KR20090014968A - A polarizer and a method for producing the polarizer - Google Patents

Abstract

A polarizing plate and a manufacturing method thereof are provided to improve adhesive property and hot water resistance between a polarizing film and a protecting film by using an adhesion layer. A polarizing film is made of polyvinyl alcohol group resin. A polarizing plate is formed by laminating a protecting film on at least one surface of the polarizing film through an adhesion layer formed of polyvinyl alcohol group resin. The adhesion layer contains polyvinyl alcohol group resin and oxy zirconium salt. The polarizing plate is formed by using an adhesion composition having a solid weight ratio of polyvinyl alcohol group resin and oxy zirconium salt, 100:10~10000. The polarizing plate is made of any one selected from polyvinyl alcohol group resin degenerated with ace acetyl group, polyvinyl alcohol group resin degenerated with positive ions, and polyvinyl alcohol group resin degenerated with negative ions.

Description

A polarizing plate and its manufacturing method {A POLARIZER AND A METHOD FOR PRODUCING THE POLARIZER}

This invention relates to the polarizing plate by which the protective film is laminated | stacked on at least one surface of the polarizing film formed of polyvinyl alcohol-type resin through an adhesive bond layer, and its manufacturing method.

A polarizing plate is the structure which laminated | stacked the protective film on one side or both sides of the polarizing film formed from the polyvinyl alcohol-type resin in which the dichroic dye was adsorption-oriented normally. A polarizing plate is a component part of a liquid crystal display device, and is bonded by an adhesive to a liquid crystal cell through another optical film as needed.

The liquid crystal display device is to be used in various environments as its use is expanded. Therefore, high environmental resistance is calculated | required by the components which comprise a liquid crystal display device. For example, in the liquid crystal display device for mobile use represented by a mobile telephone, it is desired to be usable even under moist heat, and high moisture resistance against heat is also required for the polarizing plate used therein. However, in the polarizing plate of the conventional structure, especially when it exposes in a moist heat environment for a long time, there existed a problem that polarization performance fell easily and the interface of a polarizing film and a protective film peels easily.

It is proposed to use thermoplastic cycloolefin resin as a protective film of a polarizing plate about such a problem. For example, Japanese Patent Application Laid-Open No. 5-212828 (Patent Document 1) laminates a thermoplastic saturated norbornene-based resin sheet on at least one side of a polyvinyl alcohol sheet via an acrylic pressure-sensitive adhesive layer and heat-presses the polarizing plate (composite). Sheet) is disclosed. However, since the pressure-sensitive adhesives (also called pressure-sensitive adhesives) such as acrylics have their own thickness of about 10 to 50 µm, the liquid crystal display device was inevitably thickened. In addition, the adhesive for dry lamination, a styrene-butadiene rubber adhesive, an epoxy two-component curable adhesive, etc. contain the organic solvent, and there existed a environmental problem for the worker's health. In addition, if an adhesive containing such an organic solvent is to be applied to a polarizing plate manufacturing equipment that does not use a conventional organic solvent, it has involved complicated facilities such as the establishment of an explosion-proof equipment.

Moreover, it is also known to bond a cycloolefin resin film to the polarizing film which consists of polyvinyl alcohol-type resins through an adhesive bond layer, for example, Unexamined-Japanese-Patent No. 2005-70140 (patent document 2), Unexamined-Japanese-Patent No. 2005- 181817 (Patent Document 3) and Japanese Patent Application Laid-Open No. 2005-208456 (Patent Document 4) include a urethane resin, particularly a polyester ionomer-type urethane resin, in a polarizing film made of a polyvinyl alcohol-based resin. Laminating a cycloolefin resin film through an aqueous adhesive is described. Thereby, a cycloolefin protective film can be directly laminated | stacked on the polarizing film formed from polyvinyl alcohol-type resin by the roll-to-roll method.

On the other hand, Japanese Patent Laid-Open No. 9-318814 (Patent Document 5), Japanese Patent Application Laid-Open No. 2005-173440 (Patent Document 6) and Japanese Patent Application Laid-Open No. 2005-10760 (Patent Document 7) include polarizing plates. As a protective film of the above, various adhesives for bonding the protective film to the polarizing film which consists of polyvinyl alcohol-type resin are proposed using the transparent resin film formed from the cellulose resin represented by triacetyl cellulose. Here, in the adhesive applied between films, a polyvinyl alcohol-based resin containing an acetacetyl group and a compound having a methylol group are mixed at a specific blending ratio, a pH is adjusted after the methylol group-containing compound is blended, or glyoxal The adhesive agent which mix | blended resin or mix | blended a metal alkoxide compound is described, and a polarizing plate with high water resistance can be obtained by this.

Among them, Patent Document 4 discloses, on one side of a polarizing film formed of a polyvinyl alcohol-based resin, a cycloolefin via an aqueous first adhesive containing a compound having a polyester-based ionomer-type urethane resin and a glycidyloxy group. Laminating a resin film and laminating a cellulose acetate film on the other side through an aqueous second adhesive such as an aqueous solution of a polyvinyl alcohol resin having a composition different from that of the first adhesive to form a polarizing plate is disclosed. have. Moreover, in Example 2 of each of patent documents 2 and 3, the film of norbornene-type resin which is a kind of cycloolefin resin on one side of the polarizing film formed of polyvinyl alcohol-type resin, and triacetyl cellulose on the other side It is described that the films were bonded to each other through a urethane-based adhesive to form a polarizing plate.

Japanese Unexamined Patent Application Publication No. 2005-352011 (Patent Document 8) also discloses a polarizing plate in which a cycloolefin resin film is laminated on one side of a polarizing film and a cellulose acetate film is laminated on the opposite side.

An object of the present invention is a polarizing plate in which a protective film is laminated on at least one surface of a polarizing film formed of a polyvinyl alcohol-based resin via an adhesive layer, thereby improving the adhesive layer between the polarizing film and the protective film. It is to provide a polarizing plate with improved aqueous.

Another object of the present invention is to provide a method for producing a polarizing plate capable of firmly adhering a polarizing film formed of a polyvinyl alcohol-based resin and a protective film using an aqueous adhesive substantially free of an organic solvent.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching on such an objective, the present inventors used the aqueous mixture which mix | blended specific components as an adhesive agent which bonds a polarizing film and a protective film, and the adhesion speed | rate of a polarizing film and a protective film becomes quick, and adhesiveness and water resistance after adhesion This excellent polarizing plate was found to be obtained, and the present invention was reached. That is, this invention is as follows.

