Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
  • G02F1/133528—Polarisers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
• • G02B1/105—
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
  • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
  • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
  • G02F2201/50—Protective arrangements
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F2202/00—Materials and properties
  • G02F2202/28—Adhesive materials or arrangements

Definitions

• Polarizer protective film polarizing plate, and image display device
• the present invention relates to a polarizer protective film, a polarizing plate, and an image display device such as a liquid crystal display device, an organic EL display device, and a PDP, which includes at least one polarizing plate.
• a polarizing plate is formed by applying a polarizer protective film using a cellulose resin film such as triacetyl cellulose on both sides of a polarizer made of a polyvinyl alcohol film and a dichroic material such as iodine. Those bonded with a rivul alcohol-based adhesive are used.
• Poly (meth) acrylic acid esters such as polymethylmethacrylate are known as a resin material excellent in heat resistance and optical transparency (see, for example, Patent Document 1).
• poly (meth) acrylic acid esters such as poly (methyl methacrylate) are brittle and have problems such as cracking and transportability such as breaking during film transport, and poor productivity. For this reason, it is difficult to use a poly (meth) acrylic ester such as polymethylmethalate as it is for a polarizer protective film.
• Patent Document 3 A three-layer film including an acrylic thermoplastic copolymer layer as a film suitable for a polarizer protective film having excellent heat resistance and optical transparency, excellent productivity, and toughness.
• Patent Document 1 Japanese Unexamined Patent Publication No. 2000-356714
• Patent Document 2 Japanese Patent Laid-Open No. 5-119217
• Patent Document 3 Japanese Patent Application Laid-Open No. 2004-291302
• the present invention has been made in order to solve the above-described conventional problems.
• the object of the present invention is (1) having high heat resistance, high transparency, high optical characteristics, and high mechanical strength. And providing a polarizer protective film that has excellent adhesion to the polarizer and can be made into a thin film, and (2) polarizer protection using such a polarizer protective film and a polarizer. Providing polarizing plates with excellent optical properties, high heating and humidification durability, and high-quality image display devices using such polarizing plates. That's it.
• the polarizer protective film of the present invention includes an acrylic resin containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).
• R 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
• R 2 represents an aliphatic or alicyclic hydrocarbon group having 1 to 5 carbon atoms.
• R 3 and R 4 represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
• the polarizer protective film has an in-plane retardation ⁇ nd for light having a wavelength of 590 nm of 1 Onm or less and a thickness direction retardation Rth for light of wavelength 590 nm of 10 nm or less.
• the photoelastic coefficient for light having a wavelength of 550 nm is ⁇ 2 ⁇ 10 — 12 to 2 ⁇ 10 — 12 Pa — 1 .
• these are the R 3 acetyl group and the R 4 acetyl group in the general formula (2).
• the polarizer protective film has a glass transition temperature of 11 ° C. or higher.
• the polarizer protective film has a moisture permeability of 3 to: LOOgZ m 2 ′ 24 hr.
• the polarizer protective film has a thickness of 5 to 100 / zm. is there.
• a polarizing plate is provided.
• the polarizing plate of the present invention has the polarizer protective film of the present invention on at least one surface of a polarizer formed from polybula alcohol-based resin, and the following formula after holding at 60 ° CZ95% RH for 492 hours:
• the rate of change of the degree of polarization defined in A) is 0.5 to 0.0%.
• Polarization degree change rate (%) ⁇ (P— P) ZP ⁇ X 100 (A)
• Another polarizing plate of the present invention has the polarizer protective film of the present invention on at least one side of a polarizer formed from a polyvinyl alcohol-based resin, and is 492 hours at 60 ° CZ95% RH.
• the transmittance change rate defined by the following formula (B) after being held is 0.0 to 2.5%.
• Transmittance change rate (%) ⁇ (Y -Y) / Y ⁇ X 100 (B)
• Another polarizing plate of the present invention has the polarizer protective film of the present invention on at least one side of a polarizer formed from a polyvinyl alcohol-based resin, and is held at 80 ° C for 48 hours.
• the Rth rate of change defined by the following formula (C) is 2.0 to 0.0%.
• Rth change rate (%) ⁇ (Rth -Rth) / Rth ⁇ X 100 (C)
• Another polarizing plate of the present invention has the polarizer protective film of the present invention on at least one side of a polarizer formed from a polyvinyl alcohol-based resin, and is 48 hours at 60 ° CZ90% RH. After holding, the Rth change rate defined by the following formula (D) is 2.5 to 0.0%.
• Rth change rate (%) ⁇ (Rth -Rth) / Rth ⁇ X 100 (D)
• the polarizer protective film is provided on one side of the polarizer, and the cellulose-based resin film is provided on the other side. In a preferred embodiment, the polarizer protective film is provided on both sides of the polarizer.
• an easy-adhesion layer and an adhesive layer are provided between the polarizer protective film and the polarizer.
• the adhesive layer is a layer formed from a polybutyl alcohol adhesive.
• an adhesive layer is further provided as at least one of the outermost layers.
• an image display device is provided.
• the image display device of the present invention includes at least one polarizing plate of the present invention.
• the present invention has high, heat resistance, high, transparency, high, optical properties, high, mechanical strength, excellent adhesion to a polarizer, and can be a thin film.
• a polarizer protective film can be provided. Furthermore, using such a polarizer protective film and a polarizer, to provide a polarizing plate excellent in the optical characteristics that the adhesion between the polarizer protective film and the polarizer is high, and heating and humidification durability, and A high-quality image display apparatus using such a polarizing plate can be provided.
• the polarizer protective film of the present invention has a low film retardation of approximately 0, so that no color shift appears and is advantageous for optical design.
• the polarizer protective film of the present invention has a low photoelastic coefficient, it is possible to suppress peripheral unevenness that has been a problem with a polarizing plate using a conventional cellulose-based resin film. Since the polarizer protective film of the present invention has low moisture permeability, it has high durability that is resistant to humidification conditions.
• polarizer protective film including an acrylic resin containing an atollate structural unit having specific optical characteristics and a specific cyclic structural unit as the polarizer protective film. It becomes possible to express.
• FIG. 1 is a cross-sectional view showing an example of a polarizing plate of the present invention.
• FIG. 2 is a schematic sectional view of a liquid crystal display device according to a preferred embodiment of the present invention.
• the polarizer protective film of the present invention includes an acrylic resin comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).
• R 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
• R 2 represents an aliphatic or alicyclic hydrocarbon group having 1 to 5 carbon atoms.
• R 3 and R 4 represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
• Preferable specific examples of the structural unit represented by the general formula (1) include, as corresponding monomers, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, N-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, chloromethyl (meth) acrylate, (meth) acrylic acid 2-chloroethyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2, 3, 4, 5, 6-pentahydroxyhexyl, (meth) acrylic acid 2, 3, 4, 5-tetrahydroxypentyl and the like.
• methyl methacrylate is more preferable because methyl (meth) acrylate is more preferable in terms of excellent thermal stability. That is, in the general formula (1), it is particularly preferable that R 1 is a methyl group or an R 2 force methyl group.
• the content ratio of the structural unit represented by the general formula (1) in the structure of the acrylic resin is preferable. Properly 50 to 95 mole 0/0, more preferably 55 to 90 mole 0/0, more preferably 60 to 85 mol%, particularly preferably 65 to 80 mole 0/0, most preferably 65 to 75 mole 0 / 0 .
• the effects expressed from the structural unit represented by the general formula (1) for example, high heat resistance and high transparency may not be sufficiently exhibited. If the content is more than 95 mol%, the resin is brittle and easily broken, and the high mechanical strength cannot be exhibited sufficiently, resulting in poor productivity.
• the content of the general formula (2) structural unit represented by in the structure of the acrylic ⁇ is favored properly 5-50 Monore 0/0, more preferably 10 to 45 Monore 0/0, further preferably 15 to 40 Monore 0/0, and particularly preferably 20 to 35 mol%, and most preferably 25 to 35 mol%.
• effects derived from the structural unit represented by the general formula (2) for example, high optical properties, high mechanical strength, and excellent polarizer properties. Adhesiveness and thinning may not be fully demonstrated. If the content is more than 50 mol%, for example, high heat resistance and high transparency may not be sufficiently exhibited.
• the structural unit represented by the general formula (2) in the structure of the acrylic resin is contained in the structural unit represented by the following general formula (3).
• R 3 and R 4 represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.
• R 3 and R 4 are both preferably a hydrogen atom or a methyl group, more preferably a methyl group.
• the acrylic resin may contain other structural units other than the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2).
• Other structural units include structural units formed by polymerizing unsaturated carboxylic acid ester monomers. Examples thereof include a structural unit (A) other than the structural unit represented by the general formula (1), and a structural unit (B) formed by superposing other vinyl monomers.
• Examples of the unsaturated carboxylic acid ester monomer forming the structural unit (A) include, for example, methyl acrylate, (meth) acrylate ethyl, (meth) acrylate n-propyl, (meth) acrylyl.
• Acid n-butyl (meth) acrylic acid t-butyl, (meth) acrylic acid n-hexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid chloromethyl, (meth) acrylic acid 2-black mouth Ethyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2, 3, 4, 5, 6-pentahydroxyhexyl, (meth) acrylic acid 2 , 3, 4, 5-tetrahydroxypentyl and the like. These may be used alone or in combination of two or more.
