WO2009096070A1 - アクリル樹脂含有フィルム、それを用いた偏光板及び液晶表示装置 - Google Patents
アクリル樹脂含有フィルム、それを用いた偏光板及び液晶表示装置 Download PDFInfo
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- WO2009096070A1 WO2009096070A1 PCT/JP2008/068639 JP2008068639W WO2009096070A1 WO 2009096070 A1 WO2009096070 A1 WO 2009096070A1 JP 2008068639 W JP2008068639 W JP 2008068639W WO 2009096070 A1 WO2009096070 A1 WO 2009096070A1
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- acrylic resin
- resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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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
-
- 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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/14—Mixed esters
-
- 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
- C08J2333/00—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
- C08J2333/04—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 esters
- C08J2333/06—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 esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/10—Esters of organic acids, i.e. acylates
- C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- G02F1/133528—Polarisers
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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
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/50—Protective arrangements
- G02F2201/503—Arrangements improving the resistance to shock
Definitions
- the present invention relates to an acrylic resin-containing film, a polarizing plate using the same, and a liquid crystal display device, and more specifically, by using an acrylic resin-containing film obtained by blending an acrylic resin and a cellulose ester resin,
- the present invention relates to a liquid crystal display device that improves the yield in work such as time and maintains good visibility even in long-term use.
- PMMA Polymethyl methacrylate
- the PMMA film has poor heat resistance and has a problem that its shape changes when used at high temperatures or for long-term use.
- This problem was an important issue not only as a physical property of a single film but also in a polarizing plate and a display device using such a film. That is, in the liquid crystal display device, because the polarizing plate curls with the deformation of the film, the entire panel is warped, and the design phase difference changes even when used at the position on the viewing side surface. There was a problem that the viewing angle fluctuated and the color changed.
- PC polycarbonate
- Patent Documents 3 and 4 There are disclosed a method of introducing an alicyclic alkyl group as a copolymerization component of an acrylic resin, a method of forming a cyclic structure in a molecular main chain by an intramolecular cyclization reaction.
- the present invention has been made in view of the above problems, and an object thereof is to provide an acrylic resin-containing film that is transparent, has high heat resistance, and has markedly improved brittleness.
- a liquid crystal display device is provided.
- acrylic resin-containing film comprising at least one resin selected from resins (D), wherein the acrylic resin-containing film has a haze of less than 2% and a tensile softening point of 120 to 150 ° C., and does not cause ductile fracture
- acrylic resin-containing film characterized by that.
- the acrylic resin-containing film is 30 to 90% by mass of the acrylic resin (A), 5 to 65% by mass of the cellulose ester resin (B), and has a glass transition temperature Tg of 120 ° C. other than (A) and (B). 2.
- the acrylic resin (A) has a weight average molecular weight (Mw) of 80000 to 1000000, and the total substitution degree (T) of at least one acyl group of the cellulose ester resin (B) is 2.00 to 2.99.
- the acetyl group substitution degree (ac) is 0.10 to 1.89, and the portion other than the acetyl group is substituted with an acyl group having 3 to 7 carbon atoms, and the substitution degree (r 2.
- the acrylic resin-containing film as described in 1 above which has a weight average molecular weight (Mw) of 75,000 to 250,000.
- a polarizing plate comprising the acrylic resin-containing film according to any one of 1 to 4 on at least one surface.
- the present invention improves the yield in operations such as punching of a polarizing plate and panel bonding, and even in use in harsh environments. It was possible to provide a liquid crystal display device that can maintain good visibility over the long term.
- the acrylic resin film of the present invention is one type of acrylic resin (A) and one of the cellulose ester resin (B), and other than (A), (B) and (A), (B), and has a glass transition temperature Tg.
- Tg glass transition temperature
- An acrylic resin-containing film characterized by not causing it.
- the acrylic resin-containing film of the present invention contains one kind each of acrylic resin (A) and cellulose ester resin (B), and further acrylic resin (A), cellulose ester (B) and (A), (B). And a third resin selected from resins (D) having a Tg of 120 ° C. or more and 300 ° C. or less.
- the acrylic resin-containing film of the present invention has an acrylic resin (A) of 30 to 90 mass%, a cellulose ester resin (B) of 5 to 65 mass%, and glass transition temperature Tg other than (A) and (B). It is preferable to contain 0 to 65% by mass of the resin (D) having a temperature of 120 ° C. or higher and 300 ° C. or lower.
- the acrylic resin (A) is preferably 50% by mass or more.
- the acrylic resin component is increased, dimensional changes at higher temperatures and higher humidity are suppressed, curling of the polarizing plate and warping of the panel when used as a polarizing plate can be significantly reduced, and the above properties are maintained for a long time. It becomes possible to do.
- the ductile fracture is caused by a stress that is greater than the strength of a certain material, and is defined as a fracture accompanied by significant elongation or squeezing of the material before the final fracture.
- the fracture surface is characterized by numerous indentations called dimples.
- an acrylic resin-containing film that does not cause ductile fracture means that no fracture such as fracture is observed even when a large stress is applied such that the film is bent in two at 23 ° C. and 55% RH. It is a feature.
- the demand for the brittleness of optical films is increasing from the viewpoint of reworkability and productivity as optical films become larger and thinner with the recent increase in liquid crystal display devices, and the above ductile fracture does not occur. Is required.
- An acrylic resin-containing film that does not cause ductile fracture can be selected by performing the ductile fracture test described later with the material composition of the acrylic resin, cellulose ester, and other additives used according to the present invention.
- the acrylic resin-containing film according to the present invention has a low haze, a high temperature device such as a projector, and a use in a high temperature environment such as an in-vehicle display device.
- the temperature is preferably 120 to 145 ° C, and more preferably 125 to 140 ° C.
- the number of defects within a film surface of 5 ⁇ m or more is 1/10 cm square or less. More preferably, it is 0.5 piece / 10 cm square or less, more preferably 0.1 piece / 10 cm square or less.
- the diameter of the defect indicates the diameter when the defect is circular, and when it is not circular, the range of the defect is determined by observing with a microscope according to the following method, and the maximum diameter (diameter of circumscribed circle) is determined.
- the range of the defect is the size of the shadow when the defect is observed with the transmitted light of the differential interference microscope when the defect is a bubble or a foreign object.
- the defect is a change in the surface shape, such as transfer of a roll flaw or an abrasion
- the size is confirmed by observing the defect with the reflected light of a differential interference microscope.
- the film breaks with the defect as a starting point, and the productivity may be significantly reduced.
- the diameter of a defect becomes 5 micrometers or more, it can confirm visually by polarizing plate observation etc., and when used as an optical member, a bright spot may arise.
- the coating agent may not be formed uniformly, resulting in defects (coating defects).
- the defect is a void in the film (foaming defect) generated due to the rapid evaporation of the solvent in the drying process of the solution casting, a foreign matter in the film forming stock solution, or a foreign matter mixed in the film forming. This refers to the foreign matter (foreign matter defect) in the film.
- the acrylic resin-containing film of the present invention preferably has a breaking elongation in at least one direction of 10% or more, more preferably 20% or more, as measured in accordance with JIS-K7127-1999.
- the upper limit of the elongation at break is not particularly limited, but is practically about 250%. In order to increase the elongation at break, it is effective to suppress defects in the film caused by foreign matter and foaming.
- the thickness of the acrylic resin-containing film of the present invention is preferably 20 ⁇ m or more. More preferably, it is 30 ⁇ m or more.