In the polarizing plate of the present invention, a protective film is laminated on at least one surface of a polarizing film formed of polyvinyl alcohol-based resin through a polyvinyl alcohol-based adhesive layer, and the adhesive layer contains a polyvinyl alcohol-based resin and an oxyzirconium salt. And an adhesive composition having a solid content weight ratio of polyvinyl alcohol-based resin and oxyzirconium salt of 100: 10 to 10000.

In the polarizing plate of the present invention, the polyvinyl alcohol-based resin included in the adhesive composition is selected from acetacetyl-modified polyvinyl alcohol-based resin, cation-modified polyvinyl alcohol-based resin and anion-modified polyvinyl alcohol-based resin. It is preferable that it is at least one.

Moreover, in the polarizing plate of this invention, it is preferable that the oxy zirconium salt contained in an adhesive composition is at least any one selected from zirconium oxynitrate and zirconium oxyacetate.

Moreover, in the polarizing plate of this invention, it is preferable that a protective film consists of cellulose acetate type resin or cycloolefin type resin, The protective film consisting of cellulose acetate type resin is laminated | stacked on one side of a polarizing film, and the other side of a polarizing film It is more preferable that the protective film which consists of cycloolefin resin laminated on the surface.

The present invention also includes an adhesive in which a polyvinyl alcohol-based resin and an oxyzirconium salt are contained on at least one side of the polarizing film formed of the polyvinyl alcohol-based resin, and the solid content weight ratio of the polyvinyl alcohol-based resin and the oxyzirconium salt is 100: 10 to 10000. It also provides about the manufacturing method of the polarizing plate which laminates a protective film through a composition.

In the manufacturing method of the polarizing plate of this invention, the polyvinyl alcohol-type resin contained in an adhesive composition is the acetacetyl-group modified polyvinyl alcohol-type resin, the cation-modified polyvinyl alcohol-type resin, and the anion-modified polyvinyl alcohol-type resin It is preferable that it is at least any one selected from.

Moreover, in the manufacturing method of the polarizing plate of this invention, it is preferable that the oxy zirconium salt contained in an adhesive composition is at least any one selected from zirconium oxynitrate and zirconium oxyacetate.

According to this invention, the polarizing plate which is excellent in the adhesiveness of a polarizing film and a protective film, and very excellent in hot water resistance compared with a conventional product can be manufactured. In addition, according to the present invention, since it is not necessary to use an organic solvent in the production of the polarizing plate, it is excellent in environmental aspects and safety and hygiene, and can be manufactured with the same equipment as that of a polarizing plate made of a conventional protective film / polarizing film. There is no need to invest.

The polarizing plate of this invention basically comprises the structure by which a protective film is laminated | stacked on at least one surface of the polarizing film which consists of polyvinyl alcohol-type resin through a polyvinyl alcohol-type adhesive bond layer. Hereinafter, each structure of the polarizing plate of this invention is demonstrated in detail.

<Polarizing film>

Polyvinyl alcohol-type resin which comprises a polarizing film can be obtained by saponifying a polyvinyl acetate type resin. As polyvinyl acetate type resin, the copolymer etc. of vinyl acetate and the other monomer copolymerizable with it besides the polyvinyl acetate which is a homopolymer of vinyl acetate are illustrated. As another monomer copolymerized with vinyl acetate, unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, vinyl ether, acrylamide which has an ammonium group, etc. are mentioned, for example. The saponification degree of the polyvinyl alcohol-based resin is usually 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be further modified. For example, polyvinyl formal, polyvinyl acetal, and the like modified with aldehydes can also be used. Moreover, the average degree of polymerization of polyvinyl alcohol-type resin which comprises a polarizing film is 1000-10000 normally, Preferably it is 1500-5000.

What formed such a polyvinyl alcohol-type resin into a film form (polyvinyl alcohol-type resin film) is used as a raw film of a polarizing film. The method of forming a polyvinyl alcohol-type resin into a film is not specifically limited, It can form into a film by a well-known method. Although the film thickness of a polyvinyl alcohol-type resin film is not specifically limited, For example, it is 10-150 micrometers.

The polarizing film is usually a step of uniaxially stretching such a polyvinyl alcohol-based resin film, a step of dyeing the polyvinyl alcohol-based resin film with a dichroic dye and adsorbing the dichroic dye, and a polyvinyl alcohol-based adsorbed dichroic dye. It manufactures through the process of processing a resin film with aqueous boric acid solution, and the process of washing with water after the process by this boric acid aqueous solution.

Uniaxial stretching may be performed before dyeing, may be performed simultaneously with dyeing, or may be performed after dyeing. When performing uniaxial stretching after dyeing, this uniaxial stretching may be performed before boric acid treatment, or may be performed during boric acid treatment. Of course, it is also possible to uniaxially stretch in these multiple steps. In uniaxial stretching, you may extend | stretch to 1 axis between rolls from which a circumferential speed differs, and you may extend | stretch to 1 axis using a thermal roll. Moreover, dry extending | stretching, such as extending | stretching in air | atmosphere, may be sufficient, and the wet extending | stretching which extends in the state swollen with a solvent may be sufficient. The draw ratio is usually 3 to 8 times.

To dye the polyvinyl alcohol-based resin film with a dichroic dye, for example, the polyvinyl alcohol-based resin film may be dipped in an aqueous solution containing the dichroic dye. Specifically as an dichroic dye, iodine and a dichroic dye are used. In addition, it is preferable that the polyvinyl alcohol-based resin film is subjected to an immersion treatment in water before the dyeing treatment.

When using iodine as a dichroic dye, the method of immersing and dyeing a polyvinyl alcohol-type resin film in the aqueous solution containing iodine and potassium iodide is employ | adopted normally.

The content of iodine in this aqueous solution is usually 0.01 to 1 part by weight per 100 parts by weight of water, and the content of potassium iodide is usually 0.5 to 20 parts by weight per 100 parts by weight of water. The temperature of the aqueous solution used for dyeing is usually 20 to 40 ° C, and the immersion time (dyeing time) for the aqueous solution is usually 20 to 1800 seconds.

