WO2007102340A1 - 偏光子保護フィルム、偏光板及び垂直配向方式液晶表示装置 - Google Patents
偏光子保護フィルム、偏光板及び垂直配向方式液晶表示装置 Download PDFInfo
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- WO2007102340A1 WO2007102340A1 PCT/JP2007/053608 JP2007053608W WO2007102340A1 WO 2007102340 A1 WO2007102340 A1 WO 2007102340A1 JP 2007053608 W JP2007053608 W JP 2007053608W WO 2007102340 A1 WO2007102340 A1 WO 2007102340A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- 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
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- 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
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/03—Viewing layer characterised by chemical composition
- C09K2323/031—Polarizer or dye
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
- C09K2323/03—Viewing layer characterised by chemical composition
- C09K2323/035—Ester polymer, e.g. polycarbonate, polyacrylate or polyester
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- 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
- G02F1/13363—Birefringent elements, e.g. for optical compensation
- G02F1/133634—Birefringent elements, e.g. for optical compensation the refractive index Nz perpendicular to the element surface being different from in-plane refractive indices Nx and Ny, e.g. biaxial or with normal optical axis
-
- 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
Definitions
- Polarizer protective film polarizing plate, and vertical alignment type liquid crystal display device
- the present invention relates to a polarizer protective film, a polarizing plate, and a vertical alignment type liquid crystal display device. More specifically, the present invention has excellent viewing angle characteristics as a retardation film, and light leakage during black display such as corner unevenness and browning.
- the present invention relates to a polarizer protective film in which the amount of light decreases, a polarizing plate using the same, and a vertical alignment type liquid crystal display device.
- TAC film As a polarizer protective film for a liquid crystal display device, a cellulose triacetate (triacetyl cellulose, TAC) film has been conventionally used. TAC film has high transmittance, can be easily bonded to the polybulal alcohol film of the polarizer, and has low birefringence anisotropy, so it does not give an extra retardation component to the polarizing plate, thus protecting the polarizer It has been used favorably as a film. On the contrary, TAC film has some positive birefringence anisotropy, but the anisotropy is too small to produce a sufficient phase difference even if it is stretched.
- TAC film was not suitable for aiming at widening the viewing angle by providing a retardation function to the polarizing plate itself. Then, in order to give such a polarizer-protecting TAC film birefringence anisotropy, a technique using a material that develops a phase difference by using a acetyl group of triacetyl senorelose (for example, Patent Document 1). And a technology for making a film with more retardation by adding a material that develops retardation to the film (see, for example, Patent Document 2) has been developed and put into practical use. Yes. By properly stretching the anisotropy cellulose acetate film to develop a retardation, the polarizer protective film itself can have a retardation, especially VA (vertical alignment). Type LCD The field angle can be improved.
- VA vertical alignment
- a polarizing plate manufactured using a film having a phase difference different from that of a general TAC film manufactured by such a method is as follows.
- the polarizing plate bonded to the glass substrate of a liquid crystal display device is contracted by the polybulal alcohol of the polarizer due to high temperature exposure, stress is applied to the polarizer protective film, and the retardation of the polarizer protective film changes.
- VA and IPS lateral electric field drive
- the cellulose acylate film has a small optical anisotropy, but it is not at all, but its small but present positive birefringence anisotropy causes a viewing angle of a liquid crystal display device. The color may be adversely affected.
- a material having a negative birefringence anisotropy for example, a method of adding an acrylic polymer (for example, see Patent Document 3) or a method of adding a styrene polymer (for example, , See Patent Document 4), and discloses a method of controlling the phase difference by adding a substance that cancels anisotropy.
- Patent Document 1 JP 2001-188128 A
- Patent Document 2 JP 2000-111914 A
- Patent Document 3 Japanese Patent Laid-Open No. 2003-12859
- Patent Document 4 Japanese Patent Laid-Open No. 2005-105140
- An object of the present invention is to provide a polarizer protective film that has excellent viewing angle characteristics as a retardation film and reduces light leakage during black display such as corner unevenness and white brown, a polarizing plate using the same, and a vertical film
- An alignment type liquid crystal display device is provided.
- One aspect of the present invention for achieving the above object is that cellulose acylate having a total acyl substitution degree of 2.2 or more and less than 2.5, and an acrylate ester or a methacrylate ester.
- a polarizer protective film comprising a polymer obtained by polymerization.
- FIG. 1 is a schematic diagram of a polarizer protective film having an antistatic layer and an adhesive layer.
- Polarized light comprising cellulose acylate having a total degree of acyl substitution of 2.2 to less than 2.5 and a polymer obtained by polymerizing an acrylate ester or a methacrylate ester Child protective film.
- In-plane retardation value Ro is 0 to 100 nm, thickness direction retardation value Rth force 3 ⁇ 40 to 250 nm, The polarization according to any one of the above (1) to (3), characterized in that Child protective film
- Rth ⁇ (nx + ny) / 2_nz ⁇ X d (where nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the fast axis direction in the film plane, nz Is the refractive index in the thickness direction of the film, and d is the thickness (nm) of the film.)
- a polarizing plate comprising the polarizer protective film according to any one of (1) to (4) described above as at least a polarizer protective film on a liquid crystal cell side.
- a polarizer protective film that has excellent viewing angle characteristics as a retardation film and reduces light leakage during black display such as corner unevenness and white brown, a polarizing plate and a vertical alignment method using the same A liquid crystal display device can be provided.
- the present invention includes a cellulose acylate having a total acyl substitution degree of 2.2 or more and less than 2.5, and a polymer obtained by polymerizing acrylic acid ester or methacrylic acid ester.
- the polarizer protective film is used as a retardation film for a polarizing plate, which has an excellent viewing angle, can reduce light leakage during black display such as corner unevenness and white brown, and has excellent display performance.
- the present inventors have found that a liquid crystal display device can be obtained.
- the TAC film has a small birefringence anisotropy, it has been conventionally used as a film for the purpose of protecting a polarizer. It cannot be used as it is for a retardation film having a compensation function.
- Patent Document 1 a technique using cellulose acetate propionate or the like as a film material is an additive technique for controlling birefringence (Patent Document 2). ) was developed.
- Patent Document 3 since the anisotropy of TAC film is small, there is a technology that uses acrylic polymer (Patent Document 3) and a technology that uses styrene polymer (Patent Document 4) as a means of reducing the anisotropy. ) Is disclosed.
- the phase difference of the triacetyl cell single film generally used for the protective film for polarizing plate is as follows.
- the retardation Rth in the thickness direction at 23 ° C 55% RH and wavelength 589nm is 30nm or more and 60 ⁇ m or less.
- Phase difference Ro is 5nm or less.
- a film in which the retardation in the thickness direction Rth is further reduced to reduce the retardation is also disclosed.
- the polarizing plate protective film that also serves as the retardation film is a so-called negative C, in which the above Rth is 60 nm or less and the Rth is more than 60 nm with a retardation. Plate or biaxial film.
- the polarizer protective film of the present invention is characterized in that it is a cellulose acylate film containing a single cell succinate having a total degree of acyl substitution of 2.2 or more and less than 2.5.
- the polarizer protective film according to the present invention may be referred to as a cellulose acylate film.
- Cellulose molecules are composed of many glucose units linked, and the dulose unit has three hydroxyl groups. The number of substitution of the acyl group at these three hydroxyl groups is called the degree of substitution. For example, cellulose triacetate has a acetyl group attached to all three hydroxyl groups of the glucose unit.
- the cellulose acylate used in the present invention is a carboxylic acid ester having about 2 to 22 carbon atoms, and may be an aromatic carboxylic acid ester, particularly a lower fatty acid ester of cellulose.
- the lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having a carbon atom number of S6 or less.
- the acyl group bonded to the hydroxyl group may be linear or branched or may form a ring. Further substituents may be substituted. In the case of the same substitution degree, birefringence decreases when the number of carbon atoms is large. Therefore, the number of carbon atoms is preferably selected from among acyl groups having 2 to 6 carbon atoms. It is preferable that the number of carbon atoms in the cell port monosulfate is 2 to 4 and that the number of carbon atoms is 2 to 3 is preferable.
- the polarizer protective film of the present invention has a total acyl substitution degree of 2.2 or more and less than 2.5, and a substitution degree of propionyl group of 0.7 to 1.5.
- a propionate is preferred. These can be synthesized by known methods.
- the method for measuring the substitution degree of the asinole group can be measured according to the provisions of ASTM-D817-96.
- the cellulose of the cellulose acylate of the present invention is not particularly limited, Examples include cotton linters, wood pulp (from conifers and hardwoods), and kenaf.
- the cellulose acylates obtained from them can be mixed and used at an arbitrary ratio.
- These cellulose acylates are prepared by using an organic solvent such as an organic acid such as acetic acid or methylene chloride when the acylating agent is an acid anhydride (acetic anhydride, propionic anhydride, butyric anhydride). It can be obtained by reacting with a cellulose raw material using a protic catalyst such as sulfuric acid.
- the reaction is carried out using a basic compound such as amin as a catalyst.
- a basic compound such as amin as a catalyst.