- the upper limit of the thickness is not particularly limited, but in the case of forming a film by a solution casting method, the upper limit is about 250 ⁇ m from the viewpoint of applicability, foaming, solvent drying, and the like.
- the thickness of the film can be appropriately selected depending on the application.
- the acrylic resin-containing film of the present invention preferably has a total light transmittance of 90% or more, more preferably 93% or more.
- the practical upper limit is about 99%.
- the acrylic resin-containing film of the present invention has a haze value (turbidity), which is one of the indices indicating transparency, of less than 2.0%, preferably less than 1.0%.
- the acrylic resin (A) used in the present invention includes a methacrylic resin.
- the resin is preferably composed of 50 to 99% by mass of methyl methacrylate units and 1 to 50% by mass of other monomer units copolymerizable therewith.
- Examples of other copolymerizable monomers include alkyl methacrylates having 2 to 18 alkyl carbon atoms, alkyl acrylates having 1 to 18 carbon atoms, alkyl acrylates such as acrylic acid and methacrylic acid.
- Examples thereof include unsaturated nitrile, maleic anhydride, maleimide, N-substituted maleimide, and glutaric anhydride, and these can be used alone or in combination of two or more.
- methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable from the viewpoint of thermal decomposition resistance and fluidity of the copolymer.
- n-Butyl acrylate is particularly preferably used.
- the acrylic resin (A) used in the acrylic resin-containing film of the present invention preferably has a weight average molecular weight (Mw) of 80,000 to 1,000,000 from the viewpoint of mechanical strength as a film and fluidity when producing the film. .
- the weight average molecular weight of the acrylic resin of the present invention can be measured by gel permeation chromatography.
- the measurement conditions are as follows.
- the production method of the acrylic resin (A) in the present invention is not particularly limited, and any known method such as suspension polymerization, emulsion polymerization, bulk polymerization, or solution polymerization may be used.
- a polymerization initiator a normal peroxide type and an azo type can be used, and a redox type can also be used.
- the polymerization temperature may be 30 to 100 ° C. for suspension or emulsion polymerization, and 80 to 160 ° C. for bulk or solution polymerization. Furthermore, in order to control the reduced viscosity of the produced copolymer, polymerization can be carried out using alkyl mercaptan or the like as a chain transfer agent.
- acrylic resin (A) of the present invention Commercially available products can also be used as the acrylic resin (A) of the present invention.
- Delpet 60N, 80N (Asahi Kasei Chemicals Co., Ltd.), Dialal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Electrochemical Industry Co., Ltd.) and the like can be mentioned. .
- the acrylic resin-containing film of the present invention at least one acrylic resin (A) of the present invention is used.
- the weight average molecular weight of any acrylic resin (A) is 80000 to 1000000.
- ⁇ Cellulose ester resin (B)> In the acrylic resin-containing film of the present invention, at least one cellulose ester resin (B) of the present invention is used, and at least one of them has an acyl group total substitution degree (T) of 2.00 to 2.99, The degree of acetyl group substitution (ac) is 0.10 to 1.89, and the portion other than the acetyl group is substituted with an acyl group having 3 to 7 carbon atoms, and the degree of substitution (r) Of 1.10 to 2.89 and a weight average molecular weight (Mw) of 75,000 to 250,000 (hereinafter abbreviated as cellulose ester resin (B1)).
- the cellulose ester resin (B) other than the cellulose ester resin (B1) (hereinafter abbreviated as cellulose ester resin (B2)) has an acyl group total substitution degree (T) of 1.00 to 2.99, and an acetyl group substitution.
- T acyl group total substitution degree
- a degree (ac) of 0.10 to 2.99 and a substitution degree (r) of acyl groups other than acetyl groups of 0 to 2.89 can be selected.
- the cellulose ester resin (B1) and the cellulose ester resin (B2) can be used in a ratio of 100/0 to 50/50 (mass ratio).
- One or more cellulose ester resins (B1) and (B2) may be used.
- the aliphatic acyl group has 2 to 20 carbon atoms, specifically acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl , Hexanoyl, octanoyl, lauroyl, stearoyl and the like.
- the aliphatic acyl group is meant to include those further having a substituent.
- the aromatic ring is a benzene ring in the above-described aromatic acyl group
- the substituent of the benzene ring are exemplified.
- the number of substituents X substituted on the aromatic ring is 0 or 1 to 5, preferably 1 to 3, 1 or 2 is preferred.
- substituents substituted on the aromatic ring when the number of substituents substituted on the aromatic ring is 2 or more, they may be the same or different from each other, but they may be linked together to form a condensed polycyclic compound (for example, naphthalene, indene, indane, phenanthrene, quinoline). , Isoquinoline, chromene, chroman, phthalazine, acridine, indole, indoline, etc.).
- a condensed polycyclic compound for example, naphthalene, indene, indane, phenanthrene, quinoline.
- Isoquinoline chromene, chroman, phthalazine, acridine, indole, indoline, etc.
- the cellulose ester resin (B) has a structure having a structure selected from at least one of a substituted or unsubstituted aliphatic acyl group and a substituted or unsubstituted aromatic acyl group. Used as the structure used, these may be single or mixed acid esters of cellulose.
- Cellulose ester resin (B) of the present invention having an acyl group having 2 to 7 carbon atoms as a substituent, that is, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate , Cellulose acetate benzoate, and cellulose benzoate are preferable.
- particularly preferable cellulose ester resins (B) include cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate.
- the mixed fatty acid is a lower fatty acid ester of cellulose acetate propionate or cellulose acetate butyrate having an acyl group having 2 to 4 carbon atoms as a substituent.
- the portion not substituted with an acyl group usually exists as a hydroxyl group. These can be synthesized by known methods.
- substitution degree of the acetyl group and the substitution degree of other acyl groups were determined by the method prescribed in ASTM-D817-96.
- the weight average molecular weight (Mw) of the cellulose ester resin (B1) of the present invention is preferably 75,000 to 250,000, and more preferably 100,000 to 240,000.
- the resin (D) used in the present invention is a resin having a glass transition temperature Tg of 120 ° C. or higher and 300 ° C. or lower except for the acrylic resin (A) and the cellulose ester resin (B).
- Various resins (D) can be used as long as the physical properties of the acrylic resin-containing film of the present invention are not impaired.
- unsaturated groups such as methyl (meth) acrylate-styrene resin (styrene ratio exceeding 50 mol%), styrene-maleic anhydride, styrene-fumaric acid, styrene-itaconic acid, styrene-N-substituted maleimide, etc.
- Methyl (meth) acrylate-styrene resin and indene-methyl (meth) acrylate copolymer are preferably used because they are compatible with each other.
- the resin (D) of the present invention has a Tg of 120 ° C. or higher and 300 ° C. or lower. In order to improve heat resistance, a higher Tg is preferable.
- the acrylic resin-containing film may contain acrylic particles (C).
- the acrylic particles (C) it is also effective to reduce the refractive index difference between the acrylic resin (A) and the acrylic particles (C).
- the particle diameter and addition amount of the acrylic particles (C) should be suppressed within the above range, or the surface roughness of the film contact portion during film formation should be reduced. Is also effective.
- the acrylic particles (C) according to the present invention are preferably present in the state of particles in the acrylic resin (A) and the cellulose ester resin (B) and the acrylic resin-containing film (also referred to as an incompatible state).