On the other hand, when using a dichroic dye as a dichroic dye, the method of immersing and dyeing a polyvinyl alcohol-type resin film in the aqueous solution containing water-soluble dichroic dye is employ | adopted normally. The content of the dichroic dye in this aqueous solution is usually 1 × 10 ^-4 to 10 parts by weight, preferably 1 × 10 ^{-3 to} 1 part by weight, per 100 parts by weight of water. This aqueous solution may contain inorganic salts such as sodium sulfate as a dyeing aid. The temperature of the dye aqueous solution used for dyeing is 20-80 degreeC normally, and the immersion time (dyeing time) with respect to this aqueous solution is 10 to 1800 second normally.

The boric acid treatment after dyeing with a dichroic dye is performed by immersing the dyed polyvinyl alcohol-type resin film in boric acid containing aqueous solution. The amount of boric acid in the boric acid-containing aqueous solution is usually 2 to 15 parts by weight, preferably 5 to 12 parts by weight, per 100 parts by weight of water. When using iodine as a dichroic dye, it is preferable that this boric acid containing aqueous solution contains potassium iodide. The amount of potassium iodide in the boric acid-containing aqueous solution is usually 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight, per 100 parts by weight of water. Immersion time with boric acid containing aqueous solution is 60-1200 second normally, Preferably it is 150-600 second, More preferably, it is 200-400 second. The temperature of boric acid containing aqueous solution is 50 degreeC or more normally, Preferably it is 50-85 degreeC, More preferably, it is 60-80 degreeC.

The polyvinyl alcohol-based resin film after boric acid treatment is usually washed with water. A water washing process is performed by immersing the polyvinyl alcohol-type resin film which processed boric acid in water, for example. The temperature of water in a water washing process is 5-40 degreeC normally, and immersion time is 1-120 second normally. After water washing, a drying process is performed and a polarizing film is obtained. A drying process is normally performed using a hot air dryer and a far infrared heater. The temperature of a drying process is 30-100 degreeC normally, Preferably it is 50-80 degreeC. The time for the drying treatment is usually 60 to 600 seconds, preferably 120 to 600 seconds.

In this way, the polyvinyl alcohol-based resin film is subjected to uniaxial stretching, dyeing with a dichroic dye, and boric acid treatment to obtain a polarizing film. The thickness of this polarizing film is normally in the range of 5-40 micrometers, Preferably it is in the range of 10-35 micrometers.

<Adhesive layer>

As for the polarizing plate of this invention, the adhesive bond layer interposed between the polarizing film mentioned above and the protective film laminated | stacked on at least one surface of this polarizing film contains polyvinyl alcohol-type resin and an oxyzirconia salt, and polyvinyl alcohol-type It is formed using the adhesive composition whose solid content weight ratio of resin and oxy zirconium salt is 100: 10-10000, It is characterized by the above-mentioned. Such an adhesive layer in the present invention is a polarizing film formed of a polyvinyl alcohol-based resin while being an adhesive layer formed of an aqueous adhesive composition substantially free of an organic solvent, which does not cause environmental and health hazards to workers. And a protective film can be firmly adhere | attached.

Polyvinyl alcohol-type resin contained in the adhesive composition used for forming the adhesive bond layer in this invention is obtained by saponifying polyvinyl acetate-type resin similarly to the polyvinyl alcohol-type resin used for the above-mentioned polarizing film, As polyvinyl acetate type resin, the copolymer etc. of vinyl acetate and the other monomer copolymerizable with it besides the polyvinyl acetate which is a homopolymer of vinyl acetate are illustrated. As another monomer copolymerized with vinyl acetate, unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, vinyl ether, acrylamide which has an ammonium group, etc. are mentioned, for example. It is preferable that the polyvinyl alcohol-type resin contained in such an adhesive composition has a suitable degree of polymerization, When it is set as the aqueous solution of 4 weight% concentration, for example, it is preferable that the viscosity exists in the range of 4-50 mPa * sec, Furthermore, It is more preferable to exist in the range of 6-30 mPa * sec.

Although the saponification degree of the polyvinyl alcohol-type resin contained in the adhesive composition used for the adhesive bond layer in the polarizing plate of this invention is not restrict | limited, It is preferable that it is 74 mol% or more, Furthermore, it is more preferable that it is 80 mol% or more. If the saponification degree of polyvinyl alcohol-type resin contained in an adhesive composition is low, there exists a tendency for adhesiveness to become inadequate easily.

It is preferable that the polyvinyl alcohol-type resin contained in an adhesive composition is modified. As such modified polyvinyl alcohol-based resin, at least any one selected from acetacetyl group-modified polyvinyl alcohol-based resin, cation-modified polyvinyl alcohol-based resin, and anion-modified polyvinyl alcohol-based resin may be mentioned as a suitable one. In the case where such modified polyvinyl alcohol-based resin is used, there is an advantage that the water resistance of the adhesive layer is improved.

In addition, the adhesive composition used for the adhesive bond layer in the polarizing plate of this invention may contain 2 or more types of modified polyvinyl alcohol-type resins mentioned above, and also unmodified polyvinyl alcohol-type resin (specifically, , Complete or partial saponified polyvinyl acetate) and the above-described modified polyvinyl alcohol-based resin.

Suitable adhesive polyvinyl alcohol-based resins, specifically, the high polymer Z series, WO-239 (above, Nihon Kose Chemical Co., Ltd.), PVA-403, PVA-105, KL, are described in the above-mentioned adhesive composition. -318, KL-506, KM-118, KM-618, C-506 (above, Kuraray Co., Ltd.), etc. can be used suitably.

Although the density | concentration of the above-mentioned polyvinyl alcohol-type resin in the adhesive composition used for this invention is not specifically limited, It is preferable to exist in the range of 1-10 weight part with respect to 100 weight part of water, and to exist in the range of 1-5 weight part. More preferred. When the concentration of the polyvinyl alcohol-based resin is less than 1 part by weight with respect to 100 parts by weight of water, the adhesiveness tends to be easily lowered, and the concentration of the polyvinyl alcohol-based resin exceeds 10 parts by weight with respect to 100 parts by weight of water. In the case, there exists a tendency for the optical characteristic of the polarizing plate obtained to fall easily. In addition, although water used for the adhesive composition in this invention is not specifically limited, such as pure water, ultrapure water, and tap water, Pure water or ultrapure water is preferable from a viewpoint of maintaining the uniformity and transparency of the adhesive bond layer formed.