- the force that increases the elastic modulus when the molecular weight of the cellulose acylate film is large. If the molecular weight is increased too much, the viscosity of the solution of cellulose acylate becomes too high, resulting in a decrease in productivity.
- the molecular weight of the cellulose acylate is preferably a number average molecular weight (Mn) of 40,000 to 200,000, more preferably 100000 to 200,000.
- the cellulose acylate used in the present invention preferably has an Mw / Mn ratio of 4.0 or less, more preferably from 1 ⁇ 4 to 2 ⁇ 3.
- the average molecular weight and molecular weight distribution of cellulose acylate can be measured using high-performance liquid chromatography. Using this, the number average molecular weight (Mn) and the weight average molecular weight ( ⁇ w) are calculated and the ratio is calculated. Can be calculated.
- Cellulose acylate was added to 20 ml of pure water (electrical conductivity 0.1 ⁇ S / cm or less, pH 6.8) and stirred at 25 ° C for lhr in a nitrogen atmosphere. it is preferable P H 6-7, an electrical conductivity of force ⁇ ⁇ 100 ⁇ S / cm.
- the polarizer protective film of the present invention is characterized by containing a polymer obtained by polymerizing acrylic acid ester or methacrylic acid ester.
- the polymer obtained by polymerizing the acrylic ester or methacrylic ester according to the present invention may be composed of a single monomer force or a plurality of monomer forces.
- the monomer is preferably selected from acrylic acid esters or methacrylic acid esters, but other monomers, such as anhydrous maleic acid, may be used depending on the retardation characteristics, wavelength dispersion characteristics, and heat resistance of the film to be produced. Les, including acid, styrene, etc.
- a polymer obtained by polymerizing the acrylic ester or methacrylic ester according to the present invention will be described as a polymer X.
- the polymer X according to the present invention includes an ethylenically unsaturated monomer Xa having no aromatic ring and a hydrophilic group in the molecule, and an ethylenically unsaturated monomer Xb having no aromatic ring in the molecule and having a hydrophilic group.
- weight average molecular weight is 500 or more and the effect of improving corner unevenness is great, it is excellent in compatibility with cellulose acylate and transparency.
- Rl and R3 represent H or CH3.
- R2 represents an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group.
- R4 represents _CH2_, _ ⁇ 2114_, or _ ⁇ 3116_.
- the ethylenically unsaturated monomer Xa having no aromatic ring and no hydrophilic group in the molecule includes, for example, methyl acrylate, ethyl acrylate, propyl acrylate (i-, n_), butinole acrylate (n- , I-, s-, t-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i_), heptyl acrylate (n-, i_), octyl acrylate (N-, i_), nonyl acrylate (n-, i_), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid ( ⁇ -force prolatathon), acrylic acid ( Examples include 2-hydroxyethyl), acrylic acid (2-ethoxyethyl), and the like, or those obtained by replacing the acrylic ester with a me
- the ethylenically unsaturated monomer Xb having no hydrophilic ring in the molecule and having a hydrophilic group is preferably acrylic acid or a methacrylic acid ester as a monomer unit having a hydroxyl group.
- acrylic acid 2-hydroxyethyl
- acrylic acids include those replaced with methacrylic acid, and preferably acrylic acid (2-hydroxyethyl), methacrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic acid (3-hydroxypropyl).
- the polymer X is synthesized by copolymerization using the hydrophobic monomer Xa and the hydrophilic monomer Xb.
- the ratio of the hydrophobic monomer Xa to the hydrophilic monomer Xb used in the synthesis is preferably in the range of 99 ::! To 65:35, more preferably in the range of 95: 5 to 75:25.
- the proportion of the hydrophobic monomer Xa used is large, the compatibility with cellulose acylate is improved, but the retardation value Rth in the film thickness direction is increased.
- the ratio of the hydrophilic monomer Xb used is large, the above-mentioned compatibility is deteriorated, but the effect of reducing the retardation value Rth is high.
- the ratio of the hydrophilic monomer Xb exceeds the above range, it is not preferable because haze is generated during film formation.
- a chain transfer agent such as a mercapto compound or carbon tetrachloride
- a method using a polymerization terminator such as benzoquinone dinitrobenzene in addition to the polymerization initiator, and JP 2000-128911 or 2000-344823 a method of bulk polymerization using a compound having a single thiol group and a secondary hydroxyl group as described in the publication No., or a polymerization catalyst in which the compound and an organometallic compound are used in combination.
- a chain transfer agent such as a mercapto compound or carbon tetrachloride
- a polymerization terminator such as benzoquinone dinitrobenzene in addition to the polymerization initiator
- JP 2000-128911 or 2000-344823 a method of bulk polymerization using a compound having a single thiol group and a secondary hydroxyl group as described in the publication No.
- the weight average molecular weight of the polymer X of the present invention can be adjusted by a known molecular weight adjusting method.
- a molecular weight adjusting method include a method of adding a chain transfer agent such as carbon tetrachloride, lauryl mercaptan, octyl thioglycolate, and the like.
- the polymerization temperature is usually from room temperature to 130 ° C, preferably from 50 ° C to 100 ° C. This temperature or the polymerization reaction time can be adjusted.
- the weight average molecular weight can be measured by the molecular weight measurement method.
- the addition amount of the polymer X is appropriately adjusted in order to give the film a desired retardation. In order to reduce the phase difference, it is necessary to add a small amount to increase the phase difference. However, if the amount is too small, the corner unevenness deteriorates. If the amount is too large, the film strength cannot be maintained. % To 45% by mass is preferable.
- Plasticizers that impart processability, flexibility, and moisture resistance to films, UV absorbers that provide UV absorption function, antioxidants that prevent film deterioration, microparticles (matting agent) that give film slipperiness, films A retardation control agent or the like for adjusting the retardation may be contained.
- the plasticizer used is not particularly limited, but it may cause haze in the film or It preferably has a functional group capable of interacting with cellulose acylate by hydrogen bonding or the like so as not to bleed out or volatilize from the rum.
- Examples of such functional groups include hydroxyl groups, ether groups, carbonyl groups, ester groups, carboxylic acid residues, amino groups, imino groups, amide groups, imide groups, cyano groups, nitro groups, sulfonyl groups, sulfones. Forces including an acid residue, a phosphonyl group, a phosphonic acid residue, etc. Preferred are a carbonyl group, an ester group, and a phosphonyl group.
- Phosphate ester plasticizers specifically, phosphoric acid alkyl esters such as triacetyl phosphate and tributyl phosphate, phosphoric acid cycloalkyl esters such as tricyclopentyl phosphate and cyclohexyl phosphate, and triphenyl Phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diphenyl dibiphenyl phosphate, trioctyl phosphate, tributyl phosphate, trinaphthyl phosphate, trixyllinoleophosphate, tris ortho-biphenyl phosphate, etc.
- phosphoric acid alkyl esters such as triacetyl phosphate and tributyl phosphate
- phosphoric acid cycloalkyl esters such as tricyclopentyl phosphate and cyclohex
- the phosphoric acid ester of These substituents may be the same or different, and may be further substituted.
- a mixture of an alkyl group, a cycloalkyl group, and an aryl group may be used, and substituents may be covalently bonded.
- alkylene bis (diaryl phosphate) such as ethylene bis (dimethyl phosphate), butylene bis (diethyl phosphate), alkylene bis (dialkyl phosphate), ethylene bis (diphenyl phosphate), propylene bis (dinaphthyl phosphate), etc.
- Arylene bis (diaryl phosphate) such as arylene bis (diphenyl phosphate), phenylene bis (diphenyl phosphate), phenylene bis (dibutyl phosphate), biphenylene bis (dioctyl phosphate), etc. ) And the like.
- substituents may be the same or different, and may be further substituted.
- a mixture of an alkyl group, a cycloalkyl group, and an aryl group may be used, and substituents may be covalently bonded.
- phosphate ester Part of polymer or part of molecular structure of additives such as antioxidants, acid scavengers, UV absorbers etc. which may be regularly pendant Even if it has been introduced to.
- additives such as antioxidants, acid scavengers, UV absorbers etc.
- arylene phosphate and arylene bis (diaryl phosphate) are preferred.
- triphenyl phosphate is preferred.
- Phenyllenbis (diphenyl phosphate) is preferred.
- Ethylene glycol ester-based plasticizer Specifically, ethylene glycol alkyl ester-based additives such as ethylene glycol diacetate and ethylene glycol dibutyrate, ethylene glycol dicyclopropylcarboxylate, ethylene glycol diester Examples thereof include ethylene glycol cycloalkyl ester-based additives such as cyclohexyl carboxylate, and ethylene glycol aryl ester-based additives such as ethylene glycol dibenzoate and ethylene glycol di4-methylbenzoate. These alkylate groups, cycloalkylate groups, and arylate groups may be the same or different, and may be further substituted.
- ethylene glycol ester may have a substituted partial structure strength of an ethylene glycol ester. It may be part of a polymer or may be regularly pendant. Also, an antioxidant, an acid scavenger, an ultraviolet absorber, etc. It may be introduced into part of the molecular structure of the additive.