- the acrylic particles (C) are, for example, collected a predetermined amount of the prepared acrylic resin-containing film, dissolved in a solvent, stirred, and sufficiently dissolved / dispersed. It is preferable that the weight of the insoluble matter filtered and collected using a PTFE membrane filter having a pore size is 90% by mass or more of the acrylic particles (C) added to the acrylic resin-containing film.
- the acrylic particles (C) used in the present invention are not particularly limited, but are preferably acrylic particles (C) having a layer structure of two or more layers, particularly the following multilayer structure acrylic granular composite. It is preferable.
- the multilayer structure acrylic granular composite is formed by laminating an innermost hard layer polymer, a cross-linked soft layer polymer exhibiting rubber elasticity, and an outermost hard layer polymer from the center to the outer periphery.
- Preferred embodiments of the multilayer structure acrylic granular composite used in the acrylic resin composition of the present invention include the following.
- (c) the innermost hard In the presence of a polymer comprising a layer and a crosslinked soft layer, a monomer mixture comprising 80 to 99% by mass of methyl methacrylate and 1 to 20% by mass
- Outermost hard layer weight And the obtained three-layer structure polymer is an innermost hard layer polymer (a) 5 to 40% by mass, a soft layer polymer (b) 30 to 60% by mass, and An outermost hard layer polymer (c) comprising 20 to 50% by mass, having an insoluble part when fractionated with acetone, and an acrylic granular composite having a methyl ethyl ketone swelling degree of 1.5 to 4.0 at the insoluble part .
- the innermost hard layer polymer (a) constituting the multilayer structure acrylic granular composite is 80 to 98.9% by mass of methyl methacrylate and 1 to 20 mass of alkyl acrylate having 1 to 8 carbon atoms in the alkyl group. % And a monomer mixture consisting of 0.01 to 0.3% by mass of a polyfunctional grafting agent is preferred.
- examples of the alkyl acrylate having 1 to 8 carbon atoms in the alkyl group include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like. And n-butyl acrylate are preferably used.
- the ratio of the alkyl acrylate unit in the innermost hard layer polymer (a) is 1 to 20% by mass.
- polyfunctional grafting agent examples include polyfunctional monomers having different polymerizable functional groups, such as allyl esters of acrylic acid, methacrylic acid, maleic acid, and fumaric acid, and allyl methacrylate is preferably used. .
- the polyfunctional grafting agent is used to chemically bond the innermost hard layer polymer and the soft layer polymer, and the ratio used during the innermost hard layer polymerization is 0.01 to 0.3% by mass. .
- the crosslinked soft layer polymer (b) constituting the acrylic granular composite is an alkyl acrylate having from 9 to 8 carbon atoms having an alkyl group of 1 to 8 in the presence of the innermost hard layer polymer (a). What is obtained by polymerizing a monomer mixture consisting of 10% by mass, 0.01 to 5% by mass of a multifunctional crosslinking agent and 0.5 to 5% by mass of a multifunctional grafting agent is preferred.
- n-butyl acrylate or 2-ethylhexyl acrylate is preferably used as the alkyl acrylate having 4 to 8 carbon atoms in the alkyl group.
- Examples of other monofunctional monomers that can be copolymerized include styrene and substituted styrene derivatives. As the ratio of the alkyl acrylate having 4 to 8 carbon atoms in the alkyl group and styrene increases, the glass transition temperature of the produced polymer (b) decreases as the former increases, that is, it can be softened.
- the refractive index of the soft layer polymer (b) at room temperature is set to the innermost hard layer polymer (a), the outermost hard layer polymer (c), and the hard heat. It is more advantageous to make it closer to the plastic acrylic resin, and the ratio between them is selected in consideration of these.
- polyfunctional grafting agent those mentioned in the section of the innermost layer hard polymer (a) can be used.
- the polyfunctional grafting agent used here is used to chemically bond the soft layer polymer (b) and the outermost hard layer polymer (c), and the proportion used during the innermost hard layer polymerization is impact resistance. From the viewpoint of the effect of imparting properties, 0.5 to 5% by mass is preferable.
- polyfunctional crosslinking agent generally known crosslinking agents such as divinyl compounds, diallyl compounds, diacrylic compounds, dimethacrylic compounds and the like can be used, but polyethylene glycol diacrylate (molecular weight 200 to 600) is preferably used.
- the polyfunctional cross-linking agent used here is used to generate a cross-linked structure during the polymerization of the soft layer (b) and to exhibit the effect of imparting impact resistance.
- the polyfunctional crosslinking agent is not an essential component because the crosslinked structure of the soft layer (b) is generated to some extent. Is preferably 0.01 to 5% by weight from the viewpoint of imparting impact resistance.
- the outermost hard layer polymer (c) constituting the multi-layer structure acrylic granular composite has a methyl methacrylate of 80 to 99 mass in the presence of the innermost hard layer polymer (a) and the soft layer polymer (b). % And a monomer mixture comprising 1 to 20% by mass of an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group is preferred.
- the acrylic alkylate those described above are used, but methyl acrylate and ethyl acrylate are preferably used.
- the proportion of the alkyl acrylate unit in the outermost hard layer (c) is preferably 1 to 20% by mass.
- an alkyl mercaptan or the like can be used as a chain transfer agent to adjust the molecular weight for the purpose of improving the compatibility with the acrylic resin (A).
- the outermost hard layer with a gradient such that the molecular weight gradually decreases from the inside toward the outside in order to improve the balance between elongation and impact resistance.
- the monomer mixture for forming the outermost hard layer is divided into two or more, and the molecular weight is increased from the inside by a method of sequentially increasing the amount of chain transfer agent added each time. It is possible to make it smaller toward the outside.
- the molecular weight formed at this time can also be examined by polymerizing the monomer mixture used each time under the same conditions, and measuring the molecular weight of the obtained polymer.
- the particle diameter of the acrylic granular composite which is a multilayer structure polymer preferably used in the present invention is not particularly limited, but is preferably 10 nm or more and 1000 nm or less, and more preferably 20 nm or more and 500 nm or less. More preferably, it is most preferably 50 nm or more and 400 nm or less.
- the mass ratio of the core and the shell is not particularly limited, but when the entire multilayer structure polymer is 100 parts by mass,
- the core layer is preferably 50 parts by mass or more and 90 parts by mass or less, and more preferably 60 parts by mass or more and 80 parts by mass or less.
- Examples of such commercially available multilayered acrylic granular composites include, for example, “Metablene” manufactured by Mitsubishi Rayon Co., “Kane Ace” manufactured by Kaneka Chemical Co., Ltd., “Paralloid” manufactured by Kureha Chemical Co., Ltd., Rohm and Haas “Acryloid” manufactured by KK, “Staffyroid” manufactured by Ganz Kasei Kogyo Co., Ltd., “Parapet SA” manufactured by Kuraray Co., Ltd., and the like can be used alone or in combination.
- acrylic particles (c-1) which are graft copolymers preferably used as the acrylic particles (C) preferably used in the present invention include unsaturated carboxylic acids in the presence of a rubbery polymer.
- a monomer mixture comprising an acid ester monomer, an unsaturated carboxylic acid monomer, an aromatic vinyl monomer, and, if necessary, other vinyl monomers copolymerizable therewith A polymerized graft copolymer may be mentioned.
- the rubbery polymer used for the acrylic particles (c-1) as the graft copolymer is not particularly limited, but diene rubber, acrylic rubber, ethylene rubber, and the like can be used. Specific examples include polybutadiene, styrene-butadiene copolymer, block copolymer of styrene-butadiene, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, polyisoprene, butadiene-methyl methacrylate copolymer.
