JP6390764B2 - Polarizing plate and liquid crystal display device - Google Patents

Description

  The present invention relates to a polarizing plate and a liquid crystal display device.

  Along with the generalization of liquid crystal display devices in recent years, high durability is also required for the polarizing plate constituting the liquid crystal display device. For example, JP 2012-145645 A (Patent Document 1) discloses a protective film in which the linear expansion coefficient in the direction parallel to the transmission axis of the polarizing film in the protective film is smaller than the linear expansion coefficient in the transmission axis direction of the polarizing film. The polarizing plate obtained by laminating it on the polarizing film suppresses cracking of the polarizing film in an environment with a rapid temperature change (cold shock environment) that repeats low and high temperatures. It is stated that it will be.

  On the other hand, the above polarizing plate has insufficient durability in an environment (condensation thermal shock environment) in which a rapid temperature change is repeated in a high-humidity atmosphere, and there is room for improvement.

JP 2012-145645 A

  An object of the present invention is to provide a polarizing plate that is excellent in durability under a dew and cold shock environment in addition to a cold shock environment.

  That is, the present invention is a polarizing plate in which a first protective film having a thickness of 50 μm or less as a thickest protective film is laminated on at least one surface of a polarizing film having a thickness of 30 μm or less. The ratio of the thickness of the first protective film to the thickness is greater than 1.9, and the polarizing film is conditioned for 24 hours in an atmosphere at a temperature of 23 ° C. and a relative humidity of 55%, and then in an oven at 25 ° C. Polarized light whose strain in the direction of the transmission axis of the polarizing film is 700 με or less when 0.3 minute of pure water of 23 ° C. is attached after heating to 85 ° C. at a rate of 2 ° C./min. A polarizing plate characterized by being a film is provided.

  In the above polarizing plate, a first protective film is laminated on one side of the polarizing film, and a second protective film having the same thickness as the first protective film or thinner than the first protective film is laminated on the other side. It is preferable.

  In the above polarizing plate, at least one of the first and second protective films has an in-plane retardation Re at a wavelength of 590 nm of 10 nm or less, and an absolute value of a thickness direction retardation Rth at the same wavelength of 10 nm or less, The absolute value of the thickness direction retardation Rth at a wavelength of 480 to 750 nm is preferably 15 nm or less. Moreover, said 1st and 2nd protective film can each be independently comprised from a cellulose resin or polyolefin resin.

  Moreover, this invention provides the liquid crystal display device by which the polarizing plate in any one of the above is laminated | stacked on the at least single side | surface of the liquid crystal cell.

  ADVANTAGE OF THE INVENTION According to this invention, even if it puts on a cold shock environment and a condensation cold-heat shock environment, a crack etc. do not generate | occur | produce in a polarizing film but can provide the polarizing plate excellent in durability.

The layout of a measuring jig and a polarizing film used for measuring the amount of strain. The schematic diagram when a polarizing film and a strain gauge are made to adhere.

  The present invention will be described below.

[Polarizer]
The polarizing plate of the present invention has a configuration in which a protective film having a thickness of 50 μm or less is laminated on at least one surface of a polarizing film having a thickness of 30 μm or less.

<Polarized film>
A polarizing film, which is a constituent member of a polarizing plate, is usually a process of dyeing a dichroic dye on a raw film made of a polyvinyl alcohol resin to adsorb the dichroic dye (dyeing process), A step of treating with an acid aqueous solution (boric acid treatment step), a step of washing with water (water washing treatment step), and a step of drying the film (drying step) are sequentially performed. At this time, the polyvinyl alcohol-based resin film is stretched before the dyeing process, simultaneously with the dyeing process, or after the dyeing process.

  The polyvinyl alcohol resin constituting the raw film can be produced by saponifying the polyvinyl acetate resin. The polyvinyl acetate resin may be a copolymer of vinyl acetate, which is a homopolymer of vinyl acetate, or a copolymer of vinyl acetate and other monomers copolymerizable therewith. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acid, unsaturated sulfonic acid, olefin, vinyl ether, and acrylamide having an ammonium group.

  The saponification degree of the polyvinyl alcohol resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, for example, polyvinyl formal or polyvinyl acetal modified with an aldehyde can be used. The degree of polymerization of the polyvinyl alcohol resin is usually about 1,000 to 10,000, preferably about 1,500 to 5,000.

  What formed such a polyvinyl alcohol-type resin into a film becomes an above-mentioned raw film. The film formation of the polyvinyl alcohol resin can be performed by a known method. The film thickness of the raw film is, for example, about 10 to 150 μm, preferably about 10 to 100 μm.

  In the method for producing a polarizing film, the film applied to the polyvinyl alcohol-based resin film may be uniaxially stretched or biaxially stretched. For example, when carrying out uniaxial stretching with respect to a polyvinyl alcohol-type resin film, extending | stretching can be performed before a dyeing | staining process, simultaneously with a dyeing | staining process, or after a dyeing | staining process as above-mentioned. When uniaxial stretching is performed after the dyeing treatment step, stretching may be performed before the boric acid treatment step, or stretching may be performed during the boric acid treatment step. Of course, uniaxial stretching can also be performed in a plurality of stages shown here. For uniaxial stretching, a method of stretching between rolls having different peripheral speeds, a method of stretching using a hot roll, or the like can be employed. Uniaxial stretching may be performed by dry stretching in which stretching is performed in the air, or may be performed by wet stretching in which a polyvinyl alcohol-based resin film is stretched using a solvent such as water. The draw ratio is usually about 3 to 8 times.

  The dyeing process can be performed, for example, by a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a dichroic dye. Specifically, iodine or a dichroic organic dye is used as the dichroic dye. In addition, it is preferable to perform the process which a polyvinyl alcohol-type resin film swells by immersing in water before a dyeing process.

When iodine is used as the dichroic dye, a method of dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide is usually employed.
The content of iodine in this aqueous solution is usually about 0.01 to 1 part by weight per 100 parts by weight of water, and the content of potassium iodide is usually about 0.5 to 20 parts by weight per 100 parts by weight of water. It is. The temperature of this aqueous solution is usually about 20-40 ° C. Moreover, the immersion time (dyeing time) in this aqueous solution is usually about 20 to 1,800 seconds.

On the other hand, when a dichroic organic dye is used as the dichroic dye, a method of immersing and dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic organic dye is usually employed. The content of the dichroic organic dye in this aqueous solution is usually about 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 dye solution may contain an inorganic salt such as sodium sulfate as a dyeing assistant. The temperature of the aqueous dichroic organic dye solution is usually about 20 to 80 ° C. Moreover, the immersion time (dyeing time) in this aqueous solution is usually about 10 to 1,800 seconds.

  The boric acid treatment step performed after dyeing with a dichroic dye can be performed by a method of immersing a dyed polyvinyl alcohol resin film in an aqueous boric acid solution. The boric acid content in the boric acid aqueous solution is usually about 2 to 15 parts by weight, preferably 5 to 12 parts by weight per 100 parts by weight of water. When iodine is used as the dichroic dye, the boric acid aqueous solution preferably contains potassium iodide. The content of potassium iodide in the boric acid aqueous solution is usually about 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight per 100 parts by weight of water. The immersion time in the boric acid aqueous solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature of the boric acid aqueous solution is usually 50 ° C. or higher, preferably 50 to 85 ° C., more preferably 60 to 80 ° C.

  After the boric acid treatment step, the polyvinyl alcohol resin film is usually subjected to a water washing treatment step. The water washing treatment step can be performed, for example, by a method of immersing the polyvinyl alcohol resin film after the boric acid treatment step in water or a method of spraying water on the film. When immersed in water, the temperature of the water is usually about 5 to 40 ° C., and the immersion time is usually about 1 to 120 seconds.