The adhesive composition used for this invention contains an oxy zirconium salt in addition to the polyvinyl alcohol-type resin mentioned above. Here, "oxy zirconium salt" refers to the salt containing the positive divalent group (called zirconyl) represented by ZrO, for example, zirconium oxynitrate (ZrO (NO ₃ ) ₂ ), zirconium oxyacetate (ZrO (C ₂₎ H ₃ O ₂ ) ₂ ), zirconium oxychloride (ZrOCl ₂ ), zirconium oxysulfate (ZrOSO ₄ ), zirconium oxycarbonate (ZrOCO ₃ ), zirconium ammonium oxycarbonate ((NH ₄ ) ₂ ZrO (CO ₃ ) ₂ ), Zirconium oxyoctylate (ZrO (C ₈ H ₁₅ O ₂ ) ₂ ), oxyzirconium hydroxide (ZrO (OH) ₂ ), zirconium hydroxide zirconium hydroxide (ZrO (OH) Cl), zirconium potassium oxycarbonate (K ₂ [ZrO ( CO ₃ ) ₂ ]). It is preferable that it is at least any one selected from zirconium oxynitrate and zirconium oxyacetate from a viewpoint of adhesiveness, adhesion | attachment speed, and water resistance among the above.

The oxyzirconium salts described above are suitable commercially available products such as zircosol ZN, zircosol AC-7, zirconium chloride, zircosol ZC, zircosol ZC-2, zirconyl sulfate, zircosol ZA, zircosol ZA-30, zir Cosol ZA-20, Zirconzol ZK-10, Zirconyl Octylate, Zirconyl Carbonate, Zirconium Hydroxide, R Zirconium Hydroxide, NN Zirconium Hydroxide (above, are all manufactured by Daiichi Kigso Chemical Co., Ltd.) and the like. Can be.

The adhesive composition used for this invention is 100: 10-10000 in solid content weight ratio of the above-mentioned polyvinyl alcohol-type resin and oxy zirconium salt. This is because when the oxyzirconium salt is less than 10 in the solid content weight ratio with respect to the polyvinyl alcohol resin 100, there is a problem in that the water resistance cannot be sufficiently expressed, and the oxyzirconium salt is contained in the solid content weight ratio relative to the polyvinyl alcohol resin 100. When it exceeds 10000, there exists a problem that the optical characteristic of the polarizing plate obtained easily falls, and when acidic oxy zirconium salts, such as zirconium oxynitrate, are used, metal corrosion resulting from the low pH becomes high. Moreover, it is preferable that solid content weight ratio of the polyvinyl alcohol-type resin and oxy zirconium salt in the adhesive composition used for this invention from a viewpoint of the balance of water resistance and an optical characteristic is 100: 50-100.

Moreover, as especially preferable combination of the above-mentioned polyvinyl alcohol-type resin and an oxy zirconium salt, it is a high-temperature polymer Z100 (made by Nihon Kose Chemical Co., Ltd.) as a polyvinyl alcohol-type resin, and a zircosol ZN (Daiichiki) as an oxy zirconium salt, for example. When using Kensogagaku Kogyo Co., Ltd., a polyvinyl alcohol-based resin, high polymer Z200 (manufactured by Nihon Kose Chemical Co., Ltd.), and zircosol ZA-20 (Daiichi Kigen Sogaku Kogyo Co., Ltd.) as an oxyzirconium salt (Manufactured by Co., Ltd.), KL318 (manufactured by Kuraray Co., Ltd.) as the polyvinyl alcohol-based resin, and the case of using zircosol AC-7 (manufactured by Daiichi Kigso Kagaku Kogyo Co., Ltd.) as the oxyzirconium salt. Can be mentioned. By these combinations, the pot life of an adhesive composition may be extended, and adhesiveness and water resistance may become high.

Although the thickness in particular of an adhesive bond layer in this invention is not restrict | limited, Usually, it is 0.001-5 micrometers, Preferably it is 0.01-2 micrometers, More preferably, it is 0.05-1 micrometer. When the thickness of an adhesive bond layer exceeds 5 micrometers, it will become easy to be poor in external appearance of a polarizing plate.

As for the adhesive bond layer in this invention, what added conventionally well-known suitable additives, such as a crosslinking agent, a plasticizer, a silane coupling agent, an antistatic agent, microparticles | fine-particles, was added to the adhesive composition mentioned above in the range which does not impair the effect of this invention. It may be formed using.

<Protective film>

The polarizing plate of this invention consists of a protective film laminated | stacked on at least one surface of the above-mentioned polarizing film via the above-mentioned adhesive bond layer. As a protective film in the polarizing plate of this invention, it is conventionally protected in the said field | areas, such as a cellulose acetate resin, cycloolefin resin, polyolefin resin, acrylic resin, polyimide resin, polycarbonate resin, polyester resin, etc. A protective film composed of a suitable material widely used as a material for forming a film can be used without particular limitation. It is preferable to provide the protective film comprised from cellulose acetate type resin or cycloolefin type resin among the above from a viewpoint of mass productivity and adhesiveness. Moreover, from the viewpoint of the ease of providing a surface treatment layer and the optical characteristic, in the polarizing plate of this invention, the protective film which consists of cellulose acetate-type resin is laminated | stacked on one side of a polarizing film, and cycloolefin is on the other side of a polarizing film. It can also be set as the structure which laminated | stacked the protective film comprised from system resin.

Cycloolefin resin which can be used suitably for the protective film in this invention is thermoplastic resin which has the unit of the monomer which consists of cyclic olefins (cycloolefin), such as a norbornene and a polycyclic norbornene-type monomer, for example (thermoplastic Also called cycloolefin resin). The cycloolefin resin may be a hydrogenated product of a ring-opening polymer of the cycloolefin, a ring-opening copolymer using two or more cycloolefins, or an addition polymer of an aromatic compound having a cycloolefin, a chain olefin, a vinyl group, or the like. It is also effective to introduce a polar group.

When a protective film is comprised using the copolymer of cycloolefin, linear olefin, and the aromatic compound which has a vinyl group, ethylene, propylene, etc. are mentioned as chain olefin, and as an aromatic compound which has a vinyl group, styrene and (alpha) -methylstyrene And nuclear alkyl substituted styrenes. In such a copolymer, the unit of the monomer which consists of cycloolefin may be 50 mol% or less (preferably 15-50 mol%). In particular, in the case of constituting the protective film using a ternary copolymer of a cycloolefin, a chain olefin, and an aromatic compound having a vinyl group, the unit of the monomer consisting of the cycloolefin can be made in a relatively small amount as described above. In such a terpolymer, the unit of the monomer which consists of linear olefins is 5 to 80 mol% normally, and the unit of the monomer which consists of an aromatic compound which has a vinyl group is 5 to 80 mol% normally.