- Glycerin ester plasticizers specifically, glycerol alkyl esters such as triacetin, tributyrin, glycerol diacetate caprylate, glycerol oleate propionate, glycerol tricyclopropyl carboxylate, glycerol tricyclohexyl carboxylate Glycerin cycloalkyl ester, glycerin tribenzoate, glycerin 4-methylbenzoate, etc.
- glycerol alkyl esters such as triacetin, tributyrin, glycerol diacetate caprylate, glycerol oleate propionate, glycerol tricyclopropyl carboxylate, glycerol tricyclohexyl carboxylate
- Glycerin cycloalkyl ester glycerin tribenzoate, glycerin 4-methylbenzoate, etc.
- glycerin aryl ester diglycerin tetraacetylate, diglycerin tetrapropionate, diglycerin acetate tricaprylate, diglycerin tetralaurate Diglycerin alkyl esters, diglycerin tetracyclobutyl carboxylate, diglycerin tetracyclopentyl carboxylate, etc. Grayed Li serine cycloalkyl esters, diglycerin tetra base Nzoeto, diglycerol ⁇ reel ester such as diglycerin 3-methylcarbamoyl Rubenzoeto the like.
- alkylate groups, cycloalkyl carboxylate groups, and arylate groups may be the same or different, and may be further substituted. Further, a mixture of alkylate group, cycloalkyl carboxylate group and arylate group may be used, and these substituents may be bonded by a covalent bond.
- glycerin glycerol and diglycerin part may be substituted. Partial structural strength of tellurium and diglycerin esters Part of the polymer or part of the molecular structure of additives such as antioxidants, acid scavengers, and UV absorbers that may be regularly bent. It has been introduced, even better.
- Polyhydric alcohol ester-based additives Specific examples include polyhydric alcohol ester-based additives described in paragraphs 30 to 33 of JP-A-2003-12823.
- alkylate group, cycloalkylcarboxylate group and arylate group may be the same or different, and may be further substituted. Also, a mixture of alkylate group, cycloalkylcarboxylate group, and arylate group may be used, and these substituents may be bonded by a covalent bond. Furthermore, the polyhydric alcohol part may be substituted, or the partial structural force of the polyhydric alcohol may be part of the polymer or may be regularly pendant. Also, antioxidant, acid scavenger, UV absorption It may be introduced into a part of the molecular structure of an additive such as an agent.
- Dicarboxylic acid ester plasticizers specific examples of alkyl dicarboxylic acid alkyl esters such as didodecyl malonate (C1), dioctyl dipate (C4), dibutyl sebacate (C8) IJ, Addition of alkyl dicarboxylic acid cycloalkyl esters such as dicyclopentyl succinate and dicyclohexyl adipate IJ, diphenyl succinate, alkyl dicarboxylic acid aryl ester based additives such as di-4-methylphenyl daltalate, Dihexyl 1,4-cyclohexanedicarboxylate, didecylbicyclo [2. 2.
- alkyl dicarboxylic acid alkyl esters such as didodecyl malonate (C1), dioctyl dipate (C4), dibutyl sebacate (C8) IJ
- cycloalkyl dicarboxylic acid alkyl ester such as dicarboxylate lj, dicyclohexyl 1,2, Cyclobutane dicarboxylate, dicyclopropyl 1,2-cyclohexyldicarbo Cycloalkyldicarboxylic acid cycloalkyl esters such as xylates
- cycloalkyl dicarboxylic acids such as lj, diphenyl_1,1-cyclopentyl dicarboxylate, di-2-naphthynole 1,4-cyclohexanedicarboxylate
- Acid aryl ester-based additives such as jetyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, etc.
- These alkoxy groups and cycloalkoxy groups may be the same or different, and may be mono-substituted. These substituents may be further substituted.
- the alkyl group and cycloalkyl group may be mixed, or these substituents may be covalently bonded to each other.
- aromatic ring of phthalic acid may be substituted, and a multimer such as a dimer, trimer or tetramer may be used.
- the plasticizer can be added in an amount ranging from:! To 25% by mass. If the amount is less than 1% by mass, the effect of adding a plasticizer is not recognized. If the amount is more than 25% by mass, bleeding out is likely to occur, and the stability with time of the film is lowered. Further, it is preferable for obtaining the effect of the present invention that the amount is smaller than the amount of the additive of the polymer X.
- the polarizer protective film and other films used in the liquid crystal image display device contain an ultraviolet absorber, and the ultraviolet absorber serves to prevent deterioration of the liquid crystal and the polarizing film when used outdoors. Even in the polarizer protective film of the present invention, an ultraviolet absorber is preferably used. Examples of ultraviolet absorbers that can be used in the present invention include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and the like. Force S is possible.
- an ultraviolet absorber having a strong absorption at a short wavelength and an ultraviolet absorber having an absorption at a long wavelength it is preferable to combine an ultraviolet absorber having a strong absorption at a short wavelength and an ultraviolet absorber having an absorption at a long wavelength, and as an ultraviolet absorber having a strong absorption at a short wavelength, Benzotriazole ultraviolet absorbers and benzophenone ultraviolet absorbers, which have light stability, are preferred as cyanoacrylate compounds and UV absorbers that absorb light at longer wavelengths, and have less unwanted coloration.
- a zotriazole-based ultraviolet absorber is particularly preferred.
- Examples of short-wave ultraviolet absorbers include Cyprosynthetic SEESORB 201, 202, 501, 502, 612NH, and 712. Among them, the cyanoacrylate compound SEESORB 501, 502 is preferable.
- Benzotriazole For example, TINUVIN109, TINUVIN 171, TINUVIN326, TINUVIN327, and TINUVIN328 manufactured by Chinoku 'Specialty' Chemicals Co., Ltd. can be preferably used. Since it may be deposited or volatilized on the web (the name of the dope film after casting on the metal support is referred to as web), the applied amount is 1 to 10 mass%.
- the polarizer protective film contains a polymer ultraviolet absorber that is less likely to precipitate than the low molecular weight ultraviolet absorber, together with the polymer according to the present invention.
- UV rays can be sufficiently cut in a stable state without impairing the retention property, moisture permeability, etc. and without causing phase separation in the film.
- the polymer ultraviolet absorber useful in the present invention the polymer ultraviolet absorber described in JP-A-6-148430 and a polymer containing an ultraviolet absorber monomer can be used without limitation.
- the present invention contains a UV-absorbing copolymer polymer (sometimes referred to as a polymer UV absorber or a polymer UV agent) synthesized from an UV-absorbing monomer represented by the following general formula (2). And then, it ’s better to be.
- a UV-absorbing copolymer polymer sometimes referred to as a polymer UV absorber or a polymer UV agent
- n represents an integer of 03
- R R represents a hydrogen atom, a halogen atom, or a substituent.
- X represents one COO——CONR—10C001, —NR CO—, and R R represents a hydrogen atom, an alkyl group, or an aryl group. However, the group represented by R is a polymerizable group.
- n represents an integer of 0 3 and when n is 2 or more, a plurality of R
- R to R each represents a hydrogen atom, a halogen atom or a substituent.
- halogen atom As halogen atom
- Examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom and a chlorine atom are preferable.
- the substituent include an alkyl group (for example, a methinole group, an ethyl group, an isopropyl group, a hydroxyethyl group, a methoxymethylol group, a trifanolomethyl group, a t_butyl group), an alkenyl group (for example, a bur group, Aryl group, 3_butene_1-yl group, etc.), aryl group (for example, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc.), heterocyclic group (for example, pyridyl group, benzimidazolyl, etc.) Group, benzthiazolyl group, benzoxazolyl group, etc
- R to R may have a substituent, and adjacent R to R are connected to each other to form a 5- to 7-membered
- a ring may be formed.
- R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an alkynyl group.
- alkyl group for example, a methylol group, an ethyl group, a propyl group, an isopropyl group, an n_butyl group, an isobutyl group, a t_butyl group, an amino group, an isoamino group, a hexyl group, and the like can be given.
- the alkyl group may further have a halogen atom or a substituent.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- substituents examples include , Acyl groups (eg, acetyl group, propanolino group, butyroyl group, etc.), alkoxy groups (eg, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.), amino groups, alkylamino groups (eg, methinoreamino group, etc.) Group, ethylamino group, jetylamino group, etc.), acylamine group (eg, acetylylamino group, propionylamino group, etc.), hydroxyl group, cyano group, strong rubamoyl group (eg, methylol group, carbamoyl group, ethylcarbamoyl group, dimethyl group) Carbamoyl group), acyloxy group (for example, acetooxy group, Such pivaloylferutinine / Reokishi group), an alkoxycarbonyl group (e.g.,
- cycloalkyl group examples include saturated cyclic hydrocarbons such as a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group, which may be unsubstituted or substituted. good.
- alkenyl group examples include a bur group, a allyl group, a 1-methyl-2-propenyl group, a 3-butur group, a 2-butul group, a 3_methyl_2-butur group, and an oleyl group.
- it is a bur group or a 1_methyl_2_propenyl group.