- the acrylic resin (A) and the acrylic particles (C) have similar refractive indexes because the transparency of the acrylic resin-containing film of the present invention can be obtained.
- the refractive index difference between the acrylic particles (C) and the acrylic resin (A) is preferably 0.05 or less, more preferably 0.02 or less, and particularly preferably 0.01 or less.
- a method of adjusting the monomer unit composition ratio of the acrylic resin (A) and / or a rubbery polymer or monomer used for the acrylic particles (C) The difference in refractive index can be reduced by a method of adjusting the composition ratio, and an acrylic resin-containing film excellent in transparency can be obtained.
- the difference in refractive index referred to here is a solution in which the acrylic resin-containing film of the present invention is sufficiently dissolved in a solvent in which the acrylic resin (A) is soluble to obtain a cloudy solution, which is subjected to an operation such as centrifugation.
- the measured refractive index 23 ° C., measurement wavelength: 550 nm.
- the method of blending the acrylic particles (C) with the acrylic resin (A) is not particularly limited. After the acrylic resin (A) and other optional components are previously blended, usually at 200 to 350 ° C. A method of uniformly melt-kneading with a single-screw or twin-screw extruder while adding acrylic particles (C) is preferably used.
- a solution in which acrylic particles (C) are dispersed in advance is added to and mixed with a solution (dope solution) in which acrylic resin (A) and cellulose ester resin (B) are dissolved, acrylic particles (C) and A method such as in-line addition of a solution obtained by dissolving or mixing other optional additives can be used.
- acrylic particles can also be used as the acrylic particles of the present invention.
- metabrene W-341 (manufactured by Mitsubishi Rayon Co., Ltd.)
- Chemisnow MR-2G (C3)
- MS-300X (manufactured by Soken Chemical Co., Ltd.) and the like can be mentioned.
- the acrylic resin-containing film of the present invention preferably contains 0.5 to 45% by mass of acrylic particles (C) with respect to the total mass of the resin constituting the film.
- a plasticizer can be used in combination in order to improve the fluidity and flexibility of the composition.
- plasticizer examples include phthalate ester, fatty acid ester, trimellitic ester, phosphate ester, polyester, and epoxy.
- polyester-based and phthalate-based plasticizers are preferably used.
- Polyester plasticizers are superior in non-migration and extraction resistance compared to phthalate ester plasticizers such as dioctyl phthalate, but are slightly inferior in plasticizing effect and compatibility.
- the polyester plasticizer is a reaction product of a monovalent or tetravalent carboxylic acid and a monovalent or hexavalent alcohol, and is mainly obtained by reacting a divalent carboxylic acid with a glycol.
- Representative divalent carboxylic acids include glutaric acid, itaconic acid, adipic acid, phthalic acid, azelaic acid, sebacic acid and the like.
- glycol examples include glycols such as ethylene, propylene, 1,3-butylene, 1,4-butylene, 1,6-hexamethylene, neopentylene, diethylene, triethylene, and dipropylene.
- divalent carboxylic acids and glycols may be used alone or in combination.
- the ester plasticizer may be any of ester, oligoester and polyester types, and the molecular weight is preferably in the range of 100 to 10000, but preferably in the range of 600 to 3000, the plasticizing effect is large.
- the viscosity of the plasticizer has a correlation with the molecular structure and molecular weight, but in the case of an adipic acid plasticizer, the range of 200 to 5000 mPa ⁇ s (25 ° C.) is preferable because of compatibility and plasticization efficiency. Furthermore, some polyester plasticizers may be used in combination.
- the plasticizer is preferably added in an amount of 0.5 to 30 parts by mass with respect to 100 parts by mass of the composition containing the acrylic resin (A). If the added amount of the plasticizer exceeds 30 parts by mass, the surface becomes sticky, which is not preferable for practical use.
- the composition containing the acrylic resin (A) of the present invention preferably contains an ultraviolet absorber, and examples of the ultraviolet absorber used include benzotriazole, 2-hydroxybenzophenone, and salicylic acid phenyl ester.
- the ultraviolet absorber used include benzotriazole, 2-hydroxybenzophenone, and salicylic acid phenyl ester.
- benzotriazole 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3 Triazoles such as 5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone And benzophenones.
- ultraviolet absorbers having a molecular weight of 400 or more are less likely to volatilize at a high boiling point and are difficult to disperse even during high-temperature molding, so that the weather resistance is effectively improved with a relatively small amount of addition. be able to.
- the transition from the thin coating layer to the substrate layer is particularly small and hardly precipitates on the surface of the laminate, the amount of contained UV absorber is maintained for a long time, and the durability of the weather resistance improvement effect is excellent. From the point of view, it is preferable.
- Examples of the ultraviolet absorber having a molecular weight of 400 or more include 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole, 2,2-methylenebis [4- (1, 1,3,3-tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( Hindered amines such as 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonic acid Bis (1,2,2,6,6-pentamethyl-4-piperidyl), 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] Such as til] -4- [3- (3,5-di-tert-butyl
- 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2-benzotriazole and 2,2-methylenebis [4- (1,1,3,3- Tetrabutyl) -6- (2H-benzotriazol-2-yl) phenol] is particularly preferred.
- antioxidants can be added to the acrylic resin (A) used in the acrylic resin-containing film of the present invention in order to improve the thermal decomposability and thermal colorability during molding.
- an antistatic agent can be added to impart antistatic performance to the acrylic resin-containing film.
- a flame retardant acrylic resin composition containing a phosphorus flame retardant may be used.
- Phosphorus flame retardants used here include red phosphorus, triaryl phosphate ester, diaryl phosphate ester, monoaryl phosphate ester, aryl phosphonate compound, aryl phosphine oxide compound, condensed aryl phosphate ester, halogenated alkyl phosphorus. Examples thereof include one or a mixture of two or more selected from acid esters, halogen-containing condensed phosphates, halogen-containing condensed phosphonates, halogen-containing phosphites, and the like.
- triphenyl phosphate 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phenylphosphonic acid, tris ( ⁇ -chloroethyl) phosphate, tris (dichloropropyl) Examples thereof include phosphate and tris (tribromoneopentyl) phosphate.
- production methods such as an inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, and a hot press method can be used. From the viewpoints of suppressing foreign matter defects and optical defects such as die lines, solution casting by casting is preferred.
- Organic solvents useful for forming the dope when the acrylic resin-containing film of the present invention is produced by the solution casting method are acrylic resin (A), cellulose ester resin (B), resin (D), and other additions. Any agent that dissolves the agent simultaneously can be used without limitation.
- methylene chloride as a non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, etc.
- Methylene chloride, methyl acetate, ethyl acetate and acetone can be preferably used.
- the dope preferably contains 1 to 40% by mass of a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.
- a linear or branched aliphatic alcohol having 1 to 4 carbon atoms.
- the ratio of alcohol in the dope increases, the web gels and peeling from the metal support becomes easy.
- acrylic resin (A) and cellulose ester in non-chlorine organic solvent system There is also a role of promoting dissolution of the resin (B).
- a solvent containing methylene chloride and a linear or branched aliphatic alcohol having 1 to 4 carbon atoms includes three types of resin, acrylic resin (A), cellulose ester resin (B), and resin (D). Is preferably a dope composition in which at least 15 to 45 mass% is dissolved.