Cycloolefin resins are suitable commercially available products such as Topas (manufactured by Ticona), Aton (manufactured by JSR Co., Ltd.), ZEONOR (manufactured by Nihon Xeon Co., Ltd.), ZEONEX (Nihon Zeon Co., Ltd.). ), Apel (made by Mitsui Chemicals), etc. can be used suitably. When forming these cycloolefin resin into a film and making into a film, well-known methods, such as the solvent casting method and the melt-extrusion method, are used suitably. Furthermore, cycloolefin resin previously formed into a film, such as Essina (made by Sekisui Chemical Co., Ltd.), SCA40 (made by Sekisui Chemical Co., Ltd.), and a Zeonoa film (made by Optes), etc. You may use the commercial item of a film as a protective film.

The protective film comprised from cycloolefin resin may be uniaxially stretched or biaxially stretched. The draw ratio in this case is usually 1.1 to 5 times, preferably 1.1 to 3 times.

Moreover, the cellulose acetate resin which can be used suitably for the protective film in this invention is a triacetyl cellulose film, a diacetyl cellulose, etc. as a partial or complete acetate ester of cellulose, for example.

As such a cellulose acetate resin, a suitable commercial item, such as FujiTak TD80 (manufactured by Fujishashin Film Co., Ltd.), FujiTak TD80UF (manufactured by Fujishashin Film Co., Ltd.), FujiTak TD80UZ (manufactured by Fujishashin Film Co., Ltd.), Cellulose acetate-based resin films such as KC8UX2M (manufactured by Konica Minolta Opto Co., Ltd.) and KC8UY (manufactured by Konica Minolta Opto Co., Ltd.) can be suitably used.

The thickness of the protective film used for the polarizing plate of the present invention is preferably smaller. However, if the thickness is too thin, the strength decreases and the workability tends to be inferior, and if the thickness is too thick, the transparency or the weight of the polarizing plate tends to increase. . From such a viewpoint, the thickness of the protective film in the polarizing plate of this invention is 5-200 micrometers normally in the case of the protective film comprised from cycloolefin resin, Preferably it is 10-150 micrometers, More preferably, it is 20-100 In the case of a protective film composed of a cellulose acetate resin, the thickness is usually 20 to 200 µm, preferably 30 to 150 µm, and more preferably 40 to 100 µm.

The protective film in the polarizing plate of the present invention may have been subjected to surface treatment such as an antiglare treatment, a hard coat treatment, an antistatic treatment, an antireflection treatment, and the like on the surface opposite to the surface that is attached to the polarizing film. Moreover, the coating layer which consists of a liquid crystalline compound, its high molecular weight compound, etc. may be formed in the surface on the opposite side to the surface adhering to the polarizing film of a protective film.

In addition, in the protective film in the polarizing plate of this invention, the optical functional film may be affixed on the surface opposite to the surface which sticks to a polarizing film through an adhesive layer. An adhesive is a viscoelastic body which can adhere to the surface of another substance only by pressing and can remove it, leaving little trace, if only the intensity | strength is left to a to-be-adhered surface, when peeling this from an adhered surface, and it is also called a pressure-sensitive adhesive. Examples of the optical functional film include an optical compensation film in which a liquid crystalline compound is coated and oriented on the surface of a substrate, a reflective polarization separating film that transmits a specific kind of polarization, and reflects polarization exhibiting opposite properties, and a polycarbonate resin. A retardation film made of cyclic resin, a retardation film made of cyclic polyolefin resin, a film having an antiglare function having an uneven shape on the surface, a film having a surface anti-reflection treatment, a reflection film having a reflection function on the surface, a reflection function and a transmission function together The semi-transmissive reflective film etc. which it has are mentioned.

As a commercial item which corresponds to the optical compensation film in which the liquid crystalline compound is apply | coated and orientated on the surface of a base material, For example, WV film (made by Fujishashin Film Co., Ltd.), NH film (made by Shin-Nihon Sekiyu Co., Ltd.), NR film ( Shin Nihon Sekiyu Co., Ltd.) etc. are mentioned. Moreover, DBEF (made by Sumitomo 3M Co., Ltd.) etc. are mentioned as a commercial item corresponding to the reflection type polarizing separation film which permeates a specific kind of polarization and reflects the polarization which shows the opposite property. Moreover, as a commercial item corresponding to the retardation film which consists of cyclic polyolefin resin, Aton (made by JSR Corporation), Essina (made by Sekisui Chemical Co., Ltd.), Zeonoa film (made by Optes), etc. Can be mentioned.

<Method of manufacturing polarizing plate>

The present invention further comprises a polyvinyl alcohol resin and an oxyzirconium salt on at least one side of the polarizing film formed of the polyvinyl alcohol resin, and the solid content weight ratio of the polyvinyl alcohol resin and the oxyzirconium salt is 100: 10 to 10000. It also provides about the manufacturing method of the polarizing plate which laminates a protective film through an adhesive composition. The polarizing plate of the present invention described above is not particularly limited, and the polarizing plate of the present invention is not limited to that produced by the manufacturing method of the polarizing plate of the present invention, but can be suitably produced by the manufacturing method of the polarizing plate of the present invention. .

In the manufacturing method of the polarizing plate of this invention, first, the polyvinyl alcohol-type resin and oxy zirconium salt which were mentioned above were mix | blended with solid content weight ratio within a specific range, and an adhesive composition is prepared. At this time, the viscosity of an adhesive composition can be controlled by the compounding quantity of polyvinyl alcohol-type resin. Also in the manufacturing method of the polarizing plate of this invention, as polyvinyl alcohol-type resin contained in an adhesive composition as mentioned above, the acetacetyl group-modified polyvinyl alcohol-type resin, the cation-modified polyvinyl alcohol-type resin, and anion-modified It is preferable that it is at least one selected from polyvinyl alcohol-type resin. Moreover, as an oxy zirconium salt contained in an adhesive composition, it is preferable that it is at least any one selected from zirconium oxynitrate and zirconium oxyacetate.

Bonding of the polarizing film and the protective film using such an adhesive composition can be performed by a conventionally well-known appropriate method, For example, the casting method, the Meyer bar coating method, the gravure coating method, the die coating method, the dip coating method, The spraying method etc. can mention the method of apply | coating an adhesive composition to the adhesive surface of a polarizing film and / or a protective film, and superimposing both. A casting method is a method of flowing an adhesive composition on the surface of a polarizing film or a protective film, which is a coated object, in a substantially vertical direction, in a substantially horizontal direction, or in an inclined direction between the two and spreading the coating composition. After apply | coating an adhesive composition, a polarizing film and a protective film are sandwiched and bonded by a nip roll.