- alkynyl group examples include an ethuryl group, a butadyl group, a propargyl group, a 1-methyl_2-propynyl group, a 2-butulyl group, and a 1,1-dimethyl_2-propynyl group. Of these, an ethur group and a propargyl group are preferable.
- X represents one COO—, —CONR—, ten CO—, or one NR C01.
- R represents a hydrogen atom, an alkyl group, or a cycloalkyl group.
- the alkyl group include a methylol group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an amyl group. , Isoamyl group, hexinole group and the like.
- the strong alkyl group further includes a halogen atom and a halogen atom which may have a substituent, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- an acyl group for example, acetyl group, propanoyl group, butyroyl group, etc.
- an alkoxy group for example, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, etc.
- amino group alkylamino group (for example, , Methylamino group, ethylamino group, jetylamino group, etc.)
- an anilino group eg, an anilino group, an N-methylanilino group, etc.
- an isylamino group eg, an acetylylamino group, a propionylamino group, etc.
- a hydroxyl group a cyano group
- Strong rubamoyl group eg methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group
- an acyloleoxy group for example, acetooxy
- cycloalkyl group examples include saturated cyclic hydrocarbons such as a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group, and these may be unsubstituted or substituted. good.
- the polymerizable group in the present invention means an unsaturated ethylene polymerizable group or a bifunctional polycondensable group, preferably an unsaturated ethylene polymerizable group.
- the unsaturated ethylene-based polymerizable group include biel group, allyl group, attalyloyl group, methacryloyl group, styryl group, acrylamide group, methacrylolamide group, vinyl cyanide group, 2-cyanacryloxy group, 1 , 2_epoxy group, butyl ether group, and the like are preferable, and a vinyl group, an attalyloyl group, a methacryloyl group, an acrylamide group, and a methacrylamide group are preferable. Also
- the term “having a polymerizable group as a partial structure” means that the polymerizable group is bonded directly or via a divalent or higher valent linking group.
- the divalent or higher valent linking group include, for example, an alkylene group.
- the weight average molecular weight of the polymer derived from the UV-absorbing monomer is 2000 or more and 300000 or less, preferably S, and more preferably 5000 or more and 20000 or less.
- the weight average molecular weight of the ultraviolet-absorbing copolymer used in the present invention can be adjusted by a known molecular weight adjusting method.
- a molecular weight adjusting method include a method of adding a chain transfer agent such as carbon tetrachloride, lauryl mercabtan, octyl thioglycolate, and the like.
- the polymerization temperature is usually from room temperature to 130 ° C, preferably from 50 ° C to 100 ° C.
- the ultraviolet-absorbing copolymer used in the present invention may be a homopolymer of only an ultraviolet-absorbing monomer or a copolymer with another polymerizable monomer.
- examples of other polymerizable monomers that can be polymerized include, for example, styrene derivatives (for example, styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinylnaphthalene, etc.), acrylic ester derivatives (for example, , Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, i-butyl acrylate, acrylic acid — butyl, octyl acrylate, cyclohexyl acrylate, etc.), methacrylate ester derivatives (for example, methyl methacrylate) , Ethyl acetate, propyl meth
- Copolymerization component power other than UV-absorbing monomer in polymer derived from UV-absorbing monomer may contain at least one hydrophilic ethylenically unsaturated monomer. preferable.
- the hydrophilic ethylenically unsaturated monomer is not particularly limited as long as it is hydrophilic and has an unsaturated double bond polymerizable in the molecule.
- acrylic acid or methacrylic acid etc.
- An unsaturated carboxylic acid, or an acrylic acid or methacrylic acid ester having a hydroxyl group or an ether bond for example, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, tetrahydrofurfuryl methacrylate, 2-acrylic acid 2- Hydroxetyl, 2-hydroxypropyl acrylate, 2,3-dihydroxy _2-methylpyrmethalate, tetrahydrofurfuryl acrylate, 2-ethoxyethyl acrylate, diethylene glycol ethoxylate, 3-methoxybutyl acrylate, etc.
- Atalinoleamide (N-substituted) (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N_bulurpyrrolidone, N_buroxazolidone and the like.
- hydrophilic ethylenically unsaturated monomer examples include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, and (meth) acrylate having a hydroxyl group or a carboxyl group in the molecule. Particularly preferred are acid 2-hydroxyethyl and acrylic acid 2-hydroxypropyl.
- These polymerizable monomers can be copolymerized with an ultraviolet-absorbing monomer in one kind or in combination of two or more kinds.
- the polymerization method of the ultraviolet-absorbing copolymer used in the present invention is not particularly limited, and conventionally known methods can be widely employed, and examples thereof include radical polymerization, anion polymerization, and cationic polymerization.
- radical polymerization initiators include azo compounds and peroxides, such as azobisisobutyronitrile (AIBN), azobisisobutyric acid diester derivatives, benzoyl peroxide, and hydrogen peroxide. Can be mentioned.
- the polymerization solvent is not particularly limited, but examples thereof include aromatic hydrocarbon solvents such as toluene and black benzene, halogenated hydrocarbon solvents such as dichloroethane and black chloroform, ether solvents such as tetrahydrofuran and dioxane, Examples include amide solvents such as dimethylformamide, alcohol solvents such as methanol, ester solvents such as methyl acetate and ethyl acetate, ketone solvents such as acetone, cyclohexanone, and methyl ethyl ketone, and water solvents. .
- solution polymerization that polymerizes in a homogeneous system
- precipitation in which the produced polymer precipitates Polymerization, emulsion polymerization in a micelle state, and suspension polymerization in a suspension state can also be performed. However, it can be obtained by emulsion polymerization.
- the use ratio of the above-mentioned UV-absorbing monomer, polymerizable monomer copolymerizable therewith and hydrophilic ethylenically unsaturated monomer is determined by the compatibility of the resulting UV-absorbing copolymer polymer with other transparent polymers. It is appropriately selected in consideration of the influence on the transparency and mechanical strength of the optical film.
- the content of the ultraviolet absorbing monomer in the polymer derived from the ultraviolet absorbing monomer is preferably 1 to 70 mass%, more preferably 5 to 60 mass%. If the UV monomer content in the UV-absorbing polymer is less than 1% by mass, a large amount of UV-absorbing polymer must be used when trying to satisfy the desired UV-absorbing performance. Transparency decreases due to factors such as film strength. On the other hand, if the UV monomer content in the UV-absorbing polymer exceeds 70% by mass, the compatibility with other polymers decreases, and a transparent optical film cannot be obtained. In addition, the solubility in a solvent is low, and workability and productivity in film production are poor.
- the hydrophilic ethylenically unsaturated monomer is preferably contained in the UV-absorbing copolymer in an amount of 0.:! To 50% by mass. When the amount is less than 1% by mass, the effect of improving the compatibility with the hydrophilic ethylenically unsaturated monomer does not appear, and when it exceeds 50% by mass, it is difficult to isolate and purify the copolymer. A more preferable content of the hydrophilic ethylenically unsaturated monomer is 0.5 to 20% by mass. When the UV-absorbing monomer itself is substituted with a hydrophilic group, the total content of the hydrophilic UV-absorbing monomer and the hydrophilic ethylenically unsaturated monomer is preferably within the above range.
- Two or more kinds of the UV-absorbing monomer and the (non) hydrophilic ethylenically unsaturated monomer may be mixed and copolymerized.
- the ultraviolet absorber, the ultraviolet absorbing monomer and the intermediate thereof used in the present invention can be synthesized with reference to known literature.
- U.S. Pat.Nos. 3,072,585, 3,159,646, 3,399,173, 3,761,272, 4,028,331, 5,683,861 European Patent No. 86,300,416, JP-A-63-227575, 63-185969, Polymer Bulletin. V. 20 (2), 169-176 and Chemical Abstracts V. 109, No. It can be synthesized with reference to 191389.
- the ultraviolet absorbent and ultraviolet absorbent polymer used in the present invention may be used together with a low molecular weight compound, a high molecular weight compound, an inorganic compound or the like, if necessary, when mixed with another transparent polymer. You can also.
- ultraviolet absorbers used in the present invention and others It is also possible to mix the low molecular weight UV absorber with other transparent polymer at the same time, or simultaneously mix the UV light absorbing polymer and other low molecular weight UV absorber used in the present invention with another transparent polymer. This is one of the preferred embodiments.
- additives such as an antioxidant, a plasticizer, and a flame retardant are mixed at the same time.
- the method for adding the ultraviolet absorber and the ultraviolet absorbing polymer used in the present invention to the cellulose acylate film may be contained in the cellulose acylate film or coated on the cellulose acylate film. You can do it. When it is contained in the cellulose acylate film, it may be added directly or in-line. In-line addition is a method of dissolving in an organic solvent (for example, methanol, ethanol, methylene chloride, etc.) in advance and then adding it to the dope composition with an in-line mixer or the like.
- an organic solvent for example, methanol, ethanol, methylene chloride, etc.