  A polyvinyl alcohol-type resin film turns into a polarizing film through a drying process after a washing process. The drying step can be performed using a hot air dryer or a far infrared heater. The temperature of a drying process is about 30-100 degreeC normally, Preferably it is 50-80 degreeC. The time of a drying process is about 60 to 600 seconds normally, Preferably it is 120 to 600 seconds. By the drying process, the moisture content in the polarizing film is reduced to a practical level. The moisture content is usually about 5 to 20% by weight, preferably 8 to 15% by weight in a room temperature environment (23 ° C.). When the moisture content is less than 5% by weight, the polarizing film loses its flexibility, and may be damaged or broken after drying. On the other hand, if the moisture content exceeds 20% by weight, the thermal stability tends to be insufficient.

Here, the moisture content means the ratio (% by weight) of moisture in the film to the dry weight of the polyvinyl alcohol-based resin film, and is measured by drying a sample obtained by cutting a part of the film in a heating oven or the like. be able to. Specifically, it is defined by the following equation from the weight before drying and the weight after drying of the cut sample.
Moisture content = [(weight before drying−weight after drying) / weight after drying] × 100

  As described above, a polarizing film having a dichroic dye adsorbed and oriented on a polyvinyl alcohol-based resin film can be produced. The thickness of the polarizing film can be, for example, about 1 to 40 μm.

  In the present invention, among the polarizing films described above, a polarizing film conditioned for 24 hours at 23 ° C. in an atmosphere with a relative humidity of 55% is heated from 25 ° C. to 85 ° C. at a rate of 2 ° C./min. After heating to 85 ° C., 0.3 mL of pure water at 23 ° C. is attached, and the maximum amount of change (absolute value) of the length in the transmission axis direction of the polarizing film that occurs 1 minute after this attachment is attached to the water. A distortion amount calculated from the length of the previous polarizing film in the transmission axis direction is 700 με or less, preferably 650 με or less. By adopting a polarizing film having a strain amount of 700 με or less and combining it with a protective film described later, it is assumed that condensation occurs on the polarizing plate in an environment where high temperature conditions and low temperature conditions are repeated in a humid atmosphere. Becomes a polarizing plate excellent in durability.

Here, the strain refers to the amount of change per unit length when a load is applied to the object, and the elongation ratio at this time is referred to as the strain amount. The strain amount is a value obtained as follows. .
When a tensile force (or compressive force) P is applied to the material of length L ₀ , a corresponding stress σ is generated inside the material. Therefore, the tensile strain (compressive strain) proportional to the stress σ causes the material The length L is deformed long or short. The strain amount is obtained as a ratio of the deformation length ΔL of the material to the length L ₀ and is represented by the following formula (1).
ε = (L−L ₀ ) / L ₀ = ΔL / L ₀ (1)

The measurement of the maximum change amount of the length in the transmission axis direction of the polarizing film necessary for the calculation of the strain amount is performed as follows. FIG. 1 shows a measurement jig (A) for measuring the maximum change amount and a cross-sectional view (B) when the polarizing film and the measurement jig are assembled. Referring to the figure, the polarizing film is cut into pieces having a size of 100 mm × 100 mm in the absorption axis direction × transmission axis direction, and the outer circumference is 140 mm × 140 mm on both sides of the film piece 1. A measuring jig 3 whose center is cut out to a size of 80 mm × 80 mm is arranged. At this time, the measuring jig 3 is arranged without wrinkles or wrinkles on the film piece 1 of the polarizing film, and the polarizing film and the measuring jig 3 are covered with a 10 mm wide adhesive tape 5 so that the jig does not shift during measurement. To fix.
The measuring jig 3 can be made from, for example, plastic corrugated cardboard (hollow structure extruded product made of polypropylene as a raw material). As the plastic corrugated cardboard, an appropriate commercial product can be adopted, and examples of the commercial product include a trade name “Sunply (registered trademark) HP series” available from Sumika Plustech Co., Ltd.

As shown in FIG. 2, the strain gauge that measures the maximum amount of change in the length of the polarizing film in the transmission axis direction is arranged to be parallel to the transmission axis direction of the polarizing film (direction perpendicular to the stretching direction). . A strain gauge is arrange | positioned through the adhesive agent in the center part of a polarizing film. As this adhesive, a commercially available adhesive such as a cyanoacrylate adhesive can be used.
When measuring the maximum change amount, 23 ° C. pure water dropped on the film piece of the polarizing film is dropped on a portion of the polarizing film that is bonded to the strain gauge.

<Protective film>
The polarizing plate of the present invention is obtained by laminating a first protective film having a thickness of 50 μm or less as the thickest protective film on at least one surface of the polarizing film, and the first protective film with respect to the thickness of the polarizing film. Thickness ratio is greater than 1.9. The thickness ratio is preferably 2 or more, and preferably 40 or less.

  In the present invention, the first protective film is laminated on at least one surface of the polarizing film, but the other surface of the polarizing film has the same thickness as the first protective film or a second thinner than the first protective film. It is preferable that the protective film is laminated. The first protective film and the second protective film may be the same or different.

  The first and second protective films are preferably each composed of a resin having excellent transparency, mechanical strength, thermal stability, moisture shielding properties, and the like. Examples of such a resin include, for example, an acrylic resin having a methyl methacrylate resin as a representative example, a chain polyolefin resin having a polypropylene resin as a representative example, and a polyolefin resin containing a cyclic polyolefin resin, and a cellulose resin. Resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyvinyl chloride resin, styrene resin, acrylonitrile / styrene copolymer resin, acrylonitrile / butadiene / styrene copolymer resin, polyvinyl acetate resin, poly Vinylidene chloride resin, polyamide resin, polyacetal resin, polycarbonate resin, modified polyphenylene ether resin, polysulfone resin, polyethersulfone resin, polyarylate resin, polyamideimide resin, polyimide resin Such as butter, and the like. These resins can be used alone or in combination of two or more. Moreover, resin which performed arbitrary polymer modification | denaturation with respect to these resin can also be used as resin which comprises a protective film. Examples of the polymer modification include copolymerization, crosslinking, molecular terminal modification, stereoregularity control, and mixing including a case involving a reaction between different polymers.

  Among the above-described resins, acrylic resins, polyolefin resins, cellulose resins, and polyethylene terephthalate resins are preferably used.

  The acrylic resin is generally a polymer mainly composed of methacrylic acid ester, and can be a copolymer in which a small amount of other comonomer components are copolymerized. Among such acrylic resins, a methyl methacrylate resin containing 50% by weight or more of a structural unit derived from methyl methacrylate is preferable based on the total amount of the resin. In the methyl methacrylate resin, the content of the structural unit derived from methyl methacrylate is preferably 70% by weight or more based on the total amount of the methyl methacrylate resin. A homopolymer of methyl methacrylate having a content of 100% by weight may be used.

  The methyl methacrylate-based resin can be usually obtained by polymerizing a monofunctional monomer mainly composed of methyl methacrylate in the presence of a radical polymerization initiator and a chain transfer agent. In addition to methyl methacrylate, the monofunctional monomer may be blended with a component that can be copolymerized therewith. If desired, a small amount of a polyfunctional monomer may be blended with a monofunctional monomer mainly composed of methyl methacrylate and copolymerized.

  Monofunctional monomers that can be copolymerized with methyl methacrylate include, for example, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, and 2-hydroxyethyl methacrylate. Methacrylic acid esters other than methyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, and 2-ethylhexyl acrylate; Hydroxyacrylates such as hydroxymethyl, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate Alkyl esters; unsaturated acids such as methacrylic acid and acrylic acid; halogenated styrenes such as chlorostyrene and bromostyrene; substituted styrenes such as vinyltoluene and α-methylstyrene; acrylonitrile and methacrylonitrile And unsaturated nitriles such as: maleic anhydride and unsaturated acid anhydrides such as citraconic anhydride; unsaturated imides such as phenylmaleimide and cyclohexylmaleimide. These monomers may be copolymerized alone with methyl methacrylate, or may be copolymerized in combination of two or more.