- linear or branched aliphatic alcohol having 1 to 4 carbon atoms examples include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, and tert-butanol. Ethanol is preferred because of the stability of these dopes, the relatively low boiling point, and good drying properties.
- the acrylic resin (A), the cellulose ester resin (B), and the resin (D) are dissolved by a method performed at normal pressure, a method performed at a temperature lower than the boiling point of the main solvent, a method performed at a pressure higher than the boiling point of the main solvent, A method performed by a cooling dissolution method as described in Kaihei 9-95544, JP-A-9-95557, or JP-A-9-95538, a method performed at a high pressure as described in JP-A-11-21379, etc.
- Various dissolution methods can be used, but a method of pressurizing at a temperature equal to or higher than the boiling point of the main solvent is particularly preferable.
- the total of three types of acrylic resin (A), cellulose ester resin (B) and resin (D) in the dope is preferably in the range of 15 to 45% by mass.
- An additive is added to the dope during or after dissolution to dissolve and disperse, then filtered through a filter medium, defoamed, and sent to the next step with a liquid feed pump.
- a filter medium having a collected particle diameter of 0.5 to 5 ⁇ m and a drainage time of 10 to 25 sec / 100 ml it is preferable to use.
- the aggregate remaining when the fine particles are dispersed and the aggregate generated when the main dope is added are only aggregated by using a filter medium having a collected particle diameter of 0.5 to 5 ⁇ m and a drainage time of 10 to 25 sec / 100 ml. Can be removed.
- the concentration of fine particles is sufficiently thinner than that of the additive solution, so that aggregates do not stick together during filtration and the filtration pressure does not increase suddenly.
- FIG. 1 is a diagram schematically showing a dope preparation step, a casting step, and a drying step of a solution casting film forming method preferable for the present invention.
- Large agglomerates are removed from the acrylic fine particle charging vessel 41 by the filter 44 and fed to the stock vessel 42.
- the acrylic fine particle additive solution is added from the stock kettle 42 to the main dope dissolving kettle 1. Thereafter, the main dope solution is filtered by the main filter 3, and an ultraviolet absorbent additive solution is added in-line from 16 to this.
- the main dope may contain about 10 to 50% by weight of recycled material. Since the return material contains acrylic fine particles, it is preferable to control the addition amount of the acrylic fine particle addition liquid in accordance with the addition amount of the return material.
- Recycled material is a finely pulverized acrylic resin-containing film that is generated when an acrylic resin-containing film is formed.
- the original fabric is used.
- those obtained by previously kneading and pelletizing acrylic resin and acrylic fine particles can be preferably used.
- An endless metal belt 31 such as a stainless steel belt or a rotating metal drum, which feeds the dope through a liquid feed pump (for example, a pressurized metering gear pump) to the pressure die 30 and transfers it infinitely. This is a step of casting the dope from the pressure die slit to the casting position on the support.
- a liquid feed pump for example, a pressurized metering gear pump
- the pressure die includes a coat hanger die and a T die, and any of them is preferably used.
- the surface of the metal support is a mirror surface.
- two or more pressure dies may be provided on the metal support, and the dope amount may be divided and stacked. Or it is also preferable to obtain the film of a laminated structure by the co-casting method which casts several dope simultaneously.
- Solvent evaporation step In this step, the web (the dope is cast on the casting support and the formed dope film is called a web) is heated on the casting support to evaporate the solvent.
- the web on the support after casting is preferably dried on the support in an atmosphere of 40 to 100 ° C.
- Peeling process It is the process of peeling the web which the solvent evaporated on the metal support body in a peeling position. The peeled web is sent to the next process.
- the temperature at the peeling position on the metal support is preferably 10 to 40 ° C., more preferably 11 to 30 ° C.
- the residual solvent amount at the time of peeling of the web on the metal support at the time of peeling is preferably peeled in the range of 50 to 120% by mass depending on the strength of drying conditions, the length of the metal support, and the like.
- the amount of residual solvent is determined.
- the amount of residual solvent in the web is defined by the following formula.
- Residual solvent amount (%) (mass before web heat treatment ⁇ mass after web heat treatment) / (mass after web heat treatment) ⁇ 100 Note that the heat treatment for measuring the residual solvent amount represents performing heat treatment at 115 ° C. for 1 hour.
- the peeling tension at the time of peeling the metal support from the film is usually 196 to 245 N / m. However, if wrinkles easily occur at the time of peeling, it is preferable to peel with a tension of 190 N / m or less. It is preferable to peel at a minimum tension of ⁇ 166.6 N / m, and then peel at a minimum tension of ⁇ 137.2 N / m, and particularly preferable to peel at a minimum tension of ⁇ 100 N / m.
- the temperature at the peeling position on the metal support is preferably ⁇ 50 to 40 ° C., more preferably 10 to 40 ° C., and most preferably 15 to 30 ° C.
- a drying device 35 that alternately conveys the web through a plurality of rolls arranged in the drying device and / or a tenter stretching device 34 that clips and conveys both ends of the web with a clip are used. And dry the web.
- the drying means is generally to blow hot air on both sides of the web, but there is also a means to heat by applying microwaves instead of wind. Too rapid drying tends to impair the flatness of the finished film.
- Drying at a high temperature should be performed from about 8% by mass or less of residual solvent. Throughout, drying is generally performed at 40-250 ° C. In particular, drying at 40 to 160 ° C. is preferable.
- tenter stretching apparatus When using a tenter stretching apparatus, it is preferable to use an apparatus capable of independently controlling the film gripping length (distance from the start of gripping to the end of gripping) by the left and right gripping means of the tenter.
- tenter process it is also preferable to intentionally create compartments having different temperatures in order to improve flatness. It is also preferable to provide a neutral zone between different temperature zones so that the zones do not interfere with each other.
- the stretching operation may be performed in multiple stages, and it is also preferable to perform biaxial stretching in the casting direction and the width direction.
- biaxial stretching When biaxial stretching is performed, simultaneous biaxial stretching may be performed or may be performed stepwise.
- stepwise means that, for example, stretching in different stretching directions can be sequentially performed, stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any one of the stages. Is also possible. That is, for example, the following stretching steps are possible.
- Simultaneous biaxial stretching includes stretching in one direction and contracting the other while relaxing the tension.
- the preferred draw ratio for simultaneous biaxial stretching can be in the range of x1.01 to x1.5 in both the width direction and the longitudinal direction.
- the amount of residual solvent in the web is preferably 20 to 100% by mass at the start of the tenter, and drying is preferably performed while the tenter is applied until the amount of residual solvent in the web is 10% by mass or less. More preferably, it is 5% by mass or less.
- the drying temperature is preferably 30 to 150 ° C, more preferably 50 to 120 ° C, and most preferably 70 to 100 ° C.
- the temperature distribution in the width direction of the atmosphere is small from the viewpoint of improving the uniformity of the film.
- the temperature distribution in the width direction in the tenter process is preferably within ⁇ 5 ° C, and within ⁇ 2 ° C. Is more preferable, and within ⁇ 1 ° C. is most preferable.
- Winding step This is a step of winding up the acrylic resin-containing film by the winder 37 after the residual solvent amount in the web is 2% by mass or less, and the residual solvent amount is 0.4% by mass or less. Thus, a film having good dimensional stability can be obtained.
- a generally used one may be used, and there are a constant torque method, a constant tension method, a taper tension method, a program tension control method with a constant internal stress, etc., and these may be used properly.