- the amount of the ultraviolet absorber and the ultraviolet absorbing polymer used in the present invention is not uniform depending on the type of compound and the usage conditions, but when it is an ultraviolet absorber, cellulose acylate is used. 0.2 to 3 ⁇ Og force per lm 2 S, preferably 0.4 to 2.0, more preferably 0.5 to 1.5, particularly preferably 1.5. In the case of a UV-absorbing polymer, 0.6 to 9. Og force S per lm 2 of cellulose acylate film S, preferably 1.2 to 6.0, more preferably 1.5 to 3.0 Force S especially preferred.
- UV absorber monomer that can be used in the present invention
- 2-benzotriazole) -2-hydroxy-5- (2-methacryloyloxychetyl) benzene or a similar compound thereof manufactured by Otsuka Chemical Co., Ltd.
- a polymer or copolymer obtained by singly or copolymerizing these is also preferably used, but is not limited thereto.
- PUVA-30M manufactured by Otsuka Chemical Co., Ltd. is preferably used as a commercially available polymer ultraviolet absorber. Two or more ultraviolet absorbers may be used.
- the UV absorber is added to the dope after the UV absorber is dissolved in an organic solvent such as alcohol, methylene chloride, dioxolane, or methyl acetate.
- the cellulose acylate film of the present invention may contain an antioxidant.
- an antioxidant for example, as described in JP-A-5-197073, a peroxide decomposer, It may contain a dical chain inhibitor, a metal deactivator, or an acid scavenger.
- the amount of addition of these compounds is preferably lppm to 1.0% by weight with respect to cellulose acylate, 10 to:!
- the fine particle matting agent preferably contains a fine particle matting agent in the cellulose acylate film, for example, silicon dioxide, titanium dioxide, aluminum oxide, dinoleconium oxide, calcium carbonate. It is preferable to contain inorganic fine particles such as kaolin, talc, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, calcium phosphate, and crosslinked polymer fine particles. Of these, silicon dioxide is preferable because it can reduce the haze of the film.
- the average particle size of the secondary particles of the fine particles is in the range of 0.01 to: 1. O x m, and the content is preferably 0.005 to 0.3% by mass with respect to the cellulose acylate.
- fine particles such as silicon dioxide are surface-treated with an organic material, but such a material is preferable because the haze of the film can be reduced.
- Preferred organic substances for the surface treatment include halosilanes, alkoxysilanes (particularly alkoxysilanes having a methyl group), silazane, and siloxane.
- these fine particles are usually present as aggregates, and it is preferable to form irregularities of 0.01 to 1. ⁇ on the surface of the cellulose acylate film.
- the fine particles of silicon dioxide include AEROSIL 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600 manufactured by Aerosil Co., Ltd., preferably AEROSIL 200V, R972, R972V, R974. , R202, R812.
- These matting agents may be used in combination of two or more. When two or more types are used in combination, they can be mixed and used at an arbitrary ratio. In this case, mats with different average particle sizes and materials can be used in a mass ratio of 0.1: 99.9 to 99.9 to 0.1, for example, AEROSIL 200V and R972V.
- a method for preparing a cellulose acylate dope in the present invention will be described.
- a flaky cell opening in a kettle dissolved in an organic solvent mainly composed of a good solvent for cellulosic silicate
- One succinate is dissolved with stirring to form a dope.
- a cooling dissolution method as described in JP-A-9 95544, 9-95557 or 9-95538
- dissolution methods such as a method performed at high pressure as described in JP-A-11-21379.
- the dope is filtered with a filter medium, defoamed, and sent to the next process with a pump.
- the concentration of cellulose acylate in the dope is about 10 to 35% by mass. More preferably, it is 15-25 mass%.
- the polymer X is dissolved in an organic solvent in advance and then added, or directly added to the cellulose acylate dope. Can be done. In this case, the polymer X is added so as not to become cloudy or phase-separated in the dope. The amount of added calories is as described above.
- Organic solvents as good solvents for cellulose acylate include methyl acetate, ethyl acetate, amyl acetate, ethyl formate, acetone, cyclohexanone, methyl acetate, tetrahydrofuran, 1,3-dioxolan, 4-methyl-1,3 —Joxolan, 1,4-Joquisan, 2, 2, 2 Trifnore Roetanore, 2, 2, 3, 3 Hexafnore low 1 Prono.
- the organic solvent used in the dope according to the present invention it is preferable to use a mixture of a good solvent and a poor solvent of cellulose sylate. The range is 70-98% by mass for good solvents and 2-30% by mass for poor solvents.
- the good solvent and the poor solvent used in the present invention are defined as those that dissolve the cellulose acylate used alone as good solvents and those that do not dissolve alone as poor solvents.
- the poor solvent used in the dope according to the present invention is particularly limited.
- the organic solvent is preferably selected using a good solvent for cellulose acylate.
- a low molecular weight plasticizer when used, it can be carried out by a usual addition method, either directly added into the dope, or dissolved in an organic solvent in advance and poured into the dope. Good.
- the cellulose acylate dope and various additives are made into a solution in which a small amount of cellulose acylate is dissolved. It can also be added in-line and mixed, which is preferable.
- an in-line mixer such as a static mixer SWJ (Toray static type in-pipe mixer Hi-Mixer) (manufactured by Toray Engineering).
- SWJ Toray static type in-pipe mixer Hi-Mixer
- the cellulose acylate dope must be filtered to remove foreign matter, particularly foreign matter that would be recognized as an image in a liquid crystal display device.
- the quality of the polarizer protective film is determined by this filtration.
- Filter media used for filtration should have a low absolute filtration accuracy, but if the absolute filtration accuracy is too low, the filter media may become clogged and the filter media must be replaced frequently, reducing productivity. There is a problem of letting. Therefore, the cellulose acylate-doped filter medium of the present invention preferably has an absolute filtration accuracy of 0.008 mm or less, more preferably in the range of 0.001 to 0.008 mm, and 0.003 to 0.000. A filter medium in the range of 006 mm is more preferable. There are no particular restrictions on the material of the filter medium, but ordinary filter media can be used, but plastic fibers such as polypropylene and Teflon (registered trademark) can be used.
- Filtration of the cellulose acylate dope of the present invention is a force that can be performed by a normal method.
- the method of filtering while heating under pressure at a temperature that is equal to or higher than the boiling point of the solvent at normal pressure and does not boil is a filtration method.
- the rise in pressure difference between the front and back (hereinafter sometimes referred to as filtration pressure) is small.
- the filtration pressure is preferably 1.6 ⁇ 10 6 Pa or less, more preferably 2 ⁇ 10 6 Pa or less, and even more preferably OX 10 6 Pa or less. If the cellulose of the raw material contains an unsubstituted acyl group or cellulose acylate having a low degree of acetylation, a foreign matter failure (hereinafter sometimes referred to as a bright spot) may occur. A bright spot is placed between two polarizing plates in a crossed state (crossed Nicols), a single cell succinate film is placed, light is irradiated from one side, and an optical microscope (from the opposite side)
- the diameter of the bright spot means a diameter measured by approximating the bright spot to a perfect circle.
- a process of casting the cellulose acylate dope on the metal support, a drying process on the metal support, and a peeling process of peeling the web from the metal support will be described.
- the metal support is an endless metal belt or a rotating metal drum that moves indefinitely, and its surface is a mirror surface.
- the casting step is a step of feeding the dope as described above to a pressure die through a pressure type quantitative gear pump, and casting the dope from the pressure die onto the metal support at the casting position.
- Other casting methods include a doctor blade method in which the film thickness of the cast dope film is adjusted with a blade, or a reverse roll coater in which the film is adjusted with a reverse rotating roll.
- a pressure die that can adjust the thickness and make the film thickness uniform.
- the pressure die includes a coat hanger die and a T die, and any of them is preferably used.
- two or more pressure dies may be provided on the metal support, and the dope amount may be divided and stacked.
- the drying step on the metal support is a step of heating the web on the support and evaporating the solvent.
- To evaporate the solvent there are a method in which heated air is blown from the web side and the back side of the support, a method in which heat is transferred from the back side of the support by a heated liquid, and a method in which heat is transferred from the front and back by radiant heat. A method of combining them is also preferable. Also, if the web is thin, it dries quickly.
- the temperature of the metal support may be the same or different depending on the position.
- the drying method on the metal support suitable for the present invention is, for example, preferably cast at a metal support temperature of 0 to 40 ° C, preferably 5 to 30 ° C.
- the drying wind applied to the web is preferably about 30 to 45 ° C, but is not limited thereto.
- the peeling step is a step of evaporating the organic solvent on the metal support and peeling the web before the metal support goes around, and then the web is sent to the drying step.
- the position at which the web is peeled from the metal support is called the peeling point, and the roll that assists the peeling is called the peeling roll. Force due to web thickness If the amount of residual solvent of the web at the peeling point (the following formula) is too large, it will be difficult to peel off, or conversely, if it is peeled off after sufficiently drying on the support, Part of the web may come off. Usually, the web is peeled at a residual solvent amount of 20 to 180% by mass.
- the amount of the residual solvent to be peeled is preferably 20 to 40% by mass or 60 to 150% by mass, particularly preferably 80 to 140% by mass.
- a gel casting method gel casting
- the method there are a method in which a poor solvent for cellulose acylate is removed in the dope and the gel is formed after casting the dope, and a method in which the temperature of the support is lowered to make the gel.