• Examples of other bulle monomers that form the structural unit (B) include, for example, Atari mouth nitrile, Metatali mouth-tolyl, Etaly mouth-tolyl, allyl glycidyl ether, maleic anhydride, anhydrous Titaconic acid, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl acrylate, propylaminoethyl acrylate , Dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, cyclohexylaminoethyl methacrylate, N-benzyljetamine, N-acetylvinylamine, arylamine, methallylamine, N-methylamine, 2-isopropyl - Roux X
• the content of styrene-based structural units such as styrene and a-methylstyrene is preferably 0 to 1% by weight, more preferably 0 to 0.1% by weight. It is. By setting the concentration of the styrenic structural unit to 0 to 1% by weight, it is possible to prevent deterioration of retardation and deterioration of transparency.
• the structural unit derived from the unsaturated carboxylic acid is preferably contained in an amount of 0 to: LO wt%, more preferably 0 to 5 wt%, and more preferably 0 to 1 wt%. % And force S more preferred.
• the above-mentioned acrylic resin has a weight average molecular weight of preferably 1000 to 2000000, more preferably ⁇ 5,000 to 500,000, more preferably ⁇ or 10,000 to 500,000, specially preferred ⁇ or 50000-50000, most preferred ⁇ 60000-150000. If the weight average molecular weight force is out of the above range, the effects of the present invention may not be sufficiently exhibited.
• the acrylic resin has a Tg (glass transition temperature) force of preferably 110 ° C or higher, more preferably 115 ° C or higher, still more preferably 120 ° C or higher, particularly preferably 125 ° C, and most preferably 130 ° C. ° C or higher.
• Tg glass transition temperature
• the upper limit value of Tg of the acrylic resin is not particularly limited, but is preferably 300 ° C or lower, more preferably 290 ° C or lower, further preferably 285 ° C or lower, particularly preferably 200, from the viewpoint of moldability. ° C or lower, most preferably 160 ° C or lower.
• the acrylic resin is more preferably 85% or higher as the total light transmittance of a molded product obtained by injection molding, as measured by a method according to ASTM-D-1003, is higher. More preferably, it is 88% or more, and further preferably 90% or more. If the total light transmittance is less than 85%, the transparency is lowered and there is a possibility that it cannot be used for the intended purpose.
• the acrylic resin preferably has high light transmittance, low in-plane retardation ⁇ nd and low thickness direction retardation Rth.
• the content of the acrylic resin in the polarizer protective film of the present invention is preferably 50 to 100% by weight, more preferably 60 to: LOO% by weight, still more preferably 70 to: LOO% by weight, Particularly preferred is 80 to: LOO% by weight.
• the content of the acrylic resin in the polarizer protective film of the present invention is less than 50% by weight, the high, heat resistance and high transparency inherent in the acrylic resin may not be sufficiently reflected.
• the polarizer protective film of the present invention does not impair the object of the present invention! /, In the range, polyethylene, polypropylene, polyamide, polyphenylene sulfide, polyether ether ketone. , Polyester, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyetherimide, and other thermoplastic resins, phenolic resins, melamine resins, polyester resins, silicone resins, epoxy resins It may further contain a thermosetting resin such as resin.
• UV absorbers such as hindered phenols, benzotriazoles, benzophenones, benzoates, and cyanoacrylates, or antioxidants
• lubricants such as higher fatty acids, acid esters, acid amides, higher alcohols, etc.
• Plasticizer such as montanic acid, its salt, its ester, its half ester, stearyl alcohol, stearamide and ethylene wax
• anti-coloring agent such as phosphite, hypophosphite, halogen-based or It may contain additives such as phosphorus-based or silicone-based non-halogen flame retardants, nucleating agents, amine-based, sulfonic acid-based, polyether-based antistatic agents, pigments and other colorants.
• the total content of the resin additives other than acrylic resin and acrylic elastic particles with respect to the polarizer protective film of the present invention is preferably 10% by weight or less.
• the polarizer protective film of the present invention particularly preferably contains an ultraviolet absorber in order to impart weather resistance.
• the melting point of the ultraviolet absorber is preferably 110 ° C or higher, more preferably 120 ° C or higher. If the melting point of the UV absorber is 130 ° C or higher, roll contamination during film production is less likely to occur due to less volatilization during heat-melt processing.
• the type of the UV absorber is not particularly limited, but a benzotriazole UV absorber having a molecular weight of 400 or more and a triazine UV absorber having a molecular weight of 400 or more are particularly preferable.
• Examples of commercially available products include “Tinubin 1577” (manufactured by Ciba Specialty Chemicals), “Adeka Stub LA A-31J (manufactured by Asahi Denshi Kogyo Co., Ltd.), and the like.
• a retardation reducing agent may be included in the polarizer protective film of the present invention.
• the retardation reducing agent for example, styrene-containing polymers such as acrylonitrile-styrene block copolymer and acrylonitrile-styrene block copolymer are preferable.
• the polymethyl methacrylate It is preferably 30% by weight or less, more preferably 25% by weight or less, and further preferably 20% by weight or less, based on the system fat. If added beyond this range, visible light may be scattered and transparency may be impaired, so that the properties as a polarizer protective film may be lacking.
• the polarizer protective film of the present invention may contain acrylic elastic particles in addition to the acrylic resin. Due to the acrylic elastic particles dispersed in the polarizer protective film, excellent toughness as a polarizer protective film can be obtained.
• the acrylic elastic particles preferably include a rubbery polymer.
• the rubbery polymer has, as a raw material monomer, an acrylic component such as ethyl acrylate and butyl acrylate as an essential component, and other components preferably contained as a silicone component such as dimethylsiloxane and phenylmethylsiloxane, styrene and ⁇ - Examples include styrene components such as methylstyrene, -tolyl components such as acrylonitrile and methacrylo-tolyl, conjugation components such as butadiene and isoprene, urethane components, ethylene components, propylene components, and isobutene components.
• the rubbery polymer may contain a homopolymer of raw material monomers (preferably each of the above-mentioned components)! /, Or may contain a copolymer of two or more raw material monomers. Both may be included. More preferably, it is a rubbery polymer in which two or more of the above components are combined.
• a rubbery polymer containing an acrylic component and a silicone component examples include a rubbery polymer containing an acrylic component and a styrene component, an acrylic component, and examples thereof include a rubbery polymer containing a conjugation component, a rubbery polymer containing an acrylic component, a silicone component and a styrene component.
• the rubbery polymer preferably contains a crosslinkable component such as dibutenebenzene, arylaryl acrylate, or butylene glycol ditalylate.
• the rubbery polymer preferably includes a polymer having a combination of an alkyl acrylate unit and an aromatic bur unit.
• Alkyl acrylate units especially butyl acrylate, are extremely effective in improving toughness.
• aromatic beryl units such as styrene, the acrylic elastomer particles are refracted. The rate can be adjusted.
• the refractive index difference between the acrylic elastic particles and the acrylic resin is preferably 0.01 or less. This is because high transparency can be obtained in the polarizer protective film of the present invention.
• any appropriate method can be adopted as a method for setting the refractive index difference between the acrylic elastic particles and the acrylic resin to 0.01 or less. Examples thereof include a method for adjusting the composition ratio of each monomer unit constituting the acrylic resin, and a method for adjusting the composition ratio of the rubbery polymer and each monomer contained in the acrylic elastic particles.
• an acrylate elastic particle having a small refractive index difference from acrylic resin by copolymerizing an aromatic butyl unit such as styrene with an alkyl acrylate such as butyl acrylate and adjusting the copolymerization ratio. can be obtained.
• the average particle diameter of the acrylic elastic particles is preferably 70 to 300 nm, more preferably 100 to 200 nm. If it is less than 70 nm, the effect of improving toughness may not be sufficient, and if it is greater than 300 nm, the heat resistance may decrease.
• the content of the acrylic elastic particles in the polarizer protective film of the present invention is preferably 7 to 40% by weight, more preferably 12% to 20% by weight. If the amount is less than 7% by weight, the toughness-improved ray may not be sufficient, and if it exceeds 40% by weight, the heat resistance may decrease.
• the polarizer protective film of the present invention may be stretched by longitudinal stretching and Z or lateral stretching.
• the stretching may be stretching by only longitudinal stretching (free-end uniaxial stretching) or stretching by only transverse stretching (fixed-end uniaxial stretching), but the longitudinal stretching ratio is 1.1 to 3.0 times. Further, it is preferable that the transverse stretching ratio is 1.1 to 3.0 times, sequential stretching or simultaneous biaxial stretching.
• the film strength increases only in the stretching direction, and the strength does not increase in the direction perpendicular to the stretching direction.
• the film as a whole may not have sufficient film strength.
• the longitudinal draw ratio is more preferably 1.2 to 2.5 times, and still more preferably 1.3 to 2.0 times.
• the transverse stretching ratio is more preferably 1.2 to 2.5 times, and still more preferably 1.4 to 2.0 times. If the longitudinal draw ratio and transverse draw ratio are less than 1.1 times, the draw ratio is too low and May have little fruit. When the longitudinal draw ratio and the transverse draw ratio exceed 3.0 times, the stretch breakage is likely to occur due to the smoothness of the film end face.