- the acrylic resin-containing film of the present invention is preferably a long film. Specifically, the acrylic resin-containing film is about 100 m to 5000 m, and is usually in the form of a roll.
- the film width is preferably 1.3 to 4 m, more preferably 1.4 to 2 m.
- the film thickness of the acrylic resin-containing film of the present invention is not particularly limited, but when used for a polarizing plate protective film described later, it is preferably 20 to 200 ⁇ m, more preferably 25 to 100 ⁇ m, and 30 to 80 ⁇ m. It is particularly preferred that
- the polarizing plate used in the present invention can be produced by a general method. That is, it is preferable that an adhesive layer is provided on the back side of the acrylic resin-containing film of the present invention, and is bonded to at least one surface of a polarizer produced by immersion and stretching in an iodine solution.
- surface treatment such as corona treatment can be performed.
- the adhesiveness with the polarizer can be improved.
- the film may be used on the other surface, or another polarizing plate protective film may be used.
- cellulose ester films for example, Konica Minoltack KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KV8UY-HA, KV8UX-RHA, KV8UX-RHA Co., Ltd.
- cycloolefin films for example, ZEONOR film (manufactured by ZEON Corporation), ARTON film (manufactured by JSR Corporation)
- ZEONOR film manufactured by ZEON Corporation
- ARTON film manufactured by JSR Corporation
- a polarizer which is a main component of a polarizing plate, is an element that transmits only light having a plane of polarization in a certain direction.
- a typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed.
- the polarizer is formed by forming a polyvinyl alcohol aqueous solution into a film and dyeing the film by uniaxial stretching or dyeing or uniaxially stretching, and then performing a durability treatment with a boron compound.
- an adhesive layer having a storage elastic modulus at 25 ° C. in the range of 1.0 ⁇ 10 4 Pa to 1.0 ⁇ 10 9 Pa in at least a part of the adhesive layer is used. It is preferable to use a curable adhesive that forms a high molecular weight body or a crosslinked structure by various chemical reactions after the adhesive layer is applied and bonded.
- urethane adhesives examples include, for example, urethane adhesives, epoxy adhesives, aqueous polymer-isocyanate adhesives, curable adhesives such as thermosetting acrylic adhesives, moisture curable urethane adhesives, polyether methacrylate types, Examples include anaerobic adhesives such as ester-based methacrylate type and oxidized polyether methacrylate, cyanoacrylate-based instant adhesives, acrylate-peroxide-based two-component instant adhesives, and the like.
- the adhesive may be a one-component type, or a type in which two or more components are mixed before use.
- the adhesive may be a solvent system using an organic solvent as a medium, or an aqueous system such as an emulsion type, a colloidal dispersion type, or an aqueous solution type that is a medium containing water as a main component. It may be a solvent type.
- the concentration of the adhesive solution may be appropriately determined depending on the film thickness after bonding, the coating method, the coating conditions, and the like, and is usually 0.1 to 50% by mass.
- liquid crystal display device By incorporating the polarizing plate bonded with the acrylic resin-containing film of the present invention into a liquid crystal display device, various liquid crystal display devices with excellent visibility can be produced.
- the polarizing plate according to the present invention is bonded to a liquid crystal cell via the adhesive layer or the like.
- the polarizing plate according to the present invention is a reflective type, transmissive type, transflective type LCD or TN type, STN type, OCB type, HAN type, VA type (PVA type, MVA type), IPS type, etc. Preferably used.
- the produced dope solution was 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. With the stainless steel band support,
- the solvent was evaporated from the peeled acrylic resin web at 35 ° C., slit to 1.6 m width, and then dried at a drying temperature of 135 ° C. while stretching 1.1 times in the width direction with a tenter. At this time, the residual solvent amount when starting stretching with a tenter was 10%.
- 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 1.1 times.
- the residual solvent amount of the acrylic resin-containing film 1 described in Table 1 was 0.1%, the film thickness was 60 ⁇ m, and the winding number was 4000 m.
- the acrylic resin-containing film is the same as the acrylic resin-containing film 1 except that the types and composition ratios of the acrylic resin (A), the cellulose ester resin (B), and the resin (D) are changed as shown in Table 1. 1 to 43 were produced.
- Table 1 the materials used are as follows: Symbol Weight average molecular weight Composition BR52 85000 MS BR80 95000 MMA BR83 40000 MMA BR85 280000 MMA BR88 480000 MMA BR102 360000 MMA 80N 100,000 MMA Abbreviations and seeds are as follows: MS: Methyl acrylate / styrene copolymer MMA: Methyl methacrylate BR series and 80N are Delpet 80N (manufactured by Asahi Kasei Chemicals), Dialnal BR52, BR83, BR85, BR88, BR102 (manufactured by Mitsubishi Rayon), respectively. .
- A1 to A4 were prepared by a known method.
- the composition is as follows: A1: Poly (MMA-MA) mass ratio 98: 2 Mw 70000 A2: Poly (MMA-MA) mass ratio 97: 3 Mw 800000 A3: Poly (MMA-MA) mass ratio 97: 3 Mw930000 A4: Poly (MMA-MA) mass ratio 94: 6 Mw1100000 ac: 1.92, p: 0.74 means a cellulose ester having an acetyl group substitution degree of 1.92 and a propionyl group substitution degree of 0.74.
- B represents butyrate, bz represents benzoate, pi represents pivalate, and ph represents a cellulose ester substituted with phthalate.
- the acrylic resin containing films 20 and 23 added the following ultraviolet absorber and produced dope.
- thermoplastic copolymer described in Example 1 of JP-A-2007-191706 was prepared, and a pellet composition according to Example 7 was prepared to obtain a comparative sample film 44 having a film thickness of 60 ⁇ m. .
- Example 1 of JP-A-2007-233114 was produced and used as a comparative sample film 45.
- An acrylic resin-containing film conditioned for 24 hours in an air-conditioned room at 23 ° C. and 55% RH is cut out at 120 mm (length) ⁇ 10 mm (width) under the same conditions and heated at 30 ° C./min while being pulled with a tension of 10 N. The temperature was continuously increased at a speed, and the temperature at 9 N was measured three times, and the average was obtained.
- Glass-transition temperature (Glass-transition temperature) Using a differential scanning calorimeter (DSC-7, manufactured by Perkin Elmer), the glass transition temperature (Tmg) was determined in accordance with JIS K7121 (1987), measured in a nitrogen stream at a heating rate of 20 ° C./min. Was the glass transition temperature.
- ⁇ Cannot be folded 3 times
- ⁇ Can be folded at least 1 out of 3 times (Dimensional change with respect to humidity change)
- Two marks are placed in the casting direction of the produced film and treated at 60 ° C. and 90% RH for 1000 hours. The distance between the mark (cross) before and after treatment is 23 ° C. and 55% RH. Below, it measured with the optical microscope and evaluated on the following reference
- Dimensional change rate (%) [(a1-a2) / a1] ⁇ 100 a1: Distance before heat treatment a2: Distance after heat treatment ⁇ ⁇ ⁇ ⁇ less than 0.3% ⁇ ⁇ ⁇ ⁇ 0.3 to 0.5% ⁇ ... 0.5% ⁇ (Repeat resistance)
- the prepared film is held in a constant temperature bath at 60 ° C. for 30 minutes, then held in a constant temperature bath at ⁇ 20 ° C. for 30 minutes, and again held in a constant temperature bath at 60 ° C.
- the tearing surface is very smooth and is torn straight.