Moreover, in order to improve adhesiveness, you may surface-treat a surface of a polarizing film and / or a protective film, such as a plasma process, a corona treatment, an ultraviolet irradiation process, a flame (flame) process, a saponification process, etc. suitably. As a saponification process, the method of immersing in aqueous alkali solution, such as sodium hydroxide and potassium hydroxide, is mentioned.

After laminating | stacking a polarizing film and a protective film, a drying process is performed. Although drying process is performed by spraying hot air, for example, the temperature at that time is suitably selected in 40-100 degreeC, Preferably it is 60-100 degreeC. The drying time is usually 20 to 1200 seconds.

Although an Example and a comparative example are given to the following and this invention is demonstrated in detail, this invention is not limited to these Examples. In the examples,% and parts representing the content to the amount used are based on weight unless otherwise indicated.

<Example 1>

A polyvinyl alcohol-based resin film (average degree of polymerization: 1700, saponification degree: 99.9 mol% or more) was subjected to uniaxial stretching at a draw ratio of 5 times, and contained iodine and potassium iodide while maintaining a tension state. It was immersed for 60 second in aqueous solution (iodine: potassium iodide: water = 0.05: 5: 100 (weight ratio)). Next, it was immersed for 300 second in the 65 degreeC aqueous solution (potassium iodide: boric acid: water = 2.5: 7.5: 100 (weight ratio)) containing potassium iodide and boric acid. After 20 seconds of washing with pure water at 25 ° C., the resultant was dried at 50 ° C. to obtain a polarizing film formed of polyvinyl alcohol-based resin.

Acetacetyl group-modified polyvinyl alcohol-based resin (Kose Chemical Z100, Nihon Kose Chemical Co., Ltd. make, saponification degree: 98.5 mol% or more) was dissolved in pure water to prepare an aqueous solution of 5% concentration. Separately, a 48% concentration aqueous solution of zirconium oxynitrate (zircosol ZN, manufactured by Daiichi Kigso Chemical Co., Ltd.) was obtained. The solid content weight ratio of acetacetyl-modified polyvinyl alcohol-based resin aqueous solution and zirconium oxynitrate aqueous solution to the above-mentioned aqueous solution of polyvinyl alcohol-based resin and zirconium oxynitrate, and acetoacetyl-modified polyvinyl alcohol-based resin: zirconium oxynitrate It mixed so that it might be 1: 1, and further diluted with pure water so that solid content weight ratio of the polyvinyl alcohol-type resin with respect to 100 parts of water may be 1.50, and the adhesive composition was prepared. This composition had a viscosity of 3.5 mPasec.

This adhesive composition was apply | coated on both surfaces of a polarizing film in 23 degreeC atmosphere, the protective film A which consists of 80 micrometers triacetylcellulose which surface-saponified on one side, and extending | stretching cyclic polyolefin type resin on the other side, The obtained protective film B of 70 micrometers in thickness was bonded. This was dried at 80 degreeC for two types of time of 30 second and 5 minutes, and the polarizing plate was produced (thickness of adhesive layer: about 0.1 micrometer).

<Example 2>

Acetacetyl-modified polyvinyl alcohol-based resin: zirconium oxynitrate = 1: 100 (solid content weight ratio), and further diluted with pure water so that the solid content weight ratio of polyvinyl alcohol-based resin to 100 parts of water is 0.10 to prepare Except having used the adhesive composition, it carried out similarly to Example 1, and produced the polarizing plate.

<Example 3>

Acetacetyl-modified polyvinyl alcohol-based resin: zirconium oxynitrate = 1: 1 (solid content weight ratio), and the mixture was further diluted with pure water so that the solid content weight ratio of the polyvinyl alcohol resin to 100 parts of water was 0.50 to prepare. Except having used the adhesive composition, it carried out similarly to Example 1, and produced the polarizing plate.

<Example 4>

Acetacetyl-modified polyvinyl alcohol-based resin: zirconium oxynitrate = 2: 1 (solid content weight ratio), and further diluted with pure water so that the solid content weight ratio of polyvinyl alcohol-based resin to 100 parts of water is 1.50, and prepared. Except having used the adhesive composition, it carried out similarly to Example 1, and produced the polarizing plate.

Example 5

Acetacetyl-modified polyvinyl alcohol-based resin: zirconium oxynitrate = 3: 1 (solid content weight ratio), and further diluted with pure water so that the solid content weight ratio of polyvinyl alcohol-based resin to 100 parts of water is 1.50 to prepare. Except having used the adhesive composition, it carried out similarly to Example 1, and produced the polarizing plate.

<Example 6>

Acetic acetyl-modified polyvinyl alcohol-based resin: zirconium oxynitrate = 20: 3 (solid content weight ratio), and blended in pure water so that the solid content weight ratio of polyvinyl alcohol-based resin to 100 parts of water is 1.50 Except having used the prepared adhesive composition, it carried out similarly to Example 1, and produced the polarizing plate.

<Example 7>

A carboxyl group-modified polyvinyl alcohol-based resin (Kurarepobal KL-318, manufactured by Kuraray Co., Ltd., saponification degree: 85 to 90 mol%) was dissolved in pure water to prepare an aqueous solution having a concentration of 5%. Separately, a 13% aqueous solution of zirconium ammonium oxycarbonate (zircosol AC-7, manufactured by Daiichi Kigso Chemical Co., Ltd.) was obtained. The polyvinyl alcohol-based resin solution and the aqueous zirconium ammonium oxycarbonate solution are mixed so that the solid content weight ratio of the carboxyl group-modified polyvinyl alcohol-based resin: ammonium zirconium oxycarbonate is 1: 1, and the polyvinyl alcohol-based resin is used for 100 parts of water. It was further diluted with pure water so that the solid content weight ratio of 1.50 might be 1.50 to prepare an adhesive composition. This composition had a viscosity of 4.5 mPasec. A polarizing plate was produced in the same manner as in Example 1 except that this adhesive composition was used.

<Example 8>

Adhesive prepared by compounding carboxyl group-modified polyvinyl alcohol-based resin: ammonium zirconium oxycarbonate = 1: 100 (solid weight ratio) and further diluted with pure water so that the solid content weight ratio of polyvinyl alcohol-based resin to 100 parts of water is 0.10. A polarizing plate was produced in the same manner as in Example 7 except that the composition was used.