- a metal salt in the dope.
- the amount of residual solvent used in the present invention can be expressed by the following formula.
- Residual solvent amount (mass%) ⁇ (M— N) / N ⁇ X 100
- M is the mass of the web at any point
- N is the mass when M is dried at 110 ° C for 3 hours.
- the film peeled off from the support is further dried so that the residual solvent amount is 2.0% by mass or less, more preferably 1 0% by mass, more preferably 0.5% by mass or less.
- the roll is dried while the web is transported by a roll drier in which the rolls are arranged in a staggered manner, a tenter drier that holds the width of the web with a clip, and holds the width or stretches slightly in the width direction.
- the method is adopted.
- it is particularly preferable in order to improve the humidity stability of the optical performance by holding or stretching in an arbitrary process after peeling from the support of the tenter drying apparatus and in an arbitrary residual solvent amount.
- Masle The means for drying the web is not particularly limited, and is generally carried out with hot air, infrared rays, a heating roll, microwaves, or the like. It is preferable to carry out with hot air in terms of simplicity. It is preferable to increase the drying temperature stepwise in the range of 40 to 180 ° C. More preferably, the drying temperature is in the range of 50 to 160 ° C.
- the polarizer protective film of the present invention preferably has a thickness direction retardation at 23 ° C. and 55% RH of Rth force S of 40 nm or more and 250 nm or less, more preferably 60 nm or more and 250 nm or less. Masle. Most preferably, it is lOOnm or more and 250nm or less.
- phase difference Ro defined by the following formula in the in-plane direction of the polarizer protective film according to the present invention is preferably Onm or more and lOnm or less, and is preferably in the range of 50 nm or more and lOOnm or less. More preferred.
- nx is the maximum refractive index in the film plane
- ny is the refractive index in the axial direction perpendicular to the film plane
- nz is the refractive index in the film thickness direction
- d (nm) is the film thickness.
- Ro and Rth measurements were compared using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments) For example, it can be measured at a wavelength of 590 nm.
- the refractive index of the polarizer protective film of the present invention can be controlled by a stretching operation.
- the refractive index is controlled within a preferable range by stretching 1.0 to 2.0 times in one direction of the optical film and 1.01 to 2.5 times in the direction perpendicular to the film plane. You can.
- the film can be stretched sequentially or simultaneously in the longitudinal direction of the film and the direction orthogonal to the longitudinal direction of the film, that is, the width direction. At this time, if the stretching ratio in at least one direction is too small, a sufficient phase difference cannot be obtained, and if it is too large, stretching becomes difficult and breakage may occur.
- the film when the film is stretched in the casting direction (longitudinal direction), if the contraction in the width direction is too large, the refractive index in the thickness direction of the film becomes too large. In this case, it can be improved by suppressing the width shrinkage of the film or stretching in the width direction.
- stretching in the width direction there may be a distribution of refractive index in the width direction. This is a phenomenon that occurs when the film is stretched in the width direction, the force S that can be seen when using the tenter method, and a contraction force is generated in the center of the film, and the end is fixed. It is thought to be a so-called Boeing phenomenon. Even in this case, by stretching in the longitudinal direction, the bowing phenomenon can be suppressed and the distribution of the width retardation can be improved.
- the film thickness fluctuation of the obtained film can be reduced. If the film thickness variation of the optical film is too large, the retardation will become uneven, and unevenness such as coloring may become a problem when used in a liquid crystal display.
- the film thickness variation of the polarizer protective film is preferably in the range of ⁇ 3%, and more preferably ⁇ 1%.
- a method of stretching in the biaxial directions perpendicular to each other is effective, and the stretching ratio in the biaxial directions perpendicular to each other is finally 1.0 to 2.0 in the casting direction (longitudinal direction). 2. It is preferable that the range is 1.0 times and 1.0 to 1-2 times in the width direction.
- the slow axis of the polarizer protective film can be provided in the width direction by stretching in the width direction. .
- the slow axis of the polarizer protective film in the width direction (stretch ratio in the width direction)> (in the casting direction). It is preferable to satisfy the draw ratio).
- the film of the present invention can also be applied to a so-called negative C pre-film. In that case, it is preferable that the draw ratio in the width direction and the draw ratio in the casting direction are as small as possible from the viewpoint of suppressing the in-plane retardation.
- the method of stretching the web is not particularly limited.
- a circumferential speed difference is applied to a plurality of rolls, and the roll circumferential speed difference is used to stretch the roll in the casting direction.
- Examples include a method of extending in the traveling direction and extending in the casting direction, a method of extending in the horizontal direction and extending in the width direction, or a method of extending in the vertical and horizontal directions and extending in both the vertical and horizontal directions. Of course, these methods may be used in combination.
- tenter method if the clip part is driven by the linear drive system, it is possible to perform a smooth force and stretch, and the risk of breakage and the like can be reduced.
- the width maintenance or stretching in the width direction in the film forming process is performed by a tenter, which may be a pin tenter or a clip tenter.
- the thickness of the polarizer protective film of the present invention is preferably 10 to 500 / im. In particular, 20 ⁇ or more is preferred, and 35 ⁇ or more is preferred. Also, 150 / im or less, and 120 ⁇ m or less are preferred. Particularly preferred is 35 to 90 / m. If the polarizer protective film is thicker than the above range, the polarizing plate after polarizing plate processing becomes too thick. On the other hand, if the thickness is smaller than the above range, the development of retardation becomes difficult, and the moisture permeability of the film becomes high, so that the ability to protect the polarizer from humidity decreases.
- ⁇ 1 is 1 ° or more + 1 °
- the angle is preferably 1 ° or less, more preferably 0.5 ° or more and + 0.5 ° or less.
- This ⁇ 1 can be defined as the orientation angle, and ⁇ 1 can be measured using an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments).
- the width of the polarizer protective film is 1.3 m or more, preferably in the range of 1.4 m to 2.8 m. From the viewpoint of productivity, it is preferable for a large-sized liquid crystal display device.
- an antistatic layer before and / or after stretching, an antistatic layer, a hard coat layer, an antireflection layer, a slippery layer, an easy adhesion layer, an antiglare layer, a barrier layer, and an optical compensation layer.
- a functional layer such as In particular, it is preferable to provide at least one layer selected from an antistatic layer, a hard coat layer, an antireflection layer, an easy adhesion layer, an antiglare layer, and an optical compensation layer.
- various surface treatments such as corona discharge treatment, plasma treatment, and chemical treatment can be performed as necessary.
- the polarizer protective film of the present invention preferably has an antistatic layer 2 and an adhesive layer 3 laminated in this order on one side of the polarizer protective film 1.
- the antistatic layer 2 of the polarizer protective film of the present invention is preferably a layer containing a cationic polymer having an antistatic function or a layer using a metal oxide as an antistatic agent.
- Cationic polymers preferably used in the present invention include JP-B 53-13223, JP 57-1 5376, JP-B 53-45231, JP 55-145783, JP 55-65950, and 55-6. 7746, 57-11342, 57-19735, JP-B 58-56858, JP-A-61 27853, 62-9346 have a cationic dissociation group in the side chain.
- Particularly preferred cationic polymers include polymers having units of the following general formulas [3], [la] and [lb].
- Rt hydrogen atom, alkyl group having 1 to 4 carbon atoms, cough
- M a hydrogen atom, a cation (for example, an alkali anion,
- R, R, R and R represent a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms
- R or R and R may combine to form a nitrogen-containing heterocycle such as piperazine.
- D are each a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, an arylene group, an alkenylene group, an arylene alkylene group, one R COR-, one R COOR OCOR-
- R 1, R 2, R 3, R 4 and R 5 are each a substituted or unsubstituted alkylene group, alkenile.
- A is an alkylene group, a hydroxyalkylene group or an arylenealkylene group
- B is not an alkylene group, a hydroxylalkylene group or an arylenealkylene group.
- E represents a group selected from a simple bond, -NHCOR CONH-, or D force.
- R is
- 26 26 represents a substituted or unsubstituted alkylene group, alkenylene group, arylene group, arylene alkylene group, or alkylene arylene group.
- n represents an integer of 5 to 300.
- quaternary ammonium cation polymer having a molecular bridge and a quaternary ammonium cation polymer having a molecular bridge and not containing a particularly preferred chloride ion is particularly preferably used.
- the cationic polymer used in the present invention may be used alone or in combination with several kinds of cationic polymers.
- the content of the cationic polymer in the antistatic layer is from 10 to 80% by mass, preferably from 20 to 70% by mass, based on the solid content of the layer.
- Examples of the metal oxide as the antistatic agent include tin oxide, antimony oxide, indium oxide, and zinc oxide. Of these, tin oxide is preferable.
- Examples of tin oxide-based antistatic agents include, in addition to tin oxide, antimony-doped tin oxide, indium-doped tin oxide, aluminum-doped tin oxide, tungsten-doped tin oxide, titanium oxide cerium monoxide complex, oxidation For example, a composite of titanium tin monoxide.