• the stretching temperature is preferably Tg to (Tg + 30 ° C) of the film to be stretched! If the stretching temperature is lower than Tg, the film may be broken. If the stretching temperature exceeds (Tg + 30 ° C), the film may start to melt, making it difficult to pass the paper.
• the polarizer protective film of the present invention is stretched by longitudinal stretching and Z or lateral stretching, it has excellent optical properties, excellent mechanical strength, and productivity and reworkability. improves.
• the polarizer protective film of the present invention preferably has an in-plane retardation And of 3. Onm or less, a thickness direction retardation Rth of 10. Onm or less, and a tear strength of 2. ONZmm or more. In-plane retardation And, thickness direction retardation Rth, tear strength force By being in these ranges, it is possible to achieve both excellent optical properties and excellent mechanical strength.
• the in-plane retardation And should be as small as possible, preferably 2. Onm or less, more preferably 1.5 nm or less, and even more preferably 1.0 nm or less. It is.
• the in-plane retardation And exceeds 3. Onm, the effects of the present invention, particularly, excellent optical characteristics may not be exhibited.
• the smaller the thickness direction retardation Rth the better. 7. Onm or less, more preferably 5. Onm or less, and even more preferably 3. Onm or less.
• the thickness direction retardation Rth exceeds 10. Onm, the effects of the present invention, in particular, excellent optical characteristics may not be exhibited.
• the photoelastic coefficient for light having a wavelength of 550 nm is preferably 1 2 X 10 — 12 to 2 X 10 — 12 Pa — 1 , more preferably 1 1 X 10 — 12 to 1. X 10 — 12 Pa — 1 .
• the photoelastic coefficient with respect to light having a wavelength of 550 nm is within the above range, the effects of the present invention, in particular, excellent optical characteristics can be exhibited.
• the photoelastic coefficient with respect to light having a wavelength of 550 nm is obtained by, for example, using a spectroscopic ellipsometer (product name “M-220” manufactured by JASCO Corporation) to hold both ends of the sample (size 2 cm x 10 cm) and stress. While applying (5 to 15 N), the phase difference value (23 ° CZ wavelength 550 nm) at the center of the sample can be measured, and the gradient force of the function of stress and phase difference value can be calculated.
• a spectroscopic ellipsometer product name “M-220” manufactured by JASCO Corporation
• the polarizer protective film of the present invention preferably also has excellent mechanical strength.
• Tension In the MD direction the strength is preferably 65 NZmm 2 or more, more preferably 70 NZmm 2 or more, further preferably 75 NZmm 2 or more, particularly preferably 80 NZmm 2 or more, and in the TD direction, preferably 45 NZmm 2 or more, more preferably 50 NZmm. It is 2 or more, more preferably 55 NZmm 2 or more, and particularly preferably 60 NZmm 2 or more.
• the tensile elongation is preferably 6.5% or more, more preferably 7.0% or more, even more preferably 7.5% or more, particularly preferably 8.0% or more in the MD direction, and in the TD direction, Preferably, it is 5.0% or more, more preferably 5.5% or more, still more preferably 6.0% or more, and particularly preferably 6.5% or more.
• the tensile strength or tensile elongation can be measured, for example, according to JIS K 7113.
• moisture permeability preferably 3 ⁇ : L00g / m 2 '2 4hr, more preferably 5 ⁇ 60gZm 2' is 24 hr or. If the moisture permeability exceeds 100 gZm 2 '24 hr, the moisture resistance may be inferior. If the moisture permeability is less than 3gZm 2 '24h, the adhesion may be inferior.
• the polarizer protective film of the present invention is low if the haze representing optical transparency is low !, more preferably 5% or less, more preferably 3% or less, more preferably 2% or less, More preferably, it is 1.5% or less, particularly preferably 1% or less.
• the haze is 5% or less, it is possible to visually give a good tally feeling to the film.
• the haze is 1.5% or less, even when used as a daylighting member such as a window, the visibility and daylighting performance are improved.
• the industrial utility value is high.
• the particle size of acrylic elastic particles can be controlled, and coating bases can be used for cooling rolls, calender rolls, drums, belts, and solution casting during film formation. It is also effective to reduce the surface roughness of the material.
• the thickness of the polarizer protective film of the present invention is preferably 1 to: LOO / zm, more preferably 5 to: LOO ⁇ m, and further preferably 10 to 40 ⁇ m.
• the thickness of the polarizer protective film is 1 m or more, it has appropriate strength and rigidity, and secondary calorie such as lamination and printing. Handleability is improved during the operation.
• the phase difference caused by the stress during take-up can be easily controlled, and the film can be manufactured stably and easily. If the thickness of the polarizer protective film is 100 m or less, the film can be easily wound, and the line speed, productivity, and controllability can be facilitated.
• the polarizer protective film of the present invention preferably has a 1% deformation temperature of 100 ° C or higher under high tension. More preferably, it is 110 ° C or higher.
• the 1% deformation temperature under high tension here means that for a sample with an initial length of 15 mm and a width of 4 mm sampled in the longitudinal direction of the film, when the temperature was raised from 25 ° C to 20 ° CZ under a tension of 1.5 MPa, Measured as the temperature at 1% elongation.
• the low temperature means that the heat resistance tends to be inferior.
• the upper limit of 1% deformation elongation under high tension is preferably 140 ° C. or lower in order to obtain a film having a breaking elongation of 15% or more.
• the molecular weight of acrylic resin and the content of dartal anhydride units, acrylic elastomer Adjust the glass transition temperature, particle diameter, amount added, dispersion state in the film and V, and the film properties as appropriate.
• the polarizer protective film of the [0068] present invention is preferably from it is preferred instrument Charpy impact strength of the longitudinal direction of the film is 60 kJ / m 2 or more and 90 kJ / m 2 or more.
• Charpy impact strength 60 kjZm 2 or more
• a film that can withstand high-speed slitting can be obtained.
• it is effective to increase the average particle diameter of the acrylic elastic particles within a range that does not deteriorate the optical characteristics.
• the polarizer protective film of the present invention preferably has a total light transmittance of 91% or more, more preferably 93% or more. A practical upper limit is 99%. In order to achieve excellent transparency expressed by the total light transmittance, it is necessary not to introduce an additive or copolymer component that absorbs visible light, or to reduce the refractive index of acrylic resin. It is valid.
• the polarizer protective film of the present invention may have a hard coat layer on at least one surface. The hard coat layer is provided for preventing scratches.
• Examples of the hard coat agent for forming the hard coat layer include thermosetting cross-linked resins mainly composed of organosilicon compounds, epoxy resins, melamine resins, and two or more ( Examples thereof include an active energy ray-curable cross-linkable resin having a (meth) atalylooxy group.
• the polarizer protective film of the present invention may have an antireflection film on at least one surface.
• the antireflection film is provided in order to improve the total light transmittance.
• the material for the low refractive index layer include SiO and MgF.
• As the material of the high refractive index layer TiO
• the light absorption layer is a composite film
• TiNx, Au, Ag, NiOx and other intervening elements may be included.
• the polarizer protective film of the present invention may be produced by any method, but the raw material for forming the acrylic resin (for example, the structural unit represented by the general formula (1) is formed.
• Monomers that form the structural unit represented by the general formula (2) such as methyl methacrylate and methacrylic acid), and those that form the structural unit (A).
• Saturated carboxylic acid ester monomer, other vinyl monomers that form the structural unit (B), etc. acrylic elastic particles, additives (such as UV absorbers), etc. Accordingly, it is preferable to carry out an intramolecular cyclization reaction while adding any appropriate solvent (for example, methyl ethyl ketone) and heating.
• the intramolecular cyclization reaction include dealcoholization reaction and intramolecular cyclization reaction by Z or dehydration.
• the temperature for heat degassing by the above method is not particularly limited as long as it is a temperature at which intramolecular cyclization reaction occurs by dealcohol and Z or dehydration, but preferably in the range of 180 to 300 ° C. More preferably, it is in the range of 200 to 280 ° C.
• the time for heating and degassing is not particularly limited, depending on the desired copolymer composition. Any suitable time can be set, but a range of 1 to 60 minutes is usually preferable.
• the film can be formed by extrusion (melt extrusion such as T-die method or inflation method), cast molding (melt casting method, etc.), or calendar molding. good.
• the acrylic resin containing the dartal anhydride unit represented by the general formula (3) can be basically produced by the following method.
• R 5 represents hydrogen or an alkyl group having 1 to 5 carbon atoms.
• R 6 represents hydrogen or an aliphatic or alicyclic hydrocarbon group having 1 to 5 carbon atoms
• R 7 represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
• the total sum of the blended monomers is 100% by weight, and the unsaturated rubonic acid monomer is preferably 15 to 45% by weight, more preferably 20 to 40% by weight.
• the unsaturated carboxylic acid alkyl ester monomer is preferably 55 to 85% by weight, more preferably 60 to 80% by weight.
• the content of the dartal anhydride unit represented by the general formula (3) is in a preferable range of 20 to 40% by weight, and the heat resistance, colorless transparency, and retention stability are excellent. Arc It becomes possible to obtain rill rosin.