Example 9

A 49% aqueous solution of zirconium hydroxide zirconium hydroxide (zircosol ZC-2, manufactured by Daiichi Kigso Chemical Co., Ltd.) was obtained. A 49% aqueous solution of zirconium oxychloride hydrochloride and a 5% aqueous solution of acetacetyl-modified polyvinyl alcohol-based resin (High Polymer Z100) prepared in Example 1 were acetacetyl-modified polyvinyl alcohol-based resin: It was mix | blended so that solid content weight ratio of zirconium might be 1: 1, and it diluted further with pure water so that solid content weight ratio of polyvinyl alcohol-type resin with respect to 100 parts of water may be 1.50, and the adhesive composition was prepared. This composition had a viscosity of 3.5 mPasec. A polarizing plate was produced in the same manner as in Example 1 except that this adhesive composition was used.

<Example 10>

Acetacetyl-modified polyvinyl alcohol-based resin: Adhesive composition prepared by further diluting with pure water so that the solid content weight ratio of polyvinyl alcohol-based resin with respect to 100 parts of water is set to 1: 100 (solid content weight ratio) to 100 parts of water. A polarizing plate was produced in the same manner as in Example 9 except for using.

<Example 11>

A 20% concentration aqueous solution of zirconium oxyacetate (zircosol ZA-20, manufactured by Daiichi Kigso Chemical Co., Ltd.) was obtained. A 20% aqueous solution of zirconium oxyacetate and a 5% aqueous solution of acetacetyl-modified polyvinyl alcohol-based resin (high polymer Z100) prepared in Example 1 were used for acetacetyl-modified polyvinyl alcohol-based resin: zirconium oxyacetate. It mix | blended so that solid content weight ratio might be 1: 1 and the adhesive composition was prepared. This composition had a viscosity of 3.5 mPasec. A polarizing plate was produced in the same manner as in Example 1 except that this adhesive composition was used.

<Example 12>

The adhesive composition prepared from acetacetyl-modified polyvinyl alcohol-based resin: zirconium oxyacetate = 1: 100 (solid weight ratio) and further diluted with pure water so that the solid content weight ratio of polyvinyl alcohol-based resin to 100 parts of water is 0.10. A polarizing plate was produced in the same manner as in Example 11 except for using.

Comparative Example 1

An adhesive composition prepared of acetacetyl-modified polyvinyl alcohol-based resin: zirconium oxynitrate = 20: 1 (solid weight ratio) and further diluted with pure water so that the solid content weight ratio of polyvinyl alcohol-based resin to 100 parts of water is 1.50. Except what was used, it carried out similarly to Example 1, and produced the polarizing plate.

Comparative Example 2

Carboxy group-modified polyvinyl alcohol-based resin: zirconium ammonium oxycarbonate = 20: 1 (solid weight ratio), and further diluted with pure water to prepare a solid content weight ratio of polyvinyl alcohol-based resin to 100 parts of water to prepare an adhesive composition using an adhesive composition A polarizing plate was produced in the same manner as in Example 7 except for the above.

Comparative Example 3

According to the description of Example 2 of JP-A-9-318814 (Patent Document 5), first, a polyvinyl alcohol-based resin (Gosenol AH17, manufactured by Nihon Kose Chemical Co., Ltd.), saponification degree: 97 ~ 98.5 mol%) 100 parts were dissolved in 1900 parts of water to prepare an aqueous solution of polyvinyl alcohol-based resin. Next, zirconium tetra-n-propoxide: acetylacetone = 1: 2 (molar ratio) was added to acetylacetone so that precipitation occurred. It was dripped at the aqueous solution of one polyvinyl alcohol-type resin, stirring, and it mixed at room temperature (23 degreeC) for 1 hour, and prepared the adhesive composition. A polarizing plate was produced in the same manner as in Example 1, except that the adhesive composition thus prepared was used.

<Comparative Example 4>

To 100 parts of pure water, 2.88 parts of acetacetyl-modified polyvinyl alcohol-based resin (manufactured by Gosei Chemical Z200, manufactured by Nihon Kose Chemical Co., Ltd., saponification degree: 99 mol% or more) and 1.24 parts of methylolmelamine (polyvinyl alcohol system) 43 parts of methylolmelamine) was melt | dissolved under the temperature conditions of 30 degreeC with respect to 100 parts of resin, and the adhesive composition was prepared. A polarizing plate was produced in the same manner as in Example 1 except that this adhesive composition was used.

Comparative Example 5

Except for using the adhesive composition prepared by changing the amount of acetacetyl-modified polyvinyl alcohol resin to 3.03 parts and the amount of methylol melamine to 1.15 part (36 parts of methylolmelamine relative to 100 parts of polyvinyl alcohol resin). A polarizing plate was produced in the same manner as in Example 4.

Comparative Example 6

30 parts of acetacetyl-group-modified polyvinyl alcohol-type resins (high polymer Z200) and 1.05 parts of methylol melamine (35 parts of methylol melamine with respect to 100 parts of polyvinyl alcohol-type resins) are 100 degreeC of pure waters A polarizing plate was produced in the same manner as in Comparative Example 4 except that the aqueous solution was dissolved under the conditions, and 0.4% acetic acid was added thereto to adjust the pH to 4.0 as an adhesive composition.

Comparative Example 7

30 parts of acetacetyl-group-modified polyvinyl alcohol-type resins (high polymer Z200) and 1.05 parts of methylol melamine (35 parts of methylol melamine with respect to 100 parts of polyvinyl alcohol-type resins) are 100 degreeC of pure waters A polarizing plate was produced in the same manner as in Comparative Example 4 except that the aqueous solution was dissolved under the conditions, and 0.4% acetic acid was added thereto to adjust the pH to 3.0 as an adhesive composition.

<Comparative Example 8>

Per 100 parts of pure water, polyvinyl alcohol-based resin (Kurarefobal 117H, Kuraray Co., Ltd., saponification degree: 99.3 mol% or more) and acetacetyl-modified polyvinyl alcohol-based resin (gosenol Z100, Nihon Kosega Gakugogyo Co., Ltd., saponification degree: 98.5 mol% or more, glyoxal in an aqueous solution containing 2 parts each, 0.1 part per 100 parts of total polyvinyl alcohol-based resin and acetacetyl-modified polyvinyl alcohol-based resin A polarizing plate was produced in the same manner as in Example 1, except that the adhesive composition prepared by adding 10 parts) was used.