  Examples of polyfunctional monomers that can be copolymerized with methyl methacrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. Compound in which both terminal hydroxyl groups of ethylene glycol or its oligomer are esterified with acrylic acid or methacrylic acid; Compound in which both terminal hydroxyl groups of propylene glycol or its oligomer are esterified with acrylic acid or methacrylic acid; Neopentyl glycol di (meta ) A compound obtained by esterifying a hydroxyl group of a dihydric alcohol such as acrylate, hexanediol di (meth) acrylate and butanediol di (meth) acrylate with acrylic acid or methacrylic acid; A compound obtained by esterifying the hydroxyl groups at both ends of an alkylene oxide adduct of enolic A or bisphenol A or a halogen-substituted product thereof with acrylic acid or methacrylic acid; a polyhydric alcohol such as trimethylolpropane and pentaerythritol with acrylic acid or methacrylic acid Compounds esterified with acids; compounds obtained by ring-opening addition of epoxy groups of glycidyl acrylate or glycidyl methacrylate to terminal hydroxyl groups of compounds having two or more hydroxyl groups; succinic acid, adipic acid, terephthalic acid, phthalic acid and their halogens Compounds obtained by ring-opening addition of an epoxy group of glycidyl acrylate or glycidyl methacrylate to dibasic acids such as substituted products or alkylene oxide adducts thereof; allyl (meth) acrylates; Such as sulfonyl compounds. In the case of copolymerizing a polyfunctional monomer, among these, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate and neopentyl glycol dimethacrylate are preferably used.

  Moreover, the resin modified | denatured by making it react between the functional groups which methyl methacrylate resin has can also be used. Examples of such a reaction between functional groups include, for example, demethanol condensation reaction in a polymer chain between a methyl ester group of methyl acrylate and a hydroxyl group of methyl 2- (hydroxymethyl) acrylate, and a carboxyl group of acrylic acid and 2 Examples thereof include a dehydration condensation reaction in a polymer chain with a hydroxyl group of-(hydroxymethyl) methyl acrylate.

  A commercially available product can be easily obtained for the methyl methacrylate resin. Examples of commercial products are “Sumipex” (registered trademark) sold by Sumitomo Chemical Co., Ltd., “Acrypet” (registered trademark) sold by Mitsubishi Rayon Co., Ltd. "Delpet" (registered trademark) sold by Asahi Kasei Co., Ltd., "Parapet" (registered trademark) sold by Kuraray Co., Ltd., and "Acryviewer" (registered trademark) sold by Nippon Shokubai Co., Ltd. (registered) Trademark).

  As described above, the polyolefin resin encapsulates the chain polyolefin resin and the cyclic polyolefin resin. Typical examples of the chain polyolefin resin include a polyethylene resin and a polypropylene resin. Of these, polypropylene resins are preferable. The polypropylene resin is a polymer of a chain olefin monomer having propylene as a main component, and is usually a chain olefin resin in which 80 mol% or more of repeating units are composed of propylene. The polypropylene resin may be a homopolymer of propylene, or a copolymer obtained by copolymerizing a comonomer mainly composed of propylene and copolymerizable therewith. The copolymerizable comonomer can be copolymerized at a ratio of about 1 to 20% by weight, preferably 3 to 10% by weight, based on the total amount of monomers to be copolymerized.

  As a comonomer copolymerizable with propylene, ethylene, 1-butene, or 1-hexene is preferable. Especially, since the polypropylene resin which is comparatively excellent in transparency is obtained, what copolymerized ethylene in the ratio of 1-20 weight%, preferably 3-10 weight% is preferable. By setting the copolymerization ratio of ethylene to 1% by weight or more, an effect of increasing transparency appears. On the other hand, when the copolymerization ratio of ethylene exceeds 20% by weight, the melting point of the resin is lowered, and the heat resistance required for the protective film may be impaired.

  The content of the xylene-soluble component (CXS component: CXS is an abbreviation of cold xylene soluble) at 20 ° C. in the polypropylene resin is preferably 1% by weight or less based on the total amount of the resin. % Or less is more preferable. Among the polypropylene-based resins, a propylene homopolymer having a CXS component of 1% by weight or less, and further 0.5% by weight or less is one suitable example.

  As the polypropylene resin, a commercially available product can be easily obtained. Examples of commercially available products are “Prime Polypro” (registered trademark) sold by Prime Polymer Co., Ltd., “Novatech” (registered trademark) sold by Nippon Polypro Co., Ltd. “Wintech” (registered trademark), “Sumitomo Noblen” (registered trademark) sold by Sumitomo Chemical Co., Ltd., “Sun Aroma” (registered trademark) sold by Sun Allomer Co., Ltd.

The cyclic polyolefin resin is obtained by polymerizing cyclic olefin monomers such as norbornene and other cyclopentadiene derivatives in the presence of a catalyst.
Examples of cyclic polyolefin resins include ring-opening metathesis polymerization from cyclopentadiene and olefin or (meth) acrylic acid or its ester, using norbornene or its derivative obtained by Diels-Alder reaction as a monomer, followed by hydrogenation. A ring-opening metathesis polymerization from dicyclopentadiene and an olefin or (meth) acrylic acid or ester thereof using tetracyclododecene or a derivative thereof obtained by Diels-Alder reaction as a monomer, followed by hydrogenation A ring-opening metathesis copolymerization of at least two monomers selected from norbornene, tetracyclododecene, their derivatives, and other cyclic olefin monomers, followed by hydrogenation Resulting I resin; norbornene, a cyclic olefin such as tetracyclododecene or a derivative thereof, such as linear olefins and / or resins obtained by addition copolymerization of an aromatic compound having a vinyl group.

  As the cyclic polyolefin-based resin, a commercially available product can be easily obtained. Examples of commercial products are produced by TOPAS ADVANCED POLYMERS GmbH under the trade names, and sold by “TOPAS” (registered trademark) and JSR, which are sold by Polyplastics in Japan. "Arton" (registered trademark), "Zeonor" (registered trademark) and "Zeonex" (registered trademark) sold by Nippon Zeon Co., Ltd., "Apel" sold by Mitsui Chemicals, Inc. There is.

  The cellulose resin may be an organic acid ester or mixed organic acid ester of cellulose in which part or all of the hydrogen atoms in the hydroxyl group of cellulose are substituted with an acetyl group, a propionyl group, and / or a butyryl group. Examples thereof include cellulose acetate, propionate, butyrate, and mixed esters thereof. Of these, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and the like are preferable.

  The polyethylene terephthalate resin is a resin in which 80 mol% or more of the repeating units are composed of ethylene terephthalate based on the total amount of the resin, and may contain other dicarboxylic acid components and / or other diol components. Examples of other dicarboxylic acid components include isophthalic acid, 4,4′-dicarboxydiphenyl, 4,4′-dicarboxybenzophenone, bis (4-carboxyphenyl) ethane, adipic acid, sebacic acid, 1,4 -Dicarboxycyclohexane etc. are mentioned. Examples of other diol components include propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, ethylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  Two or more kinds of these other dicarboxylic acid components and other diol components can be combined as necessary, and hydroxycarboxylic acids such as p-hydroxybenzoic acid and p-β-hydroxyethoxybenzoic acid can be used in combination. it can. Further, as other copolymerization component, a dicarboxylic acid component or a diol component containing a small amount of an amide bond, a urethane bond, an ether bond, a carbonate bond or the like can also be used.