- ⁇ Very smooth flatness
- ⁇ Slightly creased, wrinkled, and step can be confirmed
- ⁇ Clearly creased, wrinkled, and step can be confirmed (Preparation of polarizing plate)
- a 120 ⁇ m-thick long roll polyvinyl alcohol film was immersed in 100 parts by mass of an aqueous solution containing 1 part by mass of iodine and 4 parts by mass of boric acid, and stretched in the transport direction 5 times at 50 ° C. to form a polarizing film.
- the acrylic resin-containing film 1 produced in Example 1 was subjected to corona treatment on one side of the polarizing film and then bonded.
- KC8UCR-5 manufactured by Konica Minolta Opto Co., Ltd., which is a retardation film subjected to alkali saponification treatment, was bonded to the other surface of the polarizing film and dried to prepare Polarizing Plate 1.
- polarizing plates 2 to 44 were prepared using acrylic resin-containing films 2 to 44.
- the polarizing plate using the acrylic resin-containing film of the present invention was excellent in film cutting property and easy to process.
- the viewing angle of the liquid crystal display device was measured using EZ-Contrast 160D manufactured by ELDIM in an environment of 23 ° C. and 55% RH. Subsequently, the polarizing plate treated at 60 ° C. and 90% RH for 1000 hours was measured in the same manner, and evaluated according to the following criteria in four stages.
- Liquid crystal display devices 1 to 43 were prepared by attaching a polarizing plate in the same manner as in the viewing angle evaluation described above. Next, the display was displayed in black, and the color change when observed from an oblique 45 ° angle was evaluated according to the following criteria under an environment of 23 ° C. and 55% RH.
- the acrylic resin-containing film of the present invention is transparent, has high heat resistance, and has markedly improved brittleness. Furthermore, the polarizing plate produced using the acrylic resin-containing film of the present invention improves the yield in operations such as punching and panel bonding, and provides good visibility over the long term even in use in harsh environments. It can be seen that this is a liquid crystal display device that continues to be maintained.
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Abstract
Description
3、6、12、15 濾過器
4、13 ストックタンク
5、14 送液ポンプ
8、16 導管
10 紫外線吸収剤仕込釜
20 合流管
21 混合機
30 ダイ
31 金属支持体
32 ウェブ
33 剥離位置
34 テンター装置
35 ロール乾燥装置
41 粒子仕込釜
42 ストックタンク
43 ポンプ
44 濾過器
本発明のアクリル樹脂フィルムは、アクリル樹脂(A)およびセルロースエステル樹脂(B)の一種類ずつ、並びに、(A)、(B)および(A)、(B)以外であってガラス転移温度Tgが120℃以上300℃以下の樹脂(D)から選択される少なくとも1種類以上の樹脂からなるアクリル樹脂含有フィルムであって、該アクリル樹脂含有フィルムの張力軟化点が120~150℃で延性破壊を起こさないことを特徴とするアクリル樹脂含有フィルム。
本発明に用いられるアクリル樹脂(A)には、メタクリル樹脂も含まれる。樹脂としては、メチルメタクリレート単位50~99質量%、およびこれと共重合可能な他の単量体単位1~50質量%からなるものが好ましい。
カラム: Shodex K806、K805、K803G(昭和電工(株)製を3本接続して使用した)
カラム温度:25℃
試料濃度: 0.1質量%
検出器: RI Model 504(GLサイエンス社製)
ポンプ: L6000(日立製作所(株)製)
流量: 1.0ml/min
校正曲線: 標準ポリスチレンSTK standard ポリスチレン(東ソー(株)製)Mw=2,800,000~500迄の13サンプルによる校正曲線を使用した。13サンプルは、ほぼ等間隔に用いることが好ましい。
本発明のアクリル樹脂含有フィルムにおいては、本発明のセルロースエステル樹脂(B)は一種以上使用されるが、そのうち少なくとも一種は、アシル基の総置換度(T)が2.00~2.99、アセチル基置換度(ac)が0.10~1.89であって、アセチル基以外の部分が、3~7の炭素数で構成されるアシル基で置換されており、その置換度(r)が1.10~2.89で、重量平均分子量(Mw)が75000~250000である(以下、セルロースエステル樹脂(B1)と略す)。
本発明に用いられる樹脂(D)は、アクリル樹脂(A)およびセルロースエステル樹脂(B)以外であってガラス転移温度Tgが120℃以上300℃以下の樹脂である。本発明のアクリル樹脂含有フィルムの物性を損なわない範囲であれば、種々の樹脂(D)を使用することが可能である。
本発明においては、アクリル樹脂含有フィルムにアクリル粒子(C)を含有させてもよい。アクリル粒子(C)を使用する場合は、アクリル系樹脂(A)とアクリル粒子(C)との屈折率差を小さくすることも有効である。
本発明のアクリル樹脂含有フィルムにおいては、組成物の流動性や柔軟性を向上するために、可塑剤を併用することも可能である。
本発明のアクリル樹脂含有フィルムの製膜方法の例を説明するが、本発明はこれに限定されるものではない。
本発明のアクリル樹脂含有フィルムを溶液流延法で製造する場合のドープを形成するのに有用な有機溶媒は、アクリル樹脂(A)、セルロースエステル樹脂(B)、樹脂(D)、その他の添加剤を同時に溶解するものであれば制限なく用いることが出来る。
アクリル樹脂(A)、セルロースエステル樹脂(B)、樹脂(D)に対する良溶媒を主とする有機溶媒に、溶解釜中で該アクリル樹脂(A)、セルロースエステル樹脂(B)、樹脂(D)、添加剤を攪拌しながら溶解しドープを形成する工程、或いは該アクリル樹脂(A)、セルロースエステル樹脂(B)、樹脂(D)溶液に、添加剤溶液を混合してドープを形成する工程である。