Comparative Example 9

A polarizing plate was produced in the same manner as in Comparative Example 8 except that an adhesive composition having an amount of glyoxal added at 0.8 part (20 parts per 100 parts in total of polyvinyl alcohol-based resin and acetacetyl group-modified polyvinyl alcohol-based resin) was used.

<Evaluation test>

The following evaluation tests were done about the polarizing plates obtained in Examples 1-12 and Comparative Examples 1-9, respectively. The results are shown in Table 1.

[1] adhesiveness (cutter evaluation)

After leaving each polarizing plate at room temperature for 1 hour, a blade of a cutter is placed between each film of the polarizing plate (between the polarizing film and the protective film A and between the polarizing film and the protective film B), and the blade when the blade is pushed forward is entered. The method was evaluated based on the following criteria.

A: The cutter blade does not enter between any films.

B: When pushing on a blade, it stops when a blade enters 4-5 mm between at least one film.

C: When you push on the blade, at least one of the blades enters smoothly between the films (if the blades fit between one of the films, the blades do not enter the other side, or 4-5 mm stops when entered).

[2] water resistance

The following hot water resistance test (hot water immersion test) was performed about each polarizing plate left to stand for 24 hours in 23 degreeC and the environment of 55% of relative humidity, and water resistance was evaluated. First, a polarizing plate was cut into a rectangular shape of 5 cm × 2 cm with the absorption axis (stretching direction) of the polarizing plate as the long side, a sample was produced, and the dimension of the long side direction was measured correctly. Here, the sample has exhibited a unique color uniformly over the whole surface due to the iodine adsorbed to the polarizing film. Here, FIG. 1 is a figure which shows typically the evaluation test method of water resistance, FIG. 1 (A) has shown the sample 1 before hot water immersion, and FIG. 1 (B) has shown the sample 1 after hot water immersion. As shown in Fig. 1 (A), one short side of the sample was gripped by the gripper 5, and about 80% in the longitudinal direction was immersed in a 60 ° C water bath and held for 4 hours. Thereafter, the sample 1 was taken out of the water bath to wipe off moisture.

By warm water immersion, the polarizing film 4 of a polarizing plate shrinks. The shrinkage degree of this polarizing film 4 is the distance from the tip 1a (tip of a protective film) of the sample 1 in the center of the short side of the sample 1 to the tip of the polarizing film 4 which contracted. It evaluated by measuring and set it as shrink length. In addition, as shown in FIG. 1 (B), the polarizing film 4 positioned in the middle of the polarizing plate shrinks by hot water immersion, so that the region 2 in which the polarizing film 4 does not exist is formed between the protective films. . Moreover, iodine elutes from the periphery of the polarizing film 4 which contacts hot water by hot water immersion, and the part 3 with which the color was missing exists in the periphery of the sample 1. This discoloration degree was evaluated by measuring the distance from the tip of the contracted polarizing film 4 in the center of the short side of the sample 1 to the area | region where the color peculiar to a polarizing plate remains, and it was set as iodine elimination length. In addition, the sum total of the said shrinkage length and the iodine omission length was made into the total erosion length (X). That is, the total erosion length X is the distance from the tip 1a (tip of the protective film) of the sample 1 in the center of the short side of the sample 1 to the area | region in which the color peculiar to a polarizing plate remains. It can be judged that the smaller the shrinkage length, the iodine elimination length and the total erosion length X, the higher the adhesion (water resistance) in the presence of water.

In Table 1, PVA has shown the polyvinyl alcohol-type resin. From Table 1, it turns out that the polarizing plate of this invention shows sufficient adhesiveness even if a drying time is short, and the erosion from an edge part is small also in a hot water immersion test.

The embodiments and examples disclosed herein are to be considered in all respects as illustrative and not restrictive. The scope of the present invention is shown by above-described not description but Claim, and it is intended that the meaning of a claim and equality and all the changes within a range are included.

1: is a figure which shows the evaluation test method of water resistance typically, FIG. 1 (A) shows the sample 1 before hot water immersion, and FIG. 1 (B) shows the sample 1 after hot water immersion.

<Explanation of symbols for the main parts of the drawings>

1: sample

2: area in which no polarizing film exists between the protective films

3: missing color at the periphery of the polarizer

4: shrinked polarizing film

5: grip

Claims (8)

As a polarizing plate in which a protective film is laminated | stacked on at least one surface of the polarizing film formed of polyvinyl alcohol-type resin through a polyvinyl alcohol-type adhesive bond layer, The adhesive layer is a polarizing plate containing a polyvinyl alcohol-based resin and an oxyzirconium salt, and formed using an adhesive composition having a solid content weight ratio of the polyvinyl alcohol-based resin and the oxyzirconium salt of 100: 10 to 10000. The method of claim 1, wherein the polyvinyl alcohol-based resin included in the adhesive composition is at least any one selected from acetacetyl group-modified polyvinyl alcohol-based resins, cation-modified polyvinyl alcohol-based resins and anion-modified polyvinyl alcohol-based resins. One polarizer. The polarizing plate according to claim 1 or 2, wherein the oxyzirconium salt contained in the adhesive composition is at least one selected from zirconium oxynitrate and zirconium oxyacetate. The polarizing plate according to claim 1, wherein the protective film is made of cellulose acetate resin or cycloolefin resin. The polarizing plate of Claim 4 in which the protective film which consists of cellulose acetate type resin is laminated | stacked on one side of a polarizing film, and the protective film consisting of cycloolefin resin is laminated | stacked on the other side of a polarizing film. On at least one side of the polarizing film formed of polyvinyl alcohol-based resin, the polyvinyl alcohol-based resin and the oxyzirconium salt, containing a solid content weight ratio of polyvinyl alcohol-based resin and oxyzirconium salt 100-100 to 10000 through an adhesive composition The manufacturing method of a polarizing plate which laminates a protective film. The method of claim 6, wherein the polyvinyl alcohol-based resin included in the adhesive composition is at least any one selected from acetacetyl group-modified polyvinyl alcohol-based resins, cation-modified polyvinyl alcohol-based resins and anion-modified polyvinyl alcohol-based resins. The manufacturing method of one polarizing plate. The method for producing a polarizing plate according to claim 6 or 7, wherein the oxyzirconium salt contained in the adhesive composition is at least one selected from zirconium oxynitrate and zirconium oxyacetate.

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