  Polyethylene terephthalate resin can be produced by directly polycondensing terephthalic acid and ethylene glycol (and other dicarboxylic acids or other diols as required), dialkyl esters of terephthalic acid and ethylene glycol (and as required) A method of polycondensation of a dialkyl ester of another dicarboxylic acid or other diol) while undergoing a transesterification reaction, an ethylene glycol ester of terephthalic acid (and other dicarboxylic acid if necessary) (and another diol if necessary) For example, a method in which an ester) is polycondensed in the presence of a catalyst is employed. Furthermore, if necessary, additional solid phase polymerization can be performed to increase the molecular weight or reduce the low molecular weight components.

  As a method for forming the resin as described above, a method corresponding to each resin may be appropriately selected. For example, a solvent cast method in which a resin dissolved in a solvent is cast on a metal band or drum, and the solvent is removed by drying to obtain a film. The resin is heated above its melting temperature, kneaded and extruded from a die. A melt extrusion method for obtaining a film by cooling can be used. In the melt extrusion method, a single layer film can be extruded or a multilayer film can be coextruded. In general, the melt extrusion method is preferably employed for the production of a polyolefin-based resin from the viewpoint of productivity, and the solvent casting method is employed for the formation of a cellulose-based resin.

  Commercially available products of these resin films can be easily obtained. Examples of commercially available methyl methacrylate resin films are “Technoloy” (registered trademark) sold by Sumitomo Chemical Co., Ltd. and “Acrylic” sold by Mitsubishi Rayon Co., Ltd. “Light” (registered trademark) and “Acryprene” (registered trademark), “Delagrass” (registered trademark) sold by Asahi Kasei Co., Ltd., “Paragrass” (registered trademark) sold by Kuraray Co., Ltd. and “ "Comoglass" (registered trademark), "Acryviewer" (registered trademark) sold by Nippon Shokubai Co., Ltd.

  Examples of commercially available polyolefin resin films are “Arton Film” sold by JSR Co., Ltd. (“Arton” is a registered trademark of the company) and Sekisui Chemical Co., Ltd. “Essina” (registered trademark), “Zeonor Film” (registered trademark) sold by Nippon Zeon Co., Ltd., and the like.

  Examples of commercially available cellulose resin films are “Fujitac (registered trademark) TD” sold by Fuji Film Co., Ltd. and Konica Minolta Advanced Layer Co., Ltd. TAC film “KC series” (trade name).

  Examples of commercially available polyethylene terephthalate resin films include “Novaclear” (registered trademark) sold by Mitsubishi Chemical Co., Ltd. and “A-” sold by Teijin Chemicals Ltd. PET sheet ". Examples of commercially available polypropylene resin films are “FILMAX CPP film” sold by FILMAX, “Santox” sold by Sun Tox Co., Ltd., and Tosero Co., Ltd. "Tosero" sold by Toyobo Co., Ltd., "Toyobo Pyrene Film" sold by Toyobo Co., Ltd., "Trephan" (registered trademark) sold by Toray Film Processing Co., Ltd., Nippon Polyace Co., Ltd. ) "Nihon Polyace" sold by), and "Dazai FC" sold by Futamura Chemical Co., Ltd.

  The first and / or second protective films are each composed of the resin as described above, but may be subjected to a stretching treatment or a shrinking treatment depending on the application to give a retardation. . The retardation value of the first and / or second protective film has an in-plane retardation Re at a wavelength of 590 nm of 10 nm or less, an absolute value of retardation Rth in the thickness direction at the same wavelength of 10 nm or less, and a wavelength In the range of 480 to 750 nm, the absolute value of retardation Rth in the thickness direction is preferably 15 nm or less.

  When the retardation is imparted to the first and / or second protective film, the retardation value is easy to control and easily available, so that the cellulose-based resin or the chain polyolefin-based resin or the cyclic polyolefin-based resin is easily obtained. Is preferably used.

  The thickness of the first protective film is 50 μm or less, preferably 5 μm or more, more preferably 10 μm or more, and preferably 49 μm or less, more preferably 30 μm or less. The thickness of a 2nd protective film should just be the same thickness as a 1st protective film, or a thing thinner than a 1st protective film.

  The polarizing plate of the present invention is formed by laminating at least one surface of the polarizing film as the thickest protective film in which the first protective film described above is laminated on the polarizing film. The thickness ratio of one protective film is greater than 1.9.

  When the ratio of the thickness of the polarizing film to the thickness of the first protective film is in the above range, the polarizing plate is generated in the polarizing film in an environment where the high temperature condition and the low temperature condition are repeated (under a cold shock environment). Since a stress such as shrinkage is suppressed by the protective film and cracks are hardly generated in the polarizing film, the polarizing plate is excellent in durability.

  In the present invention, the polarizing film employs a polarizing film having a strain amount of 700 με or less in the transmission axis direction (direction perpendicular to the stretching direction) of the polarizing film under the specific conditions described above, and the thickness of the polarizing film and the first protective film. It is important that the ratio is within the above range.

  When the ratio of the thickness of the polarizing film and the first protective film is 1.9 or less, and the strain amount of the polarizing film is greater than 700 με, the polarizing plate has a dimensional change that occurs in the polarizing film. In a thermal shock test that assumes an environment in which high and low temperatures are repeated, and in a condensation thermal shock test that assumes an environment in which high and low temperature conditions are repeated in a humid atmosphere Tend to crack. Further, when the ratio of the thickness of the polarizing film and the first protective film is larger than 40 and the strain amount of the polarizing film is larger than 700 με, the polarizing plate has a dimensional change that the first protective film causes in the polarizing film. Since it tends to be excessively suppressed, the stress applied to the inside of the polarizing film increases, and cracks tend to occur in the polarizing film in the thermal shock test and the condensation thermal shock test.

<Adhesive (adhesive layer)>
The first protective film is laminated on at least one surface of the polarizing film described above to form a polarizing plate. A protective film is normally laminated | stacked on a polarizing film through an adhesive bond layer or an adhesive layer. The thickness of the adhesive layer or pressure-sensitive adhesive layer can be about 0.01 to 30 μm, preferably 0.01 to 10 μm, and more preferably 0.05 to 5 μm. When the thickness of the adhesive layer or the pressure-sensitive adhesive layer is within this range, the protective film and the polarizing film do not float or peel off, and an adhesive force having no practical problem can be obtained.

  In the adhesive layer or the pressure-sensitive adhesive layer, an appropriate adhesive or pressure-sensitive adhesive can be employed according to the type and purpose of the adherend, and an anchor coating agent can be used as necessary. Examples of the adhesive include a solvent-type adhesive, an emulsion-type adhesive, a pressure-sensitive adhesive, a rewet-adhesive, a polycondensation-type adhesive, a solventless-type adhesive, a film-type adhesive, and a hot-melt-type adhesive. Is mentioned. Moreover, what is necessary is just to be able to fully adhere | attach a polarizing film and a protective film as an adhesive, The adhesive layer mentioned later can also be employ | adopted with the kind of protective film.

  One preferred adhesive is an aqueous adhesive, that is, an adhesive component in which the adhesive component is dissolved or dispersed in water. Examples of such an adhesive component include a polyvinyl alcohol resin and a urethane resin having a hydrophilic group. The water-based adhesive can be prepared by mixing such an adhesive component with water together with an additive that is blended as necessary. Examples of commercially available polyvinyl alcohol resins that can be used in aqueous adhesives include “Kuraray Poval (registered trademark) KL-318” (trade name), which is a carboxyl group-modified polyvinyl alcohol sold by Kuraray Co., Ltd. There is.