- Metal oxide is usually fine particles, and the shape is particulate or needle-like. Are preferably used. The average particle size of the fine particles is 1 to about OOnm, preferably 2 to 50 nm.
- the metal oxide is dispersed in a hydrophilic solvent (zonole).
- a hydrophilic solvent zonole
- water is preferable as the hydrophilic solvent.
- hydrophilic organic solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol,
- n-amino alcohol isoamino alcohol, sec-amino alcohol, tert-amyl alcohol, 1_ethyl_1-propanol, 2_methyl_1-butanol, n_hexanol, cyclo Examples include alcohols such as hexanol.
- a binder component is used for the purpose of improving the film forming property of the antistatic layer and the adhesion to the film. It can also be added.
- a metal oxide is used as a dispersion
- a water-soluble or water-dispersible binder component is used.
- binders include polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, epoxy resins, polybutylpyrrolidone, polystyrene resins, polyethylene glycol, pentaerythritol. And cellulose acylate.
- binders are especially preferred.
- the amount of binder used is usually 200 parts by mass or less, preferably 5 to 150 parts by mass, based on 100 parts by mass of the metal oxide, although it depends on the type of metal oxide. Part.
- the surface resistance value of the antistatic layer is preferably IX 10 12 ⁇ or less and more preferably 1 X 10 U QZ or less. If the surface resistance exceeds 1 X 10 12 ⁇ / mouth, static electricity is generated and charged due to peeling of the surface protection film with insufficient antistatic function or friction of the polarizer protective film, and the circuit of the liquid crystal cell May cause damage to the LCD or poor alignment of the liquid crystal.
- the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer is a pressure-sensitive adhesive having a storage elastic modulus at 25 ° C of at least a part of the pressure-sensitive adhesive layer of 1.0 X 10 4 Pa to: 1.0 X 10 9 Pa Is preferably used.
- the type is not particularly limited, but a curable pressure-sensitive adhesive that forms a polymer or a crosslinked structure by various chemical reactions after applying and bonding the pressure-sensitive adhesive is preferably used.
- urethane pressure-sensitive adhesives examples include urethane pressure-sensitive adhesives, epoxy pressure-sensitive adhesives, aqueous polymer-isocyanate pressure-sensitive adhesives, curable pressure-sensitive adhesives such as thermosetting acrylic pressure-sensitive adhesives, moisture-cured urethane pressure-sensitive adhesives, and polyester monomethacrylate.
- curable pressure-sensitive adhesives such as thermosetting acrylic pressure-sensitive adhesives, moisture-cured urethane pressure-sensitive adhesives, and polyester monomethacrylate.
- anaerobic adhesives such as molds, ester-based methacrylates, and oxidized polyether methacrylates, cyanoacrylate-based instant adhesives, and two-component instant adhesives of talate and peroxide. It is also possible to mix an antistatic agent in the adhesive using known methods.
- the method for forming the antistatic layer and the pressure-sensitive adhesive layer is not particularly limited, and is a general method, for example, a gravure coater, a micro gravure coater, a comma coater, a bar coater, a spray coating, an ink jet method or the like. Is mentioned.
- the pressure-sensitive adhesive layer molding composition was formed on a polyethylene terephthalate film support.
- the pressure-sensitive adhesive layer was peeled off by a dynamic viscoelasticity measuring device (“A RES” manufactured by Rheometric Co., Ltd.) in a temperature rising mode (temperature rising rate 5 ° C / min, frequency 10 Hz). Measure the storage modulus at ° C.
- the polarizing plate of the present invention will be described.
- the polarizing plate can be produced by a general method.
- the back side of the polarizer protective film of the present invention is subjected to an alkali hatching treatment.
- the polarizer protective film that has been subjected to the hatching treatment is bonded to at least one surface of a polarizer prepared by immersing and stretching a polybulal alcohol film in an iodine solution using a completely hatched polybulal alcohol aqueous solution. Is preferred Les.
- the polarizer protective film may be used on the other surface, or another polarizer protective film may be used.
- the polarizer protective film used on the other surface is a cellulose resin having an in-plane retardation Ro of 590 nm, 0 to 10 nm, and Rth of 30 to 30 nm. It is preferable to use a rate film.
- KC8UX, KC4UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR 5, KC8UY, KC4UY, KC10UDR, KC8UY—HA, KC8UX— RHA (manufactured by Kominiki Minoltaput Co., Ltd.) and the like are preferably used.
- the polarizer protective film of the present invention is industrially produced as a long film, and an embodiment in which a polarizing plate is constituted by bonding with a polarizer produced as a long film is most useful. Further, it can be used as a mere retardation film that does not have a function as a polarizer protective film, such as further bonding to a polarizing plate.
- a polarizer which is a main component of a polarizing plate, is an element that passes only light with a plane of polarization in a certain direction, and a typical polarizer known at present is a polybulu alcohol-based polarizing finale. However, this is not limited to this, although there are ones in which polybutyl alcohol film is dyed with iodine and ones in which dichroic dye is dyed.
- the polarizer a polyvinyl alcohol aqueous solution is formed into a film and dyed by uniaxial stretching or dyed or uniaxially stretched and then preferably subjected to a durability treatment with a boron compound.
- a polarizer having a thickness of 5 to 30 / im is preferably used.
- the polarizing plate can be constructed by further bonding a protective film on one side and a separate film on the other side.
- the protective film and the separate film are used for the purpose of protecting the polarizing plate when the polarizing plate is shipped, product inspection, etc.
- the non-protein film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal cell.
- a separate film is used for the purpose of covering the adhesive layer bonded to a liquid crystal cell, and is used for the surface side which bonds a polarizing plate to a liquid crystal cell.
- Mounting the polarizing plate to the liquid crystal display device can produce various liquid crystal display devices with excellent visibility by bonding the polarizer protective film surface according to the present invention to the liquid crystal cell side.
- the liquid crystal cell is preferably bonded using an acrylic pressure-sensitive adhesive.
- the polarizer protective film of the present invention is a reflection type, transmission type, transflective type LCD or TN type, ST N type, OCB type, HAN type, VA type (PVA type, MVA type: vertical alignment method), IPS It is preferably used in LCDs of various drive systems such as molds. In particular, it is preferably used for a vertical alignment type liquid crystal display device.
- the large vertical screen LCD device with a 30-inch or larger screen has the effect that the eyes are not tired even when viewing for a long time with little color unevenness and wavy unevenness.
- polymers X having different molecular weights were prepared by changing the addition amount of the chain transfer agent mercaptopropionic acid and the addition rate of azobisisobutyronitrile.
- the weight average molecular weight of the polymer X is shown in Tables 1 and 2 by the following measurement method.
- the weight average molecular weight was measured using high performance liquid chromatography.
- the filtered precipitate was dissolved in 500 ml of 1 mol / L NaOH aqueous solution, and 35 g of zinc powder 40% NaOH aqueous solution lOg was added dropwise. After dropping, the mixture was stirred for about 2 hours, filtered, washed with water, and neutralized with hydrochloric acid to neutralize the filtrate. The precipitated precipitate is filtered, washed with water, dried, and then recrystallized with a mixed solvent of ethyl acetate and acetone to obtain 2 (2 '—hydroxy-5' _t-butyl-phenyl) _ 5 _carboxylic acid-2H-benzotriazole. Obtained
- reaction solution is poured into water, and the precipitated crystals are filtered, washed with water, dried, and recrystallized with ethyl acetate to give the exemplified compound MUV —19 2 (2 ′ —hydroxy-1 5 ′ _t_butyl monophenyl).
- _5_carboxylic acid_ (2-methacryloyloxy) ethyl ester 1 2H-benzotriazole was obtained.
- the deposited precipitate was collected by filtration and vacuum-dried at 40 ° C to obtain 9.lg of a polymer UV agent P_l which was a grayish white powdery polymer.
- This copolymer was confirmed to have a number average molecular weight of 4500 by GPC analysis based on standard polystyrene. Further, from the NMR spectrum and UV spectrum, the above copolymer was found to be 2 (2′-hydroxy-5 ′ _t_butyl-phenol) 1-5 carboxylic acid mono (2-methacryloyloxy) ethyl ester 1 2H-benzotri It was confirmed to be a copolymer of azole and methyl methacrylate.
- Cell mouth succinate (cell mouth acetoacetate propionate (indicated as CAP in Table 1 and Table 2), vacuum dried at 60 ° C for 24 hours. Degree of substitution of acetyl group 1.5, degree of substitution of propionyl group 0.95, total acyl substitution degree 2.45)
- the above dope solution was prepared with Finemet NF manufactured by Nippon Seisen Co., Ltd., filtered at the next stage, and uniformly cast on a stainless steel band support at a temperature of 22 ° C and a width of 2 m using a belt casting apparatus. .
- the stainless steel band support was used to evaporate the solvent until the residual solvent amount reached 100%, and was peeled off from the stainless band support with a peeling tension of 162 N / m.
- the exfoliated cellulose acylate web was evaporated at 35 ° C, slitted to a width of 1.6m, and then stretched 1.1 times in the width direction with a tenter, while being dried at 135 ° C. And dried.