• a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization or the like by radical polymerization can be basically used. .
• Solution polymerization, bulk polymerization, and suspension polymerization are particularly preferable from the viewpoint of fewer impurities.
• the polymerization temperature for producing the copolymer (a) is preferably 95 ° C or lower, more preferably 95 ° C or less, from the viewpoint of preventing coloring of the resin and having a good color tone. It is 85 ° C or lower, more preferably 75 ° C or lower.
• the lower limit of the polymerization temperature is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of productivity taking the polymerization rate into consideration.
• the polymerization temperature may be raised as the polymerization progresses, but in this case as well, it is preferable to control the upper limit temperature to 95 ° C or lower throughout the process. It is preferable to carry out at a relatively low temperature of 75 ° C or less.
• the polymerization time for producing the copolymer (a) is preferably 60 to 360 minutes, more preferably 90 to 180 minutes from the viewpoint of production efficiency.
• the acrylic resin is used within the range of the preferable polymerization average molecular weight as described above (preferably 1000-2000000, particularly preferably
• the molecular weight of the copolymer (a) is also a weight average molecular weight, preferably ⁇ 1,000 to 2,000,000, and particularly preferably ⁇ 80000 to 150000.
• the molecular weight of the copolymer (a) is, for example, a radical polymerization initiator such as an azo compound or a peroxide compound, or an alkyl mercaptan, carbon tetrachloride, carbon tetrabromide, dimethylacetamide. It can be controlled by adjusting the amount of a chain transfer agent such as dimethylformamide or triethylamine. In particular, a method of adjusting the amount of addition of the alkyl mercaptan, which is a chain transfer agent, can be preferably employed from the viewpoint of stability of polymerization, ease of handling, and the like.
• alkyl mercaptan examples include n-octyl mercaptan, t-decyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan, and among others, tododecyl mercaptan, n-dodecyl mercabtan is preferably used.
• the amount of the alkyl mercabtan added is the total amount used for the production of the copolymer (a). It is preferably 0.2 to 5.0 parts by weight per 100 parts by weight of the body, more preferably 0.3 to 4.0 parts by weight, and still more preferably 0.4 to 3.0 parts by weight. .
• the copolymer (a) When the copolymer (a) is heated in the presence or absence of a suitable catalyst, it is dehydrated from the carboxyl groups of two adjacent unsaturated carboxylic acid units in the copolymer (a). Or an adjacent unsaturated carboxylic acid unit and an unsaturated carboxylic acid alkyl ester unit force alcohol is eliminated to produce one unit of the dartaric anhydride unit.
• Examples of a method for heating the copolymer (a) to dehydrate and Z or dealcoholate, that is, to perform an intramolecular cyclization reaction include a method using a heated extruder having a vent, an inert gas atmosphere, and the like.
• a method using an apparatus that can be heated and devolatilized under pressure or under vacuum is also preferable from the viewpoint of productivity.
• Specific examples of the apparatus for carrying out the intramolecular cyclization reaction include, for example, a single-screw extruder, twin-screw extruder, tri-screw extruder, continuous type or batch equipped with a "unimelt" type screw.
• a formula-kinder type kneader or the like can be used.
• twin-screw extruder is preferable in terms of continuous productivity, reaction temperature, time, and shear rate, and quality stability.
• the screw length Z diameter ratio (LZD) of the extruder is preferably 40 or more.
• LZD the screw length Z diameter ratio
• a specific apparatus for performing the intramolecular cyclization reaction is more preferably an apparatus having a structure capable of introducing an inert gas such as nitrogen. This is because when the intramolecular cyclization reaction by heating in the presence of oxygen tends to increase yellowness, it is preferable to sufficiently substitute the inside of the system with an inert gas such as nitrogen.
• an inert gas such as nitrogen
• the heating temperature for the intramolecular cyclization reaction is preferably 180 to 300, more preferably 200 to 280 ° C, from the viewpoint of allowing the reaction to proceed smoothly.
• the heating time for the intramolecular cyclization reaction may be appropriately set according to the desired copolymerization and synthesis, but is preferably 1 to 60 minutes, more preferably 2 to 30 minutes. More preferably, it is 3 to 20 minutes.
• an acidic catalyst At the time of heating for the intramolecular cyclization reaction, it is also preferable to add one or more of an acidic catalyst, an alkaline catalyst, and a salt catalyst.
• the acidic catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, phosphoric acid, phosphorous acid, phenolphosphonic acid, and methyl phosphate.
• the basic catalyst include metal hydroxides, amines, imines, alkali metal derivatives, alkoxides and the like.
• the salt-based catalyst include acetic acid metal salt, stearic acid metal salt, carbonate metal salt, and hydroxyammonium salt.
• a basic catalyst or a salt-based catalyst containing an alkali metal can be preferably used because it exhibits an excellent reaction promoting effect with a relatively small addition amount.
• alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium phenoxide, potassium methoxide, potassium ethoxide
• Alkoxide compounds such as potassium phenoxide
• organic carboxylates such as lithium acetate, sodium acetate, potassium acetate and sodium stearate.
• sodium hydroxide, sodium methoxide, lithium acetate Sodium acetate can be preferably used.
• Some salt-based catalysts show acidity or basicity when made into an aqueous solution. These are treated as salt-based catalysts and are distinguished from acidic catalysts and alkaline catalysts. These catalysts may be used alone or in combination of two or more.
• the addition amount of the catalyst is preferably 0.01 to 1 part by weight per 100 parts by weight of the copolymer (a).
• the amount is 0.01 parts by weight or more, the effectiveness as the catalyst can be obtained, and when the amount is 1 part by weight or less, the color of the catalyst has an adverse effect on the coloring of the thermoplastic polymer or is transparent. Can be prevented from decreasing.
• the acrylic elastic particles are dispersed in the acrylic resin or its precursor, the acrylic elastic particles are in a state where the surface layer is laminated with an acrylic resin having a glass transition temperature of 60 ° C or higher. Or a state in which a vinyl monomer is graft copolymerized It is preferable. By doing so, adhesion and aggregation between the acrylic elastic particles are prevented, the handling and properties are improved, and the dispersibility in the acrylic resin is also improved.
• the shell portion is The “acrylic resin having a glass transition temperature of 60 ° C. or higher” to be formed preferably contains an unsaturated carboxylic acid alkyl ester unit or an unsaturated carboxylic acid unit.
• the intramolecular cyclization reaction proceeds also in the shell portion by heating, and the shell portion and the matrix resin are assimilated, so that the transparency of the polarizer protective film of the present invention is inhibited by the shell portion. Can be prevented. Further, since the acrylic elastic particles are firmly held in the matrix resin, mechanical properties such as impact resistance are improved.
• methyl (meth) acrylate is more preferably used, which is preferably an alkyl (meth) acrylate.
• the monomer used as a raw material for the unsaturated carboxylic acid unit is preferably (meth) acrylic acid.
• Methacrylic acid is more preferably used.
• the weight ratio of the core to the shell in the core 'shell-type acrylic elastic particles is preferably 50 to 90% by weight of the core, more preferably 60 to 80%. Weight%.
• the vinyl monomer has a vinyl group.
• other bulle monomers may be copolymerized in accordance with the compatibility with the rubbery polymer or matrix resin contained in the acrylic elastic particles.
• the amount of the vinyl monomer to be imparted to the acrylic elastic particles is, as a weight ratio of rubbery polymer: vinyl monomer, (10-80): (20-90) force S More preferably, (20 to 70): (30 to 80), and still more preferably (30 to 60): (40 to 70).
• the effect of this embodiment can be obtained by setting the bule monomer to 20% by weight or more.
• the vinyl monomer content is 90% by weight or less, it is possible to suppress a decrease in impact strength.
• Graft-copolymerized acrylic elastic particles may contain a component derived from an unfavorable vinyl monomer by graft copolymerization, but from the viewpoint of impact strength.
• the graft ratio is preferably 10 to 100%.
• the graft ratio is a weight ratio of a graft copolymerized monomer among the bull monomers provided to the rubber polymer.
• the strength, impact strength and molding strength of 0.1 to 0.6 dlZg are not particularly limited. From the viewpoint of balance with strength, it is preferably used.
• Polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be employed as a method for making acrylic elastic particles into a graft copolymerization type.
• the particle diameter, content, and refractive index of the core-shell type or graft copolymer type acrylic elastic particles are evaluated with respect to a rubbery polymer excluding the shell part and the graft copolymer part.
• the particle diameter can be evaluated by excluding the force-shell part such as cross-sectional observation with a transmission electron microscope and the graft copolymer part.
• the content can be evaluated by the insoluble component strength after dissolving in a solvent such as acetone which dissolves acryl resin.
• acrylic elastic particles and other additives into the precursor of acrylic resin
• a method of uniformly melting and kneading with a single screw or twin screw extruder can be employed.
• acrylic elastomer particles and other additives are added to the copolymer (a), which is a precursor of acrylic resin, and simultaneously with the intramolecular cyclization reaction using a twin screw extruder or the like, Mixing by melting and kneading the neutral particles (B) and other additives can be performed.
