer)
The polarizing plate of the present invention is formed by adhering a polarizing film and a protective film using the adhesive composition for polarizing plate of the present invention, and a protective film is provided on at least one surface, preferably both surfaces of the polarizing film. It is done.
Thus, the obtained polarizing plate is excellent in water-resistant adhesive property that the adhesive layer does not elute even when immersed in water for a long time, and can be applied to a display device used under particularly severe conditions. Is.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded.
In the examples, “parts” and “%” mean weight basis.

Example 1
(1) Production of AA-PVA-Based Resin 3600 parts of powdered unmodified PVA (average polymerization degree 1200, saponification degree 99.2 mol%, average particle diameter 200 μm) are charged in a temperature-adjustable ribbon blender. 1000 parts of acetic acid was added to swell, and the mixture was heated to 60 ° C. while stirring at a rotation speed of 20 rpm. Thereafter, 550 parts of diketene was added dropwise over 3 hours, and the mixture was further reacted for 1 hour. After completion of the reaction, AA-PVA powder was prepared by washing with methanol. The degree of acetoacetylation was 5.3 mol%, and the degree of saponification and the average degree of polymerization were the same as those of unmodified PVA as a raw material.

(2) Preparation of adhesive composition 100 parts of 4% aqueous solution of AA-PVA-based resin (A1) obtained above, 2 parts of 10% aqueous solution of sodium glyoxylate (B1) as glyoxylate (B), 0.056 parts of ammonium zirconium carbonate (C1-1) (0.2 parts of AC-7 manufactured by Daiichi Rare Element Chemical Co., Ltd.) was mixed as a metal-based crosslinking agent (C) to prepare an adhesive composition.

(3) Production of polarizing film A 50 μm thick PVA film made of PVA resin having a polymerization degree of 2600 and a saponification degree of 99.8 mol% was immersed in water at 30 ° C., followed by iodine 0.2 g / L, iodide. Immersion / stretching in a dyeing solution at 30 ° C. containing 20 g / L of potassium, and further dipping / stretching in a boric acid treatment solution at 53 ° C. containing 50 g / L of boric acid and 50 g / L of potassium iodide. A polarizing film having a thickness of 0.0 and a thickness of 28 μm was obtained.

(4) Production of polarizing plate The polarizing film obtained in the above (3) is coated with an aqueous solution of the adhesive composition obtained in the above (2), and consists of triacetyl cellulose having a thickness of 25 μm from above. A protective film was bonded, laminated under a pressure of 0.25 MPa, and dried at 70 ° C. for 10 minutes to obtain a polarizing plate.
The water contact angle of the protective film made of triacetylcellulose was measured by a droplet method in an atmosphere of 23 ° C. and 50% RH using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) (n = 10 The average value was 16 degrees.

(4) Evaluation [Waterproof adhesive strength]
From the obtained polarizing plate, a sample of 100 mm × 25 mm was cut out with the extending direction of the polarizing film as the long side, and attached to a glass plate with a double-sided tape to obtain a sample for evaluation. The sample for evaluation was immersed in water at 60 ° C. for 1 day, and the change in the adhesive surface between the polarizing film and the protective film was visually observed and evaluated as follows. The results are shown in Table 1.
○ ・ ・ No peeling point × ・ ・ There is peeling point

Comparative Example 1
In Example 1, a polarizing plate was prepared in the same manner as in Example 1 except that zirconium ammonium carbonate (C1-1) was not blended, and was similarly evaluated. The results are shown in Table 1.

Comparative Example 2
In Example 1, a polarizing plate was prepared and evaluated in the same manner as in Example 1 except that 4 parts of a 10% aqueous solution of sodium glyoxylate was mixed and ammonium zirconium carbonate (C1-1) was not mixed. The results are shown in Table 1.

Comparative Example 3
In Example 1, 0.056 parts of ammonium zirconium carbonate (C1-1) was blended, and a polarizing plate was prepared in the same manner as in Example 1 except that sodium glyoxylate was not blended. The results are shown in Table 1.
The evaluation results of Examples and Comparative Examples are shown in Table 1.

  In Example 1 using the adhesive composition of the present invention, there was no peeling of the adhesive surface even after immersion in hot water at 60 ° C. for one day, and the appearance remained good. On the other hand, in Comparative Examples 1 and 2 that did not contain the metal-based crosslinking agent (C), peeling occurred on the adhesion surface. Moreover, the comparative example 3 which did not contain glyoxylate (B) and contained only the metal-based crosslinking agent (C) also peeled off on the adhesive surface.

  The polarizing plate obtained using the adhesive composition of the present invention is excellent in water-resistant adhesion, and such a polarizing plate is effectively used for a liquid crystal display device, particularly a display device used under severe conditions. It is done.

Claims (9)

  A polarizing plate adhesive composition comprising a modified group-containing polyvinyl alcohol resin (A) having active hydrogen, a glyoxylate (B), and a metal crosslinking agent (C).   The adhesive composition for polarizing plates according to claim 1, wherein the modified group-containing polyvinyl alcohol resin (A) having active hydrogen is an acetoacetyl group-containing polyvinyl alcohol resin (A1).   The adhesive composition for polarizing plates according to claim 1 or 2, wherein the glyoxylate (B) is an alkali metal salt of glyoxylic acid (B1).   The adhesive composition for polarizing plates according to any one of claims 1 to 3, wherein the metal-based crosslinking agent (C) is an inorganic acid salt (C1).   The adhesive composition for polarizing plates according to claim 4, wherein the inorganic acid salt (C1) is an inorganic acid salt (C1-1) of a zirconium compound.   The content of the glyoxylate (B) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the modified group-containing polyvinyl alcohol resin (A) having active hydrogen. 5. Adhesive composition for polarizing plates in any one of 5.   The content of the metal-based crosslinking agent (C) is 0.001 to 20 parts by weight with respect to 100 parts by weight of the modified group-containing polyvinyl alcohol resin (A) having active hydrogen. The adhesive composition for polarizing plates in any one of -7.   Content of a metal type crosslinking agent (C) is 0.001-10 weight part with respect to 1 weight part of glyoxylate (B), The polarizing plate in any one of Claims 1-6 characterized by the above-mentioned. Adhesive composition.   A polarizing plate obtained by bonding a polarizing film and a protective film using the adhesive composition for polarizing plates according to claim 1.