The water-based adhesive can contain a crosslinking agent as necessary. Examples of the crosslinking agent include amine compounds, aldehyde compounds, methylol compounds, water-soluble epoxy resins, isocyanate compounds, and polyvalent metal salts. When a polyvinyl alcohol resin is used as an adhesive component, an aldehyde compound such as glyoxal, a methylol compound such as methylol melamine, a water-soluble epoxy resin, or the like is preferably used as a crosslinking agent.
Here, the water-soluble epoxy resin is, for example, a polyamide obtained by reacting epichlorohydrin with a polyamide polyamine which is a reaction product of a polyalkylene polyamine such as diethylenetriamine or triethylenetetramine and a dicarboxylic acid such as adipic acid. It can be an epoxy resin. Examples of commercially available water-soluble epoxy resins include “Smiles Resin (registered trademark) 650 (30)” (trade name) sold by Sumika Chemtex Co., Ltd.

  When employing a water-based adhesive for the production of the polarizing plate, the water-based adhesive is applied to the bonding surface of the polarizing film and / or protective film, the two are bonded together, and then the water-based adhesive is dried. A polarizing plate can be obtained by curing. Prior to pasting, it is also effective to give the protective film easy adhesion treatment such as saponification treatment, corona discharge treatment, or plasma treatment to enhance wettability. A drying temperature can be about 60-100 degreeC, for example. Further, after the drying treatment, curing at a temperature slightly higher than room temperature, for example, a temperature of about 30 to 50 ° C. for about 1 to 10 days is preferable because the adhesive force can be further increased.

  Another preferred adhesive is a curable adhesive that is cured by irradiation with active energy rays or heating, and examples thereof include an epoxy adhesive. In the present invention, an epoxy-based adhesive is suitably used from the viewpoint of ease of handling, adhesive strength, and the like. Here, the epoxy-based adhesive is an adhesive having an epoxy resin as an effective component, and this epoxy resin has at least two epoxy groups in the molecule and is a polymerization reaction involving ring opening of the epoxy group. Refers to a compound or polymer that cures by In accordance with the custom in this field, even a monomer is referred to as an epoxy resin.

  Curing of the epoxy resin is generally performed by cationic polymerization of the epoxy resin. From the viewpoint of productivity, this curing is preferably performed by irradiation with active energy rays.

  The epoxy resin contained in the curable adhesive is preferably one that does not contain an aromatic ring in the molecule from the viewpoints of weather resistance, refractive index, cationic polymerizability, and the like. Examples of epoxy resins that do not contain an aromatic ring in the molecule include hydrogenated epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. An epoxy resin suitably contained in such a curable adhesive is known and described in detail in, for example, Japanese Patent Application Laid-Open No. 2004-245925, but the outline is also described here.

  The hydrogenated epoxy resin is a nuclear hydrogenated polyhydroxy compound obtained by selectively performing a nuclear hydrogenation reaction under pressure conditions in the presence of a catalyst on an aromatic polyhydroxy compound that is a raw material of an aromatic epoxy resin. It can be glycidyl etherified. Aromatic polyhydroxy compounds include, for example, bisphenols such as bisphenol A, bisphenol F and bisphenol S; novolac resins such as phenol novolac resins, cresol novolac resins and hydroxybenzaldehyde phenol novolac resins; tetrahydroxydiphenylmethane, tetra Examples thereof include polyfunctional compounds such as hydroxybenzophenone and polyvinylphenol. A glycidyl ether can be obtained by performing a nuclear hydrogenation reaction on such an aromatic polyhydroxy compound and reacting the resulting hydrogenated polyhydroxy compound with epichlorohydrin. Suitable hydrogenated epoxy resins include hydrogenated bisphenol A glycidyl ether.

  The alicyclic epoxy resin is a compound having at least one epoxy group bonded to the alicyclic ring in the molecule. The “epoxy group bonded to the alicyclic ring” means a bridged oxygen atom —O— in the structure represented by the following formula, and m is an integer of 2 to 5.

A compound in which one or a plurality of hydrogen atoms in (CH ₂ ) _m in this formula are removed and bonded to another chemical structure can be an alicyclic epoxy resin. Further, one or more hydrogen atoms in (CH ₂ ) _m forming the alicyclic ring may be appropriately substituted with a linear alkyl group such as a methyl group or an ethyl group. Among alicyclic epoxy resins, an epoxy resin having an epoxycyclopentane structure (m = 3 in the above formula) or an epoxycyclohexane structure (m = 4 in the above formula) exhibits excellent adhesion. Therefore, it is preferably used. Specific examples of the alicyclic epoxy resin are given below. Here, the compound names are given first, and then the chemical formulas corresponding to each are shown, and the same reference numerals are given to the compound names and the chemical formulas corresponding thereto.

A: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate,
B: 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylate,
C: ethylene bis (3,4-epoxycyclohexanecarboxylate),
D: Bis (3,4-epoxycyclohexylmethyl) adipate,
E: bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate,
F: diethylene glycol bis (3,4-epoxycyclohexyl methyl ether), G: ethylene glycol bis (3,4-epoxycyclohexyl methyl ether),
H: 2,3,14,15-diepoxy-7,11,18,21-tetraoxatrispiro [5.2.2.5.2.2] henicosane,
I: 3- (3,4-epoxycyclohexyl) -8,9-epoxy-1,5-dioxaspiro [5.5] undecane,
J: 4-vinylcyclohexene dioxide,
K: Limonene dioxide
L: bis (2,3-epoxycyclopentyl) ether,
M: Dicyclopentadiene dioxide and the like.

  The aliphatic epoxy resin can be a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof. More specifically, diglycidyl ether of propylene glycol; diglycidyl ether of 1,4-butanediol; diglycidyl ether of 1,6-hexanediol; triglycidyl ether of glycerin; triglycidyl ether of trimethylolpropane; ethylene Polyglycidyl ether of polyether polyol (for example, diglycidyl ether of polyethylene glycol) obtained by adding alkylene oxide (ethylene oxide or propylene oxide) to aliphatic polyhydric alcohol such as glycol, propylene glycol and glycerin It is done.

  In the curable adhesive, the epoxy resin may be used alone or in combination of two or more. Especially, it is preferable that this epoxy resin contains the alicyclic epoxy resin which has at least one epoxy group couple | bonded with the alicyclic ring in a molecule | numerator.

  The epoxy equivalent of the epoxy resin contained in the curable adhesive is usually in the range of 30 to 3,000 g / equivalent, preferably 50 to 1,500 g / equivalent. When the epoxy equivalent is less than 30 g / equivalent, there is a possibility that the flexibility of the polarizing plate after curing is lowered or the adhesive strength is lowered. On the other hand, when the epoxy equivalent exceeds 3,000 g / equivalent, the compatibility with other components contained in the adhesive may be lowered.

In the present invention, as described above, it is preferable to employ a cationically polymerizable epoxy resin. Therefore, it is preferable that the curable adhesive contains a cationic polymerization initiator. The cationic polymerization initiator generates a cationic species or a Lewis acid by irradiation or heating with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and initiates an epoxy group polymerization reaction. From the viewpoint of storage stability and workability, it is preferable that the cationic polymerization initiator is provided with the potential to act catalytically by irradiation with active energy rays or heating.
Hereinafter, a cationic polymerization initiator that generates a cationic species or Lewis acid by irradiation of active energy rays and initiates a polymerization reaction of an epoxy group is referred to as a “photo cationic polymerization initiator”, and generates a cationic species or a Lewis acid by heat. The cationic polymerization initiator that initiates the polymerization reaction of the epoxy group is referred to as “thermal cationic polymerization initiator”.

  The method of adding a cationic photopolymerization initiator and irradiating an active energy ray to cure the adhesive enables curing at room temperature, reducing the need to consider the heat resistance of the polarizing film or distortion due to expansion. This is advantageous in that the protective film and the polarizing film can be favorably bonded. In addition, since the photocationic polymerization initiator acts catalytically by light, it is excellent in storage stability and workability even when mixed with an epoxy resin.