• the resin constituting the polarizer protective film of the present invention for the purpose of removing foreign substances.
• coloring of rosin can be prevented and it can be usefully used as a film for optical applications.
• a resin dissolved in a solvent such as tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone preferably at a temperature of 25 ° C or higher and 100 ° C or lower, sintered metal, porous ceramic, It can be filtered with a filter such as sand or wire mesh.
• the polarizer protective film of the present invention can be formed by melt film formation or solution film formation.
• melt film formation there are an inflation method, a T-die method, a calendering method, a cutting method, etc., and the T-die method can be particularly preferably employed.
• the solution casting include a casting method on a polymer film, a casting drum method, a casting method on a metal belt, and the casting method on a polymer film can be preferably used.
• each manufacturing method will be described as an example.
• an Estatruder type melt extrusion apparatus equipped with a single-screw or twin-screw extruder can be used.
• the L / D of the screw is preferably 25 to 120 in order to prevent coloring.
• the melt extrusion temperature for producing the polarizer protective film of the present invention is preferably 150 to 350 ° C, more preferably 200 to 300 ° C.
• the T-die method melted resin is weighed with a gear pump and then discharged from the T-die base.
• the film can be obtained by bringing it into close contact with a cooling medium such as a drum by an electrostatic application method, an air chamber method, an air knife method, a press roll method, or the like.
• the press roll method is preferable for obtaining a film having a small haze with less thickness unevenness.
• the matrix resin is preferably dissolved in a solvent.
• a solvent tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and the like can be used.
• acetone is preferably used as methyl ethyl ketone.
• the cast on polymer film method uses a bar coater, die coater, etc. to cast a solution in which the raw resin composition is cast onto a metathermal film such as polyethylene terephthalate to evaporate and remove the solvent.
• Do dry method
• wet method is a method of solidifying a solution with a coagulation liquid (wet method).
• the low-refractive index layer, high-refractive index layer, light absorption layer and the like constituting the antireflection film can be formed by using a vacuum thin film forming technique such as vapor deposition or sputtering.
• the polarizer protective film of the present invention can be used by being laminated on another substrate.
• multilayer extrusion molding including adhesive resin layer or multilayer inflation molding on substrates such as glass, polyolefin resin, ethylene vinylidene copolymer, polyester, etc., which will be the rear layer. It can also be laminated. If the heat-fusibility is high, the adhesive layer may be omitted.
• the polarizing plate of the present invention has the polarizer protective film of the present invention on at least one side of a polarizer formed from polyvinyl alcohol-based resin.
• the polarizing plate of the present invention has the polarizer protective film of the present invention on at least one side of a polarizer formed from a polyvinyl alcohol-based resin, and was held at 60 ° CZ95% RH for 492 hours.
• the degree of change in polarization degree defined by the following formula (A) is 0.5 to 0.0%.
• Polarization degree change rate (%) ⁇ (P— P) ZP ⁇ X 100 (A)
• the rate of change in polarization degree is preferably -0.45 to 0.00%, more preferably -0.40 to 0.00. 00%, more preferably 0.35 to 0.00%, particularly preferably 0.30 to 0.00%.
• the rate of change in polarization degree is 0.5 to 0.0%
• a polarizing plate excellent in heating / humidification durability can be obtained.
• the polarizing plate excellent in heating and humidification durability can be provided by using the polarizer protective film of the present invention.
• the polarizing plate of the present invention has the polarizer protective film of the present invention on at least one side of a polarizer formed from a polyvinyl alcohol-based resin, and was held at 60 ° CZ95% RH for 492 hours.
• the transmittance change rate defined by the following formula (B) is 0.0 to 2.5%.
• Transmittance change rate (%) ⁇ (Y -Y) / Y ⁇ X 100 (B)
• the above transmittance change rate is preferably 0.0 to 2.3%, more preferably 0.0 to 2.1%, preferably ⁇ Furthermore or 0.0 to 2.0 0/0 .
• the transmittance change rate is 0.0 to 2.5%
• a polarizing plate having excellent heating and humidification durability can be obtained.
• the polarizing plate excellent in heating and humidification durability can be provided by using the polarizer protective film of the present invention.
• the polarizing plate of the present invention has the polarizer protective film of the present invention on at least one side of a polarizer formed from a polyvinyl alcohol-based resin, and is maintained at 80 ° C for 48 hours.
• the Rth change rate defined by the following formula (C) is 2.0 to 0.0%.
• Rth change rate (%) ⁇ (Rth -Rth) / Rth ⁇ X 100 (C)
• the Rth change rate is preferably 1.5 to 0.0%, more preferably 1.2 to 0.0%, and still more preferably 1.0 to 0.0%.
• the polarizing plate excellent in heat durability can be provided by using the polarizer protective film of the present invention.
• the polarizing plate of the present invention comprises at least a polarizer formed from a polyvinyl alcohol-based resin.
• the Rth change rate defined by the following formula (D) after holding the polarizer protective film of the present invention on one side for 48 hours at 60 ° CZ90% RH is 2.5 to 0.0%. is there.
• Rth change rate (%) ⁇ (Rth -Rth) / Rth ⁇ X 100 (D)
• the Rth change rate is preferably 2.3 to 0.0%, more preferably 2.2 to 0.0%, and still more preferably 2.1 to 0.0%.
• the polarizing plate excellent in heating and humidification durability can be provided by using the polarizer protective film of the present invention.
• One of the preferred embodiments has the polarizer protective film on one side of the polarizer and the cellulose-based resin film on the other side.
• One of the preferred embodiments has the polarizer protective film on both sides of the polarizer.
• One of the preferred embodiments of the polarizing plate of the present invention is that, as shown in FIG. 1, one surface of a polarizer 31 is bonded to the polarizing plate of the present invention via an adhesive layer 32 and an easy-adhesion layer 33.
• the polarizer 31 is bonded to the polarizer protective film 34, and the other surface of the polarizer 31 is bonded to the polarizer protective film 36 through the adhesive layer 35.
• the polarizer protective film 36 may be the polarizer protective film of the present invention, or may be any other appropriate polarizer protective film.
• a polarizer formed from the polybulal alcohol-based resin has a polybulal alcohol-based resin film dyed with a dichroic substance (typically iodine, a dichroic dye). A stretched one is used.
• the degree of polymerization of the polybula alcoholic resin constituting the polybulal alcoholic resin film is preferably 100 to 5000, more preferably 1400 to 4000.
• the polybulualcohol-based resin film constituting the polarizer can be formed by any appropriate method (for example, casting method, casting method, extrusion method in which a solution in which the resin is dissolved in water or an organic solvent is cast). Can be molded.
• the thickness of the polarizer can be appropriately set according to the purpose and application of the LCD in which the polarizing plate is used, but is typically 5 to 80 / zm.
• any appropriate method can be adopted depending on the purpose, materials used, conditions and the like.
• the polyvinyl alcohol-based resin film is expanded.
• the method used for a series of manufacturing processes, including hydration, dyeing, cross-linking, stretching, washing with water, and drying process is adopted.
• the treatment is performed by immersing the polyvinyl alcohol-based resin film in a bath containing the solution used in each step.
• the order, number of times, and the presence / absence of each treatment of swelling, dyeing, crosslinking, stretching, washing with water, and drying can be appropriately set according to the purpose, materials used, conditions and the like.
• the stretching process may be performed after the dyeing process or before the dyeing process, or may be performed simultaneously with the swelling process, the dyeing process, and the crosslinking process. Further, for example, it can be suitably employed to perform the crosslinking treatment before and after the stretching treatment. Further, for example, the water washing process may be performed only after a specific process that may be performed after all the processes.
• the swelling step is typically performed by immersing the polyvinyl alcohol-based resin film in a treatment bath (swelling bath) filled with water. This treatment cleans the surface of the poly (vinyl alcohol) resin film and the anti-blocking agent, and swells the polyvinyl alcohol resin film to prevent unevenness such as uneven dyeing.
• Glycerin, potassium iodide, or the like can be appropriately added to the swelling bath.
• the temperature of the swelling bath is typically about 20-60 ° C, and the immersion time in the swelling bath is typically about 0.1-10 minutes.
• the dyeing step is typically performed by immersing the polyvinyl alcohol-based resin film in a treatment bath (dye bath) containing a dichroic substance such as iodine.
• a dichroic substance such as iodine.
• water is generally used, but an appropriate amount of an organic solvent compatible with water may be added.
• the dichroic substance is typically used at a ratio of 0.1 to 1.0 part by weight with respect to 100 parts by weight of the solvent.
• the dye bath solution preferably further contains an auxiliary agent such as iodide. This is because the dyeing efficiency is improved.
• the auxiliary is used in a proportion of preferably 0.02 to 20 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the solvent.
• iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, An example is titanium iodide.
• the temperature of the dyeing bath is typically about 20 to 70 ° C, and it is immersed in the dyeing bath. The time is typically about 1 to 20 minutes.
• the crosslinking step is typically performed by immersing the dyed polyvinyl alcohol resin film in a treatment bath (crosslinking bath) containing a crosslinking agent.
• a crosslinking agent can be adopted as the crosslinking agent.
• Specific examples of the crosslinking agent include boron compounds such as boric acid and borax, darioxal, dartalaldehyde and the like. These can be used alone or in combination.