- the residual solvent amount when starting stretching with a tenter was 10%. After stretching with a tenter, relax at 130 ° C for 5 minutes, and then finish drying while conveying the drying zone at 120 ° C and 130 ° C with many rolls. A 10 mm width and 5 zm knurling process was applied to the core, and it was wound on a 6-inch inner diameter core with an initial tension of 220 N / m and a final tension of lONZm to obtain a cellulose acylate film 1. The draw ratio in the MD direction calculated from the rotational speed of the stainless steel band support and the operating speed of the tenter was 1.01 times. The residual solvent amounts of the cellulose acylate films listed in Tables 1 and 2 were 0.1%, the film thickness f was 60 ⁇ m, and the minor number f was 4000 m.
- cellulose acylate type, type of polymer X, addition amount, type of additive, addition Cellulose acylate films 2 to 30 were produced in the same manner as cellulose acylate film 1 except that the addition amount was changed as shown in Tables 1 and 2.
- a cellulose acylate film 31 was produced in the same manner as the cellulose acylate film 9 except that the solvent was evaporated so that the residual solvent amount when starting stretching with a tenter was 2%.
- CAP is cellulose acetate propionate
- DAC is diacetyl cellulose (L_50, manufactured by Daicel Chemical Industries)
- TAC is cellulose triacetate (cellulose triacetate synthesized from linter cotton, acetyl group) Degree of substitution 2.87).
- the retardation control agent 1 used the following compounds.
- Rth ⁇ (nx + ny) / 2-nz ⁇ X d
- the maximum refractive index in the plane of the film is nx, and the axial direction is perpendicular to the plane.
- TPP triphenyl phosphate
- EPEG ethyl phthalyl ethyl glycolate
- TPP Triphenyl phosphate
- EPEG Ethylphthalyl ethyl glycolate
- a 120 ⁇ m-thick polyvinyl alcohol film was immersed in 100 kg of an aqueous solution containing 1 kg of iodine and 4 kg of boric acid, and stretched 6 times at 50 ° C. to produce a polarizer.
- Cell mouth succinate films 1-31 which had been subjected to alkali saponification treatment on one side of the polarizer, were bonded to each other using a fully saponified polyvinyl alcohol 5% aqueous solution as an adhesive.
- Konica Minolta-Tac KC8UX (manufactured by Konica Minoltaput Co., Ltd.) was bonded to the other surface of the polarizer.
- the film sample was saponified, washed with water, neutralized and washed with water under the above conditions, and then dried at 80 ° C.
- the liquid crystal panel was manufactured in the same manner as described above, and it was examined whether or not the image could be seen from obliquely above.
- composition B as a polarizing plate on the viewing side, a polarizing plate produced using Konica Minolta-Tak KC 8UX (manufactured by Konica Minoltatop Co., Ltd.) was bonded to both sides of the polarizer, and the backlight side The produced polarizing plates 13 and 16 were bonded to a liquid crystal cell. At that time, the cellulose acylate films 13 and 16 produced above were bonded so as to be on the liquid crystal cell side.
- Configuration A The evaluation criteria for Composition B are shown below.
- the polarizing plate previously bonded to the liquid crystal display L17F4F1 manufactured by NEC Mitsubishi Electric Visual Systems Co., Ltd. was peeled off, and the above-prepared present invention and the comparative polarizing plate were bonded to a liquid crystal cell.
- the direction of bonding of the polarizing plate is the cellulose ester film surface force according to the present invention, the glass surface side of the liquid crystal cell, and the absorption axis is oriented in the same direction as the previously bonded polarizing plate.
- a liquid crystal panel was manufactured in the same manner as described above, and it was examined whether the image could be confirmed when viewed from the side.
- the evaluation criteria for Composition C are shown below.
- the cellulose acylate film was hatched and bonded to a polyvinyl alcohol polarizer, and it was confirmed whether it could be peeled by hand after being bonded and dried.
- the prepared liquid crystal display device was stored at 60 ° C and 90% RH for 1000 hours, and then the liquid crystal display device was turned on, and after 6 hours, the presence or absence of light leakage in black display was confirmed. [0198] A: No light leaks are observed
- Cellulose acylate film 1 to 13 of the composition of the present invention 13 / Polarizing plate 1 to 13 are generally excellent in viewing angle, polarizing plate processing, corner unevenness, and crowding unevenness. It is clear that is there.
- the cellulose acylate film 13 / polarizing plate 13 having a high Rth value has excellent viewing angle characteristics even when the configuration of the polarizing plate in the liquid crystal display device is B.
- the separate film of the adhesive layer is peeled off, and the polarizing plate is charged instead of the pre-bonded polarizing plate of Sony 30-inch LCD TV KDL-32S1000, which is a vertical alignment type liquid crystal display device.
- the surface on which the prevention layer and the pressure-sensitive adhesive layer were formed was bonded to a liquid crystal cell.
- the polarizing plate of the present invention has an excellent antistatic effect, so that there is no dust failure during bonding, cracking or chipping during punching, and there is no disorder in the alignment of the liquid crystal panel. Productivity during manufacturing has been improved.
- Illustrative compound IP- 24 0.5 parts by weight 5% acetone solution of cellulose diacetate 10 parts by weight Methyl ethyl ketone 35 parts by weight
- the above coating composition was applied to one side of the cellulose acylate film prepared above by using a die coater with a dry film thickness of 0.2 ⁇ m, and 100 ° C. And dried for 24 seconds to form a layer.
- the surface specific resistance value force of the sample after coating at 23 ° C and 55% RH was in the range of 2 X 10 8 ⁇ to 2 X 10 9 ⁇ , and had good antistatic performance.
- butyl acrylate acrylic acid: 2-hydroxyethyl acrylate: 100: 5: 0.1 (mass ratio) copolymer containing talinole polymer with a weight average molecular weight of 1.8 million A solution (24% solids) was used.
- Coronate L made by Nippon Polyurethane Co., Ltd., an isocyanate-based polyfunctional compound, is added to the above acrylic polymer solution to 2.5 parts with respect to 100 parts of polymer solids, and 0.6 parts of additive (KBM_403, manufactured by Shin-Etsu Silicone Co., Ltd.). Then, a solvent for adjusting viscosity (ethyl acetate) was added to prepare an adhesive solution (solid content 11%).
- the adhesive solution was applied on the antistatic layer by the reverse roll coating method so that the thickness after drying was 25 zm, and then a separate film (polyethylene terephthalate substrate: Diafoil MRF38, Mitsubishi) Chemical polyester) was applied and dried in a hot air circulation oven to form an adhesive layer.
- the storage elastic modulus of the pressure-sensitive adhesive layer at 25 ° C was 4.4 X 10 6 Pa.
- the pressure-sensitive adhesive layer molding composition was formed on a polyethylene terephthalate film support.
- the pressure-sensitive adhesive layer was peeled off by a dynamic viscoelasticity measuring device (“A RES” manufactured by Rheometric Co., Ltd.) in a temperature rising mode (temperature rising rate 5 ° C / min, frequency 10 Hz). Measure the storage modulus at ° C.
- a polarizer protective film that has excellent viewing angle characteristics as a retardation film and reduces light leakage during black display such as corner unevenness and white brown, a polarizing plate and a vertical alignment method using the same A liquid crystal display device can be provided.
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Abstract
Description
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- 2007-02-27 KR KR1020087021766A patent/KR101286893B1/ko active IP Right Grant
- 2007-02-27 CN CNA2007800078625A patent/CN101395507A/zh active Pending
- 2007-03-05 US US11/681,919 patent/US8416369B2/en active Active
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JP2010046834A (ja) * | 2008-08-19 | 2010-03-04 | Fujifilm Corp | セルロースアシレート積層フィルムおよび偏光板 |
JP5234113B2 (ja) * | 2008-09-20 | 2013-07-10 | コニカミノルタアドバンストレイヤー株式会社 | 位相差フィルム、偏光板、液晶表示装置 |
JP2010102309A (ja) * | 2008-09-26 | 2010-05-06 | Daicel-Cytec Co Ltd | 偏光板及びその製造方法 |
US9151870B2 (en) | 2010-12-08 | 2015-10-06 | Konica Minolta, Inc. | Optical film, and polarizing plate and liquid crystal display device using same |
JP2018521939A (ja) * | 2015-05-19 | 2018-08-09 | エシロール アンテルナシオナル (コンパニー ジェネラル ドプティック) | タングステンがドープされた酸化第二スズコロイド懸濁液及びその調製方法 |
Also Published As
Publication number | Publication date |
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TWI434856B (zh) | 2014-04-21 |
KR101286893B1 (ko) | 2013-07-16 |
TW200745168A (en) | 2007-12-16 |
JP5223669B2 (ja) | 2013-06-26 |
JP5252103B2 (ja) | 2013-07-31 |
CN101395507A (zh) | 2009-03-25 |
US20070222920A1 (en) | 2007-09-27 |
US8416369B2 (en) | 2013-04-09 |
JPWO2007102340A1 (ja) | 2009-07-23 |
JP2012177925A (ja) | 2012-09-13 |
KR20080106422A (ko) | 2008-12-05 |
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