Examples of the photocationic polymerization initiator include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts, and iron-arene complexes. The compounding quantity of a photocationic polymerization initiator is 0.5-20 weight part normally with respect to 100 weight part of epoxy resins, Preferably it is 1 weight part or more, Preferably it is 15 weight part or less.
When the amount of the cationic photopolymerization initiator is less than 0.5 parts by weight, the curing becomes insufficient and the mechanical strength and adhesive strength of the cured product tend to decrease. On the other hand, when the compounding quantity of a photocationic polymerization initiator exceeds 20 weight part, the ionic substance in hardened | cured material will increase, the hygroscopic property of hardened | cured material will become high, and durability performance may fall.

  When mix | blending a photocationic polymerization initiator, a curable adhesive agent can contain a photosensitizer further as needed. By using a photosensitizer, the reactivity of cationic polymerization can be improved, and the mechanical strength and adhesive strength of the cured product can be improved. Examples of the photosensitizer include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo compounds, diazo compounds, halogen compounds, and photoreducible dyes. When mix | blending a photosensitizer, it is preferable to make the quantity into the range of 0.1-20 weight part with respect to 100 weight part of curable adhesives.

  On the other hand, examples of the thermal cationic polymerization initiator include benzylsulfonium salt, thiophenium salt, thioranium salt, benzylammonium, pyridinium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, and amine imide.

  The curable adhesive containing an epoxy resin is preferably cured by photocationic polymerization as described above, but it can be cured by thermal cationic polymerization by blending the above thermal cationic polymerization initiator, or photocationic polymerization. And thermal cationic polymerization. In the case of curing by both photocationic polymerization and thermal cationic polymerization, it is preferable to add both a photocationic polymerization initiator and a thermal cationic polymerization initiator to the curable adhesive.

  The curable adhesive may further contain a compound that promotes cationic polymerization, such as an oxetane compound or a polyol compound. An oxetane compound is a compound having a 4-membered ring ether in the molecule. When mix | blending an oxetane compound, the compounding quantity is 5-95 weight% normally based on the whole quantity of a curable adhesive agent, Preferably it is 5-50 weight%. The polyol compound can be alkylene glycol including ethylene glycol, hexamethylene glycol, polyethylene glycol or the like, or an oligomer thereof, polyester polyol, polycaprolactone polyol, polycarbonate polyol and the like. When the polyol compound is blended, the blending amount is usually 50% by weight or less, preferably 30% by weight or less, based on the total amount of the curable adhesive.

  Furthermore, as long as the adhesiveness is not impaired, the curable adhesive has other additives such as an ion trap agent, an antioxidant, a chain transfer agent, a sensitizer, a tackifier, a thermoplastic resin, a filler, A flow regulator, a plasticizer, an antifoamer, etc. can be contained. Examples of the ion trapping agent include inorganic compounds including powdered bismuth-based, antimony-based, magnesium-based, aluminum-based, calcium-based, titanium-based, and mixed systems thereof. Examples of the antioxidant include And hindered phenolic antioxidants.

  When a curable adhesive is employed for the production of the polarizing plate, the curable adhesive is applied to the bonding surface of the polarizing film or the protective film, or both of the bonding surfaces, and then bonded via the adhesive. And an active energy ray is irradiated or it heats, an uncured adhesive bond layer can be hardened and a polarizing film and a protective film can be pasted up. As an adhesive coating method, for example, various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be adopted.

  This curable adhesive can be basically a solvent-free adhesive that does not substantially contain a solvent, but each coating method has an optimum viscosity range, so that the viscosity can be adjusted. A solvent may be included. The solvent is preferably an organic solvent that dissolves each component including an epoxy resin well without degrading the optical performance of the polarizing film. For example, hydrocarbons represented by toluene and ethyl acetate are preferred. Ester etc. can be used.

  When the adhesive is cured by irradiation with active energy rays, the above-mentioned various types of active energy rays can be used. However, ultraviolet rays are preferable because they are easy to handle and easily control the amount of irradiation light. Active energy rays such as ultraviolet irradiation intensity and irradiation dose do not affect various optical performance including polarization degree of polarizing film, and various optical performance including transparency and retardation characteristics of protective film. Therefore, it is determined as appropriate so as to maintain an appropriate productivity.

  When the adhesive is cured by heat, the adhesive may be heated by a generally known method. Usually, the thermal cationic polymerization initiator blended in the curable adhesive is heated to a temperature higher than the temperature at which cationic species and Lewis acid are generated, and the heating temperature is, for example, about 50 to 200 ° C.

[Adhesive layer]
In the polarizing plate of the present invention, a pressure-sensitive adhesive layer is usually laminated on the first or second protective film, and is bonded to a liquid crystal cell or the like through this.

  The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer may be any material that has excellent optical transparency and excellent adhesive properties including moderate wettability, cohesiveness, adhesiveness, etc., but also has excellent durability and the like. Is preferably used. Specifically, an adhesive containing an acrylic resin (acrylic adhesive) is preferably used as the adhesive forming the adhesive layer.

  The acrylic resin contained in the acrylic pressure-sensitive adhesive is a resin mainly composed of an acrylic acid alkyl ester such as butyl acrylate, ethyl acrylate, isooctyl acrylate, and 2-ethylhexyl acrylate. This acrylic resin is usually copolymerized with a polar monomer. The polar monomer is a compound having a polymerizable unsaturated bond and a polar functional group. Here, the polymerizable unsaturated bond is generally derived from a (meth) acryloyl group, and the polar functional group. The group can be a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, or the like. Specific examples of polar monomers include (meth) acrylic acid, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, 2-N, N-dimethylaminoethyl ( Examples include meth) acrylate and glycidyl (meth) acrylate.

The acrylic pressure-sensitive adhesive usually contains a crosslinking agent together with the acrylic resin.
A typical example of the crosslinking agent is an isocyanate compound having at least two isocyanato groups (—NCO) in the molecule.

  Various additives may be further blended in the adhesive. Suitable additives include silane coupling agents and antistatic agents. A silane coupling agent is effective in increasing the adhesive strength with glass. Antistatic agents are effective in reducing or preventing the generation of static electricity. In general, when attaching a polarizing plate to a liquid crystal cell via an adhesive layer, the surface protective film (separator) that has been temporarily protected by covering the adhesive layer is peeled off and then attached to the liquid crystal cell. The static electricity generated when the surface protective film is peeled off causes the alignment failure of the liquid crystal in the liquid crystal cell, and this phenomenon may cause the display failure of the liquid crystal display device. As a means for reducing or preventing the generation of static electricity, it is effective to add an antistatic agent to the adhesive.

  The pressure-sensitive adhesive layer is prepared by dissolving a pressure-sensitive adhesive component as described above in an organic solvent to prepare a pressure-sensitive adhesive composition, which is directly applied onto a protective film of a polarizing plate and then directly removed by removing the solvent. Alternatively, the above-mentioned pressure-sensitive adhesive composition is applied to a release-treated surface of a base film made of a resin film subjected to a release treatment, and the solvent is removed by drying to form a pressure-sensitive adhesive layer, which is used as a protective film for a polarizing plate It can be formed by a transfer method that is stuck on top. When the pressure-sensitive adhesive layer is formed on the protective film by the former direct coating method, a resin film (also called a separator) that has been subjected to a release treatment is bonded to the surface, and the pressure-sensitive adhesive layer surface is temporarily attached until use. It is customary to protect the wear. The latter transfer method is often employed from the viewpoint of the handleability of the pressure-sensitive adhesive composition that is an organic solvent solution. In this case, the release-treated base film used for forming the pressure-sensitive adhesive layer first is used. It is also advantageous in that it can be used as a separator after being attached to a polarizing plate.