• a solvent used for the solution of the crosslinking bath water is generally used, but an appropriate amount of an organic solvent having compatibility with water may be added.
• the crosslinking agent is typically used at a ratio of 1 to 10 parts by weight per 100 parts by weight of the solvent.
• the solution of the crosslinking bath preferably further contains an auxiliary agent such as iodide. This is because uniform characteristics are easily obtained in the surface.
• the concentration of the auxiliaries is preferably 0.05 to 15% by weight, more preferably 0.5 to 8% by weight. Specific examples of iodide are the same as those in the dyeing process.
• the temperature of the crosslinking bath is typically about 20 to 70 ° C, preferably 40 to 60 ° C.
• the immersion time in the crosslinking bath is typically about 1 second to 15 minutes, preferably 5 seconds to 10 minutes.
• the stretching step may be performed at any stage as described above. Specifically, it may be carried out after the crosslinking treatment, which may be carried out after the dyeing treatment or before the dyeing treatment, or may be carried out simultaneously with the swelling treatment, the dyeing treatment and the crosslinking treatment.
• the cumulative draw ratio of the polybulal alcohol-based resin film needs to be 5 times or more, preferably 5 to 7 times, more preferably 5 to 6.5 times. If the cumulative draw ratio is less than 5 times, it may be difficult to obtain a polarizing plate with a high degree of polarization. When the cumulative draw ratio exceeds 7 times, the polyvinyl alcohol-based resin film (polarizer) may be easily broken. Arbitrary appropriate methods may be employ
• the polyvinyl alcohol-based resin film is stretched at a predetermined magnification in a treatment bath (stretching bath).
• a solution obtained by adding various metal salts, iodine, boron or zinc compounds in a solvent such as water or an organic solvent (for example, ethanol) is preferably used.
• the washing step is typically performed by immersing the polyvinyl alcohol-based resin film subjected to the above-described various treatments in a treatment bath (water washing bath). By the water washing process, unnecessary residues of the poly (vinyl alcohol) resin film can be washed and poured.
• the washing bath may be an aqueous solution of iodide (eg, potassium iodide or sodium iodide) which may be pure water.
• concentration of the aqueous iodide solution is preferably 0.1 to 10% by mass.
• An auxiliary agent such as zinc sulfate or zinc chloride may be added to the iodide aqueous solution.
• the temperature of the washing bath is preferably 10 to 60 ° C, more preferably 30 to 40 ° C.
• the immersion time is typically 1 second to 1 minute.
• the water washing process may be performed only once or multiple times as necessary. In the case of carrying out a plurality of times, the kind and concentration of the additive contained in the washing bath used for each treatment can be appropriately adjusted.
• the water washing step includes a step of immersing the polymer film in a potassium iodide aqueous solution (0.1 to 10% by mass, 10 to 60 ° C.) for 1 second to 1 minute, and a step of rinsing with pure water.
• a potassium iodide aqueous solution 0.1 to 10% by mass, 10 to 60 ° C.
• any appropriate drying method for example, natural drying, air drying, heat drying
• the drying temperature is typically 20 to 80 ° C.
• the drying time is typically 1 to: LO minutes.
• a polarizer is obtained.
• the polarizing plate of the present invention it is preferable to have an easy-adhesion layer and an adhesive layer between the polarizer and the polarizer including the polarizer and the polarizer protective film of the present invention.
• the adhesive layer is preferably a layer formed with a polybulal alcohol adhesive force.
• the polyalcohol-based adhesive contains a polybulualcohol-based resin and a cross-linking agent.
• the polyvinyl alcohol-based resin is not particularly limited, but for example, polybulal alcohol obtained by saponification of polyvinyl acetate; a derivative thereof; and a single copolymer having a co-polymerization property with vinyl acetate. Saponified products of copolymers with monomers; modified polyvinyl alcohols obtained by acetalization, urethanization, etherification, grafting, phosphoric esterification, etc.
• polyvinyl alcohol examples include unsaturated carboxylic acids such as (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, (meth) acrylic acid, and esters thereof; a -olefins such as ethylene and propylene; (Meth) aryl sulfonic acid (soda), sulfonic acid Soda (monoalkyl malate), soda alkyl malate disulfonate, N-methylol acrylamide, alkali salt of acrylamide alkyl sulfonate, N-butyrpyrrolidone,
• unsaturated carboxylic acids such as (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, (meth) acrylic acid, and esters thereof
• a -olefins such as ethylene and propylene
• N bulpyrrolidone derivatives and the like. These polybulal alcoholic resins can be used for only one type, or two or more types can be used in combination.
• the polyvinyl alcohol-based resin preferably has an average degree of polymerization from the viewpoint of adhesiveness.
• polyvinyl alcohol-based resin a polyvinyl alcohol-based resin having a acetoacetyl group can be used.
• the polybutyl alcohol-based resin having a acetoacetyl group is a highly reactive polyvinyl alcohol-based adhesive having a functional group, and is preferable in terms of improving the durability of the polarizing plate.
• the polybulal alcohol-based resin containing the acetoacetyl group is obtained by reacting the polybulal alcohol-based resin with diketene by a known method.
• a polyvinyl alcohol-based resin is dispersed in a solvent such as acetic acid, and diketene is added thereto, and a polybutyl alcohol-based resin is dissolved in a solvent such as dimethylformamide or dioxane in advance.
• a method of adding diketene to this is also mentioned.
• the method of making diketene gas or liquid diketene contact directly to polyvinyl alcohol is mentioned.
• the degree of modification of the acetoacetyl group of the polyvinyl alcohol-based resin having a acetoacetyl group is not particularly limited as long as it is 0.1 mol% or more. If it is less than 1 mol%, the adhesive layer has insufficient water resistance, which is inappropriate.
• Asetasechiru group modification degree is preferably from 0.1 to 40 mole 0/0, more preferably 1 to 20 mol%.
• the degree of modification of the acetoacetyl group is a value measured by NMR.
• crosslinking agent those used for polyvinyl alcohol-based adhesives can be used without particular limitation.
• a compound having at least two functional groups having a reactivity with polybulal alcohol-based resin can be used.
• alkylenediamines having two amino groups and an alkylene group such as ethylenediamine, triethyleneamine, hexamethylenediamine (among others) Hexamethylenediamine is preferred); tolylene diisocyanate, hydrogenated tolylene diisocyanate, trimethylene propane tolylene diisocyanate adduct, triphenol-methylene methane triisocyanate, methylene bis (4-phenol methane triisocyanate), Isophorone diisocyanates and their isocyanates such as ketoxime block or phenol block; ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin di or triglycidyl ether, 1,6-hexanediol diglycidyl ether, tri Epoxys such as methylolpropan
• the amount of the crosslinking agent to be added is preferably 0.1 to 35 parts by weight, more preferably 10 to 25 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol-based resin.
• a crosslinking agent can be blended in a range of more than 30 parts by weight and 46 parts by weight or less with respect to 100 parts by weight of the polybulal alcohol-based resin.
• the polybutyl alcohol adhesive further includes coupling agents such as silane coupling agents and titanium coupling agents, various tackifiers, UV absorbers, antioxidants, heat stabilizers, Stabilizers such as decomposition stabilizers can also be blended.
• coupling agents such as silane coupling agents and titanium coupling agents, various tackifiers, UV absorbers, antioxidants, heat stabilizers, Stabilizers such as decomposition stabilizers can also be blended.
• the polarizer protective film of the present invention can be subjected to an easy adhesion treatment to improve the adhesion to the surface in contact with the polarizer.
• Easy adhesion treatment includes corona treatment, plasma treatment, low pressure UV Surface treatment such as saponification treatment, saponification treatment, etc., and it is preferable to form an easy adhesion layer (anchor layer) after performing an easy adhesion treatment.
• Examples of the easy-adhesion layer include a silicone layer having a reactive functional group.
• the material of the silicone layer having a reactive functional group is not particularly limited.
• an isocyanate group-containing alkoxysilanol, an amino group-containing alkoxysilanol, a mercapto group-containing alkoxysilanol, a carboxy-containing alkoxysilanol, an epoxy group -Containing alkoxysilanols, butyl type unsaturated group-containing alkoxysilanols, halogen group-containing alkoxysilanols, isocyanato group-containing alkoxysilanols, and amino silanols are preferred.
• the adhesive strength can be strengthened by adding a titanium-based catalyst or a tin-based catalyst for efficiently reacting the silanol.
• other additives may be added to the silicone having the reactive functional group. More specifically, terpene resin, phenol resin, terpene-phenol resin, rosin resin, xylene resin, and other tackifiers, UV absorbers, antioxidants, heat stabilizers, and other stabilizers, etc. May be used.
• the silicone layer having a reactive functional group is formed by coating and drying by a known technique.
• the thickness of the silicone layer is preferably 1 to 300 nm, more preferably 1 to 1 OO nm, further preferably 1 to 80 nm, and particularly preferably 5 to 70 nm after drying.
• silicone having a reactive functional group may be diluted with a solvent.
• the diluent solvent is not particularly limited, and examples thereof include alcohols.
• the dilution concentration is not particularly limited, but is preferably 1 to 5% by weight, more preferably 1 to 3% by weight.