[Liquid Crystal Display]
The polarizing plate of this invention is used suitably for a liquid crystal display device. The liquid crystal display device includes a liquid crystal panel. This liquid crystal panel includes a liquid crystal cell and a polarizing plate laminated on one or both sides of the liquid crystal cell, and the liquid crystal cell and the polarizing plate are bonded via an adhesive layer as described above. This liquid crystal cell can be of various types such as IPS mode, VA mode, and TN mode. On the opposite side of the liquid crystal cell to which the polarizing plate of the present invention is bonded, the same type of polarizing plate or a known polarizing plate can be bonded.

  When arrange | positioning the polarizing plate of this invention in the visual recognition side of a liquid crystal cell, let the protective film (protective film located in the visual recognition side most) from the liquid crystal cell be a film which has the anti-glare property to which haze was provided. be able to. Examples of a method for imparting haze to the protective film include a method of producing a film by mixing inorganic fine particles or organic fine particles with a resin as a raw material constituting the protective film, and a resin mixed with fine particles and fine particles are not mixed. A method of manufacturing a two-layer film by multilayer extrusion using a resin, or a method of manufacturing a three-layer film by using a resin mixed with fine particles as an outer layer, curing inorganic fine particles or organic fine particles on one side of the film For example, there is a method in which a coating solution mixed with a functional binder resin is coated and the binder resin is cured to provide an antiglare layer.

  Examples of the inorganic fine particles include silica, colloidal silica, alumina, alumina sol, aluminosilicate, alumina-silica composite oxide, kaolin, talc, mica, calcium carbonate, calcium phosphate, and the like. Examples of the organic fine particles include crosslinked polyacrylic acid particles, methyl methacrylate / styrene copolymer resin particles, crosslinked polystyrene particles, crosslinked polymethyl methacrylate particles, silicone resin particles, and polyimide particles.

  When haze is imparted to the protective film, the haze value is preferably in the range of 6 to 45%. If the haze value is less than 6%, a sufficient antiglare effect may not be obtained. On the other hand, when the haze value exceeds 45%, the screen of the liquid crystal display device on which the protective film is arranged may be whitened, resulting in a decrease in image quality. Haze is a value defined as the ratio of diffuse transmittance to total light transmittance. Measured using a commercially available haze meter in accordance with JIS K 7136: 2000 “How to determine haze of plastics and transparent materials” can do. An example of a commercially available haze meter is “HM-150” (product name) sold by Murakami Color Research Laboratory. In measuring the haze value, in order to prevent warping of the film, for example, an optically transparent adhesive is used, and a measurement sample in which the film surface is bonded to a glass substrate so that the antiglare surface becomes the surface is used. Is preferred.

  In addition, when the polarizing plate of the present invention is disposed on the viewing side of the liquid crystal cell, a conductive layer, a hard coat layer, a low reflection layer is provided on the outermost surface (surface opposite to the polarizing film) of the protective film far from the liquid crystal cell. Functional layers including layers and the like can be provided. As the coating liquid containing the binder resin constituting the antiglare layer, a resin composition capable of expressing these functions can also be selected.

  When the polarizing plate of the present invention is disposed on the back side of the liquid crystal cell, the protective film on the side far from the liquid crystal cell (backlight side) has the above-described transparency, mechanical strength, thermal stability, moisture shielding properties, etc. Instead of a resin film composed of a resin excellent in brightness, a brightness enhancement film can be selected. The brightness enhancement film can be easily obtained from commercial products. For example, "DBEF" (registered trademark) and "APF" sold by Sumitomo 3M Co., Ltd. (Product name). In addition, when employ | adopting a brightness enhancement film as a protective film used as the side (backlight side) far from a liquid crystal cell, it can laminate | stack with an above-described adhesive.

  When the polarizing plate of the present invention is bonded to a liquid crystal cell, the protective film of the protective film located on the liquid crystal cell side (between the liquid crystal cell and the polarizing film), whether on the viewing side or the back side, It is preferable to have a retardation in the above-described range, and it is more preferable that the phase difference is composed of a cellulose resin or a polyolefin resin.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further more concretely, this invention is not limited by these examples. In the following examples, the calculation of the amount of distortion of the polarizing film and the measurement of the thickness of the polarizing film and the protective film were performed by the following methods.

  The strain amount of the polarizing film was determined as follows. First, the polarizing film is cut into a size in which the absorption axis direction × transmission axis direction is 100 mm × 100 mm, and this polarizing film piece is cut into a size of 140 mm × 140 mm and a center portion of 80 mm × 80 mm. 1 mm of heat-resistant insulating polyimide adhesive tape [trade name of Nitto Denko Corporation] so that they are sandwiched as shown in FIG. No. 360 series ”] was used to fix the polarizing film and the pradane to obtain a measurement sample. A general-purpose foil strain gauge “KFG-5-120-C1” sold by Kyowa Denki Co., Ltd. was bonded to the center of the polarizing film so that it was parallel to the transmission axis direction of the polarizing film. The polarizing film and the strain gauge were bonded with a cyanoacrylate adhesive [trade name “Aron Alpha (registered trademark) 201” sold by Toa Gosei Co., Ltd.]. The strain gauge was connected to the high-speed data logger “UCAM-65A” sold by Kyowa Denki Co., Ltd. Thereby, the dimensional change in the transmission axis direction of the polarizing film was measured. Next, this measurement sample is left in the oven, and the temperature in the oven is raised from 25 ° C. to 85 ° C. at a rate of 2 ° C./min to 85 ° C., and then the sample is taken out and bonded to a strain gauge. 0.3 mL of pure water at 23 ° C. was added dropwise to the polarizing film portion. The maximum amount of dimensional change (absolute value) that occurred in one minute after dropping pure water was recorded, and the amount of strain was calculated by the above equation (1).

  The thickness of the polarizing film and the protective film was measured with a digital micrometer “MH-15M” (product name) manufactured by Nikon Corporation.

(Production Example 1)
After immersing a polyvinyl alcohol film [trade name “VF-PE # 3000” of Kuraray Co., Ltd.] having an average polymerization degree of about 2400 and a saponification degree of 99.9 mol% and a thickness of 30 μm in pure water at 37 ° C., It was immersed in an aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.04 / 1.5 / 100 at 30 ° C. Thereafter, it was immersed at 56.5 ° C. in an aqueous solution having a weight ratio of potassium iodide / boric acid / water of 12 / 3.6 / 100. Subsequently, the film was washed with pure water at 10 ° C. and then dried at 85 ° C. to prepare a polarizing film 1 having a thickness of about 12 μm in which iodine was adsorbed and oriented on polyvinyl alcohol. Stretching was performed mainly in the steps of iodine staining and boric acid treatment, and the total stretching ratio was 4.8 times. The strain amount of the polarizing film was 611 με.

(Production Example 2)
After immersing a polyvinyl alcohol film (trade name “VF-PE # 6000” manufactured by Kuraray Co., Ltd.) having an average polymerization degree of about 2400 and a saponification degree of 99.9 mol% and a thickness of 60 μm in pure water at 37 ° C. The sample was immersed in an aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.04 / 1.5 / 100 at 30 ° C. Thereafter, it was immersed at 56.5 ° C. in an aqueous solution having a weight ratio of potassium iodide / boric acid / water of 12 / 3.6 / 100. Subsequently, the film was washed with pure water at 10 ° C. and then dried at 85 ° C. to prepare a polarizing film 2 having a thickness of about 23 μm in which iodine was adsorbed and oriented on polyvinyl alcohol. Stretching was performed mainly in the steps of iodine dyeing and boric acid treatment, and the total stretching ratio was 5.3 times. The strain amount of the polarizing film was 711 με.

  In the following Examples and Comparative Examples, a polarizing plate was prepared from the polarizing film prepared above and the following protective film.

<Protective film>
Protective film A: Triacetylcellulose (TAC) film with hard coat, thickness 49 μm, product name “KY-40-C2A3” obtained from Konica Minolta Opto.
Protective film B: TAC film, thickness 25 μm, product name “KC2UAW” obtained from Konica Minolta Opto.
Protective film C: TAC film with hard coat, thickness 44 μm, product name “40CHC” obtained from Toppan Printing Co., Ltd.
Protective film D: Cycloolefin polymer (COP) molded product, thickness 20 μm, trade name “ZEONOR FILM” (registered trademark) obtained from Nippon Zeon Co., Ltd.
Protective film E: Cycloolefin polymer (COP) molded product, thickness 23 μm, trade name “ZEONOR FILM” (registered trademark) obtained from Nippon Zeon Co., Ltd.

[Example 1]
(Preparation of aqueous adhesive)
3 parts of carboxyl group-modified polyvinyl alcohol “KL-318” (trade name) obtained from Kuraray Co., Ltd. was dissolved in 100 parts of water, and water-soluble polyamide epoxy obtained from Sumika Chemtex Co., Ltd. was dissolved in the aqueous solution. A water-based adhesive was prepared by adding 1.5 parts of the resin “SUMIREZ RESIN (registered trademark) 650 (30)” (trade name, 30% solid content aqueous solution).

(Preparation of polarizing plate)
The saponification process was performed to the bonding surface of the protective film A and the protective film D, respectively. The protective film A is bonded to one surface of the polarizing film 1 via the aqueous adhesive prepared above, and the protective film D is bonded to the other surface via the same aqueous adhesive, respectively, at 80 ° C. for 5 minutes. It dried and the polarizing plate was produced.

[Evaluation]
On the surface of the protective film D of the polarizing plate prepared above opposite to the polarizing film 1, an acrylic pressure-sensitive adhesive sheet was bonded to prepare a polarizing plate with a pressure-sensitive adhesive layer. This polarizing plate with a pressure-sensitive adhesive layer is cut into a 5.1 inch size (width: about 113 mm × length: about 64 mm), the release film is peeled off from the pressure-sensitive adhesive layer side, and a glass plate is placed through the exposed pressure-sensitive adhesive layer. Pasted. Using this as a sample for evaluation, a thermal shock environment test and a dew condensation thermal shock environment test were conducted.

This thermal shock environmental test was conducted using a thermal shock test apparatus (product name “TSA-71L-A-3” sold by ESPEC Corporation) with a polarizing plate attached to a glass plate. The conditions were 85 ° C. exposure for 30 minutes and low temperature conditions −40 ° C. exposure for 30 minutes as one cycle.
In addition, the temperature transition time was set to 1 minute, the temperature transition time was set to 0 minutes at the time of temperature transition, and conditions were set so as not to cause condensation on the optical member without introducing outside air at the time of temperature transition. As a result, the polarizing film was not cracked even after repeating 400 cycles.

  The condensation thermal shock environment test was performed under the above-described thermal shock environment test under the condition that dew was intentionally generated in the optical member by introducing outside air into the apparatus for 5 minutes at the time of temperature transition. As a result, the polarizing film did not crack even after 50 cycles. This measurement was performed in an environment set at 23 ° C. and a relative humidity of 55%.

  After conducting a thermal shock environment test (cycle number: 400 times) and a condensation thermal shock environment test (cycle number: 50 times), the presence or absence of cracks was visually confirmed. In Table 1 described later, “◯” indicates that there was no change from before the test, and “X” indicates that a crack occurred after the test.

[Experiment 2]
A polarizing plate was produced in the same manner as in Example 1 except that the protective film A was changed to the protective film B and the protective film D was changed to the protective film E.

  The polarizing plate with an adhesive layer was produced by bonding an acrylic adhesive sheet to the surface of the protective film E of the polarizing plate opposite to the polarizing film 1. The pressure-sensitive adhesive layer-attached polarizing plate was cut into a 5.1-inch size in the same manner as in Example 1, and the pressure-sensitive adhesive layer was bonded to a glass plate to obtain a sample for evaluation. A thermal shock environment test and a dew condensation thermal shock environment test were performed on the sample for evaluation in the same manner as in Example 1. As a result, in the thermal shock environment test, the polarizing film did not crack even after 400 cycles. Further, in the condensation and thermal shock environment test, the polarizing film did not crack even after 50 cycles.

[Comparative Example 1]
A polarizing plate was produced in the same manner as in Example 1 except that the protective film A was changed to the protective film C, the protective film D was changed to the protective film E, and the polarizing film 1 was changed to the polarizing film 2.

  The polarizing plate with an adhesive layer was produced by bonding an acrylic adhesive sheet to the surface of the protective film E of the polarizing plate opposite to the polarizing film 3. The pressure-sensitive adhesive layer-attached polarizing plate was cut into a 5.1-inch size in the same manner as in Example 1, and the pressure-sensitive adhesive layer was bonded to a glass plate to obtain a sample for evaluation. A thermal shock environment test and a dew condensation thermal shock environment test were performed on the sample for evaluation in the same manner as in Example 1. As a result, in the thermal shock environment test, cracks did not occur in the polarizing film even when the 400 cycle thermal shock environment test was repeated. On the other hand, in the condensation thermal shock environment test, cracks were observed in the polarizing film after 50 cycles.

[Comparative Example 2]
A polarizing plate was produced in the same manner as in Example 1 except that the protective film A was changed to the protective film B and the polarizing film 1 was changed to the polarizing film 2.

  An acrylic pressure-sensitive adhesive sheet was bonded to the protective film D surface of this polarizing plate to prepare a polarizing plate with a pressure-sensitive adhesive layer. The obtained polarizing plate with the pressure-sensitive adhesive layer was cut into a 5.1 inch size, and the pressure-sensitive adhesive layer was bonded to a glass plate. went. As a result, in the thermal shock environment test, cracks occurred in the polarizing film after 400 cycles. Further, in the condensation / cold thermal shock environment test, cracking occurred in the polarizing film after 50 cycles.

1. A film fragment of a polarizing film,
3. Measurement jig,
5. Polyimide tape,
7). Strain gauge

Claims (5)

A polarizing plate in which a first protective film having a thickness of 5 μm or more and 50 μm or less is laminated on at least one surface of a polarizing film having a thickness of 1 μm or more and 26 μm or less,
The ratio of the thickness of the first protective film to the thickness of the polarizing film is greater than 1.9 and not greater than 4.1, and
The polarizing film was conditioned for 24 hours under an atmosphere of 23 ° C. and 55% relative humidity, and then heated in an oven from 25 ° C. to 85 ° C. at a rate of 2 ° C./min. Is a polarizing film having a maximum strain of 700 με or less in the direction of the transmission axis of a polarizing film produced when 0.3 mL of 23 ° C. pure water is attached to a polarizing film having a size of 100 mm × 100 mm for 1 minute. There is a polarizing plate.   The first protective film is laminated on one side of the polarizing film, and the second protective film having the same thickness as the first protective film or thinner than the first protective film is laminated on the other side. The polarizing plate as described. At least one of the first and second protective films has an in-plane retardation Re at a wavelength of 590 nm of 10 nm or less, an absolute value of retardation Rth in the thickness direction at the same wavelength of 10 nm or less, and a wavelength of 480 to 750 nm. The polarizing plate according to claim 2 , wherein an absolute value of retardation Rth in the thickness direction is 15 nm or less. The polarizing plate according to claim 2, wherein the first and second protective films are each independently composed of a cellulose resin or a polyolefin resin.   A liquid crystal display device, wherein the polarizing plate according to claim 1 is laminated on at least one side of a liquid crystal cell.

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