• the adhesive layer is formed by applying the adhesive on one side or both sides of the polarizer protective film and on either side or both sides of the polarizer. After laminating the polarizer protective film and the polarizer, a drying process is performed to form an adhesive layer composed of a coated and dried layer. This can also be bonded after forming the adhesive layer. Bonding of the polarizer and the polarizer protective film can be performed with a roll laminator or the like. The heating and drying temperature and drying time are appropriately determined according to the type of adhesive.
• the thickness of the adhesive layer becomes too thick after drying, it is not preferable from the viewpoint of the adhesive property of the polarizer protective film, and therefore, preferably 0.1 to 50 nm, more preferably 1 to 50 nm. The More preferably, it is 5-40 nm.
• the polarizer protective film can be bonded to the polarizer on both sides of the polarizer on one side of the polarizer protective film.
• the polarizer protective film of the polarizer is bonded by adhering to one side of the polarizer on one side of the polarizer protective film and bonding the cellulosic resin film to the other side. It is out.
• the cellulose-based resin film is not particularly limited, but triacetyl cellulose is preferable in terms of transparency and adhesiveness.
• the thickness of the cellulosic resin film is preferably 30 to: L00 ⁇ m, more preferably 40 to 80 ⁇ m. If the thickness force is less than 30 ⁇ m, the Finolem strength decreases and the workability is inferior. If the thickness force is more than 100 m, the light transmittance decreases significantly in durability.
• the polarizing plate according to the present invention may have an adhesive layer as at least one of the outermost layers! (Such a polarizing plate may be referred to as an adhesive polarizing plate). Particularly preferably, a pressure-sensitive adhesive layer for adhering to another member such as another optical film or a liquid crystal cell can be provided on the side of the polarizer protective film where the polarizer is not adhered.
• the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited.
• an acrylic polymer, silicone-based polymer, polyester, polyurethane, polyamide, polyether, fluorine-based or rubber-based polymer is a base polymer.
• those having excellent optical transparency such as an acrylic pressure-sensitive adhesive, exhibiting appropriate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, and having excellent weather resistance, heat resistance and the like can be preferably used.
• an acrylic pressure-sensitive adhesive made of an acrylic polymer having a carbon number of ⁇ 12 is preferred.
• a liquid crystal display device that prevents foaming and peeling due to moisture absorption, prevents optical characteristics from being deteriorated due to a difference in thermal expansion, prevents warping of the liquid crystal cell, and is high quality and has excellent durability. From the point of formability, etc., an adhesive layer having a low moisture absorption rate and excellent heat resistance is preferred.
• the above-mentioned pressure-sensitive adhesive layer is, for example, a natural product or a synthetic resin, in particular, a tackifying resin, glass fiber, glass beads, metal powder, other fillers such as inorganic powders, Pigment, wearing It may contain additives that can be added to the adhesive layer such as colorants and antioxidants. Moreover, the adhesive layer etc. which contain microparticles
• the above-mentioned pressure-sensitive adhesive layer can be attached by an appropriate method.
• an adhesive solution of about 10 to 40% by weight in which a base polymer or a composition thereof is dissolved or dispersed in a solvent composed of a single solvent or a mixture of appropriate solvents such as toluene and ethyl acetate is prepared.
• the pressure-sensitive adhesive layer may be provided on one or both sides of the polarizing plate as a superposed layer of different compositions or types. Moreover, when providing in both surfaces, it can also be set as adhesive layers with a different composition, a kind, thickness, etc. in the front and back of a polarizing plate.
• the thickness of the pressure-sensitive adhesive layer can be appropriately determined according to the purpose of use and adhesive force, and is preferably 1 to 40 ⁇ m, more preferably 5 to 30 ⁇ m, and particularly preferably 10 ⁇ 25 ⁇ m. If it is thinner than 1 ⁇ m, the durability will be poor, and if it is thicker than 40 m, it will be liable to float or peel off due to foaming, resulting in poor appearance.
• an anchor layer may be provided between the layers.
• an anchor layer selected from polyurethane, polyester, and a polymer having an amino group in the molecule is used, and a polymer having an amino group in the molecule is particularly preferably used. Is done. For polymers containing amino groups in the molecule, the amino group in the molecule reacts with the carboxyl group in the adhesive, the polar group in the conductive polymer, or interacts with the ionic interaction. Good adhesion is ensured.
• Polymers containing an amino group in the molecule include, for example, polyethyleneimine, polyallylamine, polybulamine, polybulurpyridine, polybulurpyrrolidine, and dimethylaminoethyl represented by a copolymerization monomer of the aforementioned acrylic adhesive.
• Examples thereof include a polymer of an amino group-containing monomer such as acrylate.
• an antistatic agent may be added.
• Antistatic agents for imparting antistatic properties include ionic surfactants, polyaniline Examples include conductive polymer systems such as phosphorus, polythiophene, polypyrrole, and polyquinoxaline, and metal oxide systems such as tin oxide, acid antimony, and indium oxide.
• a conductive polymer system is preferably used.
• water-soluble conductive polymers such as polyarlin and polythiophene, or water-dispersible conductive polymers are particularly preferably used. This is because when a water-soluble conductive polymer or a water-dispersible conductive polymer is used as a material for forming the antistatic layer, it is possible to suppress deterioration of the optical film substrate due to the organic solvent during the coating process.
• a compound, a benzotriazole compound, a cyanoacrylate compound, a nickel complex compound, or the like that is treated with an ultraviolet absorber such as a compound having an ultraviolet absorbing ability may be used.
• the polarizing plate of the present invention is not limited to be provided on either the viewing side or the knocklight side of the liquid crystal cell, or on both sides.
• the image display device of the present invention includes at least one polarizing plate of the present invention.
• a liquid crystal display device will be described as an example, but it goes without saying that the present invention can be applied to any display device that requires a polarizing plate.
• Specific examples of image display devices to which the polarizing plate of the present invention can be applied include self-luminous display such as an electroluminescence (EL) display, a plasma display (PD), and a field emission display (FED). Apparatus.
• FIG. 2 is a schematic cross-sectional view of a liquid crystal display device according to a preferred embodiment of the present invention. In the illustrated example, a transmissive liquid crystal display device will be described, but it goes without saying that the present invention is also applied to a reflective liquid crystal display device and the like!
• the liquid crystal display device 100 includes a liquid crystal cell 10, a retardation film 20 and 20 'disposed between the liquid crystal cell 10, and a polarizing plate 30 disposed outside the retardation films 20 and 20'. 30 ′, a light guide plate 40, a light source 50, and a reflector 60. Polarizing axes of polarizing plates 30 and 30 ' It is arranged so as to be orthogonal to.
• the liquid crystal cell 10 includes a pair of glass substrates 11 and 11 ′ and a liquid crystal layer 12 as a display medium disposed between the substrates.
• One substrate 11 is provided with a switching element (typically a TFT) for controlling the electro-optical characteristics of the liquid crystal, a scanning line for supplying a gate signal to the switching element, and a signal line for supplying a source signal. (Both not shown).
• the other glass substrate 11 ′ is provided with a color layer constituting a color filter and a light shielding layer (black matrix layer) (both not shown) o
• the distance (cell gap) between the substrates 11 and 11 is It is controlled by the spacer 13.
• the polarizing plate of the present invention described above is employed as at least one of the polarizing plates 30 and 30 ′.
• the liquid crystal molecules of the liquid crystal layer 12 are arranged in a state in which the polarization axis is shifted by 90 degrees. In such a state, incident light that is transmitted through only one direction of light by the polarizing plate is twisted 90 degrees by the liquid crystal molecule. As described above, since the polarizing plates are arranged so that their polarization axes are orthogonal to each other, the light (polarized light) that has reached the other polarizing plate is transmitted through the polarizing plate. Therefore, when no voltage is applied, the liquid crystal display device 100 performs white display (normally white method).
• the condition when the polarizing plate (100 mm X 100 mm) was twisted by hand and evaluated was evaluated according to the following criteria.
• A The polarizer and the polarizer protective film are integrated with each other so that peeling does not occur.
• the appearance of the obtained polarizing plate was evaluated.
• the evaluation was performed visually on a 50 mm ⁇ 50 mm polarizing plate according to the following criteria.
• Floating means that the polarizer and the polarizer protective film are not in close contact with each other, and streaks means that the polarizer protective film or the polarizer is adhered to itself although it is a very small area.
• the peripheral unevenness of the obtained polarizing plate was evaluated. Evaluation was made by attaching a 32-inch polarizing plate to the glass so that the upper plate was 0 ° and the lower plate 90 °, illuminated with a backlight from the lower plate side, and evaluated for light exposure according to the following criteria. Evaluation of light loss is based on a measuring instrument (two-dimensional color distribution measuring device, manufactured by Konica Minolta, trade name: CA—1500w) installed on the opposite side of the polarizing plate knock light (position 50 centimeters away from the top plate). It was performed using. Furthermore, the obtained polarizing plate was subjected to a heating test (80 ° C., 240 hours) and a humidification test (60 ° C., 90% RH, 240 hours), respectively. evaluated.
• a heating test 80 ° C., 240 hours
• a humidification test 60 ° C., 90% RH, 240 hours
• the refractive indices nx , ny and nz of the sample film are measured with an automatic birefringence measuring device (manufactured by Oji Scientific Instruments Co., Ltd., automatic birefringence meter KOBRA—WPR), and the in-plane retardation And and thickness direction retardation Rth was calculated.
• the measurement temperature was 23 ° C and the measurement wavelength was 590 nm.
• the pressure-sensitive adhesive polarizing plate was punched out at 25 mm ⁇ 50 mm so that the polarizing plate absorption axis was 45 ° with respect to the long side, and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive polarizing plate was attached to a glass plate to obtain a measurement sample. Put a measurement sample in a constant temperature and humidity chamber at 60 ° CZ95% RH and take it out at a predetermined time After 30 minutes from the removal, the polarization change rate and the transmittance change rate were measured with DOT-3 (Murakami Color Research Laboratory).
• a pressure-sensitive adhesive polarizing plate was attached so that the polarizing plate absorption axis was 45 ° on the upper plate and 135 ° on the lower plate with respect to the long side, with a glass plate interposed therebetween, and used as a measurement sample.
• the measurement sample was put into an incubator at 80 ° C, taken out at a predetermined time, and Rth was measured.
• a pressure-sensitive adhesive polarizing plate was attached so that the polarizing plate absorption axis was 45 ° on the upper plate and 135 ° on the lower plate with respect to the long side, with a glass plate interposed therebetween, and used as a measurement sample.
• a measurement sample was put into a constant temperature and humidity chamber at 60 ° CZ90% RH, and was taken out at a predetermined time, and Rth was measured.
• the time when the internal temperature reached 70 ° C was set as the polymerization start time, and the polymerization was terminated for 180 minutes. Thereafter, the reaction system was cooled, the polymer was separated, washed and dried according to the usual method to obtain a bead-shaped copolymer (a-1).
• the copolymer (a-1) had a polymerization rate of 98% and a weight average molecular weight of 130,000.
• the thermoplastic polymer (A-1) had a dartaric anhydride structural unit of 28 wt%, a methyl methacrylate structural unit of 68 wt%, and a methyl methacrylate structural unit strength of wt%.
• Acrylic elastic particles were synthesized separately from the thermoplastic polymer (A-1).
• the following composition (B) was added as an initial adjustment solution in a glass container (capacity 5 liters) equipped with a cooler.
• composition (B) While stirring the initial adjustment solution (composition (B)) in a nitrogen atmosphere, the following composition (C) was added and reacted at 70 ° C for 30 minutes to obtain a rubbery polymer. .
• composition (C) 53 parts by weight of butyl acrylate
• composition (D) was continuously added at 70 ° C for 90 minutes with continued stirring, and after completion of the addition, the mixture was further maintained for 90 minutes to form a shell layer.
• the obtained polymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to obtain core-shell type rubber-containing polymer acrylic elastic particles (B-1). Obtained.
• the average particle size of the rubbery polymer portion of the acrylic elastic particles (B-1) measured with an electron microscope was 170 nm. Further, the refractive index difference between the obtained acrylic elastic particles (B-1) and the thermoplastic polymer (A-1) was 0.002.
• a 300 ml separable flask equipped with a stirrer was charged with 50 g of the obtained acrylic resin (C-1) and 150 g of 2-butanone, and stirred with a double helical ribbon stirring blade for 24 hours.
• the resulting solution was filtered through a 1 ⁇ m cut glass filter to obtain an acrylic resin solution.
• a part of the obtained acrylic resin solution was taken on a glass plate on which a polyethylene terephthalate film (thickness: 100 m) was fixed, and a uniform film was formed using a bar coater. This was heated at 50 ° C for 10 minutes to obtain a self-supporting film. The obtained film is peeled off from the polyethylene terephthalate film and fixed to a metal frame, and further heated at 100 ° C for 10 minutes, 120 ° C for 20 minutes, 140 ° C for 20 minutes, and 170 ° C for 40 minutes. A polarizer protective film (D-1) containing an acrylic resin having a ring structure was obtained. [Example 1]
• Silane coupling agent APZ— 6601 manufactured by Toray 'Dowcoung' Silicone Co., Ltd. 1100 parts of the solution prepared by adding 66.7 parts of isopropyl alcohol to a corona-treated surface of the film obtained above Apply with # 5 to evaporate volatiles.
• the thickness of the easily adhesive layer after evaporation was 50 nm.
• Polybutyl alcohol adhesive aqueous solution prepared by adjusting an aqueous solution containing 20 parts by weight of methylol melamine to 100 parts by weight of polyvinyl alcohol resin modified with acetoacetyl group (acetylene degree 13%) to a concentration of 0.5% by weight was prepared.
• the surface of the polarizer protective film (D-1) with an easy-adhesion layer is applied to one side of the polarizer, and the other side is a saponified 40 ⁇ m thick triacetyl cellulose film (manufactured by Koryo Minolopt Co. Bonding was performed using the polyvinyl alcohol-based adhesive aqueous solution prepared above so that the saponification surface of the product name: KC4UYW was in contact.
• the polybulal alcohol adhesive aqueous solution was applied to the easy-adhesion layer side and the triacetyl cellulose side of the polarizer protective film (D-1), respectively, and dried at 85 ° C. for 10 minutes to obtain a polarizing plate.
• the base polymer contains an acrylic polymer with a weight average molecular weight of 2 million consisting of a copolymer of butyl acrylate: acrylic acid: 2-hydroxyethyl acrylate: 100: 5: 0.1 (weight ratio)
• a solution (30% solids) was used.
• a solvent for adjusting viscosity ethyl acetate
• an adhesive solution solid content 12%.
• a release film polyethylene terephthalate substrate: Diafoil MRF38, manufactured by Mitsubishi Polyester
• Table 1 shows the results of evaluating the adhesion, appearance, and peripheral unevenness between the polarizer protective film and the polarizer in the obtained polarizing plate.
• Table 2 shows the degree of polarization change, transmittance change, Rth change rate with heating, and Rth change rate with heating and humidification.
• Example 1 the surface of the triacetyl cellulose film of the polarizing plate was subjected to corona treatment at a discharge amount of 13 3w ⁇ minZm 2 and then the release film on which the pressure-sensitive adhesive layer was formed was bonded. In the same manner as in Example 1, an adhesive-type polarizing plate was produced.
• Table 1 shows the results of evaluating the adhesion, appearance, and peripheral unevenness between the polarizer protective film and the polarizer in the obtained polarizing plate.
• Example 1 an adhesive-type polarizing plate was produced in the same manner as in Example 1 except that the polarizer protective film (D-1) was bonded to both sides of the polarizer.
• Table 1 shows the results of evaluating the adhesion, appearance, and peripheral unevenness between the polarizer protective film and the polarizer in the obtained polarizing plate.
• Table 2 shows the Rth change rate under heating and the Rth change rate under heating and humidification in the obtained polarizing plate.
• Acrylic ultraviolet curable resin (Dainippon Ink Chemical Co., Ltd., Unidic 17-806) 100 parts, UV polymerization initiator (Ciba 'Specialty' Chemicals Inc., Irgacure 90 7) 5 parts, and leveling agent ( Daifuku Ink Chemical Co., Ltd., MegaFac F407) 0.5 part was dispersed in toluene to prepare a coating solution having a solid concentration of 40%.
• the coating solution was applied on the triacetyl cellulose surface of the polarizing plate produced in Example 1 with a bar coater, and then heated at 90 ° C for 3 minutes to form a coating film. Thereafter, the coating film was cured by irradiating with ultraviolet rays to form a hard coat layer (thickness 8 ⁇ m).
• Table 2 shows the polarization degree change rate and the transmittance change rate in the obtained polarizing plate.
• Example 1 polyvinyl saponified above was prepared so that the saponification-treated surfaces of a 40 m-thick triacetyl cellulose film (trade name: KC4UYW) produced by saponification on both surfaces of the polarizer were in contact with each other.
• a pressure-sensitive adhesive polarizing plate was produced in the same manner as in Example 1 except that the bonding was performed using an alcohol-based adhesive aqueous solution.
• Table 1 shows the results of evaluating the adhesion, appearance, and peripheral unevenness between the polarizer protective film and the polarizer in the obtained polarizing plate.
• Table 2 shows the degree of polarization change, transmittance change, Rth change rate with heating, and Rth change rate with heating and humidification.
• Example 1 and Example 3 are superior to the peripheral unevenness after the heating test as compared with Comparative Example 1 (no light loss).
• the evaluation of the peripheral unevenness after the heating test was ⁇ (light-blurring was observed at the edge), but in Example 2, the thickness of the polarizing plate was larger than that in Comparative Example 1.
• the thickness of the polarizing plate was larger than that in Comparative Example 1.
• Example 1 and Example 4 were superior to Comparative Example 1 in terms of both the degree of polarization change and the transmittance change rate.
• Example 3 compared to Comparative Example 1, excellent results were obtained in both the Rth change rate under heating and the Rth change rate under heating and humidification.
• the polarizer protective film and polarizing plate of the present invention can be suitably used for various image display devices (liquid crystal display devices, organic EL display devices, PDPs, etc.).

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