ドープを送液ポンプ(例えば、加圧型定量ギヤポンプ)を通して加圧ダイ30に送液し、無限に移送する無端の金属ベルト31、例えばステンレスベルト、或いは回転する金属ドラム等の金属支持体上の流延位置に、加圧ダイスリットからドープを流延する工程である。
ウェブ(流延用支持体上にドープを流延し、形成されたドープ膜をウェブと呼ぶ)を流延用支持体上で加熱し、溶媒を蒸発させる工程である。
金属支持体上で溶媒が蒸発したウェブを、剥離位置で剥離する工程である。剥離されたウェブは次工程に送られる。
尚、残留溶媒量を測定する際の加熱処理とは、115℃で1時間の加熱処理を行うことを表す。
剥離後、ウェブを乾燥装置内に複数配置したロールに交互に通して搬送する乾燥装置35、及び/またはクリップでウェブの両端をクリップして搬送するテンター延伸装置34を用いて、ウェブを乾燥する。
・幅手方向に延伸-幅手方向に延伸-流延方向に延伸-流延方向に延伸
また、同時2軸延伸には、一方向に延伸し、もう一方を張力を緩和して収縮させる場合も含まれる。同時2軸延伸の好ましい延伸倍率は幅手方向、長手方向ともに×1.01倍~×1.5倍の範囲でとることができる。
ウェブ中の残留溶媒量が2質量%以下となってからアクリル樹脂含有フィルムとして巻き取り機37により巻き取る工程であり、残留溶媒量を0.4質量%以下にすることにより寸法安定性の良好なフィルムを得ることが出来る。
本発明に用いられる偏光板は一般的な方法で作製することが出来る。すなわち、本発明のアクリル樹脂含有フィルムの裏面側に接着層を設け、沃素溶液中に浸漬延伸して作製した偏光子の少なくとも一方の面に、貼り合わせることが好ましい。
本発明のアクリル樹脂含有フィルムを貼合した偏光板を液晶表示装置に組み込むことによって、種々の視認性に優れた液晶表示装置を作製することが出来る。本発明に係る偏光板は、前記粘着層等を介して液晶セルに貼合する。
攪拌機及び塩化カルシウム管付き環流冷却管を備えた50ミリリットルの3つ口フラスコに、インデン5g、メチルメタアクリレート5g、トルエン30gを加え、25℃の水浴中で均一になるまで攪拌した。次いで、塩化鉄の0.05gを添加して重合を開始した。反応開始後1時間で、更に塩化鉄(III)0.09gを添加した。
〈アクリル樹脂含有フィルムの作製〉
(アクリル樹脂含有フィルム1の作製)
(ドープ液の調製)
BR85(三菱レイヨン社製、アクリル樹脂) 70質量部
セルロースエステル(セルロースアセテートプロピオネート アシル基総置換度2.75、アセチル基置換度0.19、プロピオニル基置換度2.56、Mw=200000、Tg144℃) 20質量部
セルロースエステル(セルロースアセテートプロピオネート アシル基総置換度2.73、アセチル基置換度1.41、プロピオニル基置換度1.32、Mw=200000、Tg165℃) 10質量部
メチレンクロライド 300質量部
エタノール 40質量部
(アクリル樹脂含有フィルムの製膜)
上記作製したドープ液を、ベルト流延装置を用い、温度22℃、2m幅でステンレスバンド支持体に均一に流延した。ステンレスバンド支持体で、残留溶剤量が100%になるまで溶媒を蒸発させ、剥離張力162N/mでステンレスバンド支持体上から剥離した。
略 号 重量平均分子量 組 成
BR52 85000 MS
BR80 95000 MMA
BR83 40000 MMA
BR85 280000 MMA
BR88 480000 MMA
BR102 360000 MMA
80N 100000 MMA
略号及び種は以下の通り、
MS:メチルアクリレート・スチレン共重合体
MMA:メチルメタクリレート
BRシリーズと80Nは、それぞれ、デルペット80N(旭化成ケミカルズ社製)、ダイヤナールBR52、BR83、BR85、BR88、BR102(三菱レイヨン社製)である。
A1:ポリ(MMA-MA)質量比98:2 Mw70000
A2:ポリ(MMA-MA)質量比97:3 Mw800000
A3:ポリ(MMA-MA)質量比97:3 Mw930000
A4:ポリ(MMA-MA)質量比94:6 Mw1100000
ac:1.92、p:0.74はアセチル基置換度1.92、プロピオニル基置換度0.74のセルロースエステルを意味する。また、bはブチレート、bzはベンゾエート、piはピバレート、phはフタレートの置換されたセルロースエステルを表す。
OAcSc:オクタアセチルサッカロースMw680(東京化成製)Tg=95℃
尚、アクリル樹脂含有フィルム20,23は、下記紫外線吸収剤を添加してドープを作製した。
チヌビン109(チバスペシャルティケミカルズ(株)製) 1.5質量部
チヌビン171(チバスペシャルティケミカルズ(株)製) 0.7質量部
アクリル樹脂含有フィルム23
LA-31(ADEKA社製) 1.5質量部
得られたアクリル樹脂含有フィルム1~45について以下の評価を実施し、結果を表2~表4に示す。
上記作製した各々のフィルム試料について、23℃、55%RHの空調室で24時間調湿した後、同条件下においてフィルム試料1枚をJIS K-7136に従って、ヘーズメーター(NDH2000型、日本電色工業(株)製)を使用して測定した。
テンシロン試験機(ORIENTEC社製、RTC-1225A)を用いて、以下のような評価を行った。
示差走査熱量測定器(Perkin Elmer社製DSC-7型)を用いて、窒素気流中、昇温速度20℃/分で測定し、JIS K7121(1987)に従い求めた中間点ガラス転移温度(Tmg)をガラス転移温度とした。
23℃、55%RHの空調室で24時間調湿したアクリル樹脂含有フィルムを、同条件下、100mm(縦)×10mm(幅)で切り出し、縦方向の中央部で、曲率半径0mm、折り曲げ角が180°でフィルムがぴったりと重なるように山折り、谷折りと2つにそれぞれ1回ずつ折りまげ、この評価を3回測定して、以下のように評価した。尚、ここでの評価の折れるとは、割れて2つ以上のピースに分離したことを表す。
×・・・3回のうち少なくとも1回は折れる
(湿度変化に対する寸法変化)
作製したフィルムの流延方向に、目印(十字)を2箇所つけて60℃、90%RHで1000時間処理し、処理前と処理後の目印(十字)の距離を23℃55%RHの条件下、光学顕微鏡で測定し、下記基準で評価した。
a1:熱処理前の距離
a2:熱処理後の距離
○・・・0.3%未満
△・・・0.3~0.5%
×・・・0.5%~
(繰り返し耐性)
作製したフィルムを、60℃の恒温槽で30分保持した後、ついで-20℃の恒温槽で30分保持し、再び60℃の恒温槽で保持するという、-20℃⇔60℃の状態をそれぞれ30分間保持するサイクルサーモ耐久(60℃→-20℃→60℃で1サイクル)を300回繰り返して、耐久後のフィルムを、23℃55%RHの条件下、下記基準で評価した。
△・・・僅かにヘーズの上昇が見られ、クラックの発生がない
×・・・ヘーズの上昇が見られる、またはクラックの発生がある
(カッティング性)
23℃、55%RHの空調室で24時間調湿した試料を、同条件下、軽荷重引き裂き(エルメンドルフ)試験機(東洋精機(株)製)を用いてフィルムを引き裂き、以下のように評価した。
作製したフィルムに関して、23℃、55%RHの空調室で24時間調湿したフィルム外観を目視で評価し、以下のように評価した。
△:ややツレや皺、段が確認できる
×:はっきりとツレや皺、段が確認できる
(偏光板の作製)
厚さ120μmの長尺ロールポリビニルアルコールフィルムを沃素1質量部、ホウ酸4質量部を含む水溶液100質量部に浸漬し、50℃で5倍に搬送方向に延伸して偏光膜を作った。次に、この偏光膜の片面にアクリル接着剤を用いて、実施例1で作製したアクリル樹脂含有フィルム1にコロナ処理を施したのち、貼合した。更に偏光膜のもう一方の面にアルカリケン化処理した位相差フィルムであるコニカミノルタオプト社製KC8UCR-5を貼り合わせ、乾燥して偏光板1を作製した。同様にしてアクリル樹脂含有フィルム2~44を用いて偏光板2~44を作製した。
〈液晶表示装置の作製〉
シャープ(株)製32型テレビAQ-32AD5の予め貼合されていた両面の偏光板を剥がして、上記作製した偏光板をそれぞれKC8UCR-5が液晶セルのガラス面側になるように、かつ、予め貼合されていた偏光板と同一の方向に吸収軸が向くように貼合し、液晶表示装置を各々作製した。
以上のようにして作製した液晶表示装置1~45を用いて下記の評価を行った。
○:視野角変動が僅かに認められる
△:視野角変動が認められる
×:視野角変動が非常に大きい
(カラーシフト)
上記記載の視野角評価と同様に偏光板を貼り付け、液晶表示装置1~43を作製した。
次に、ディスプレイを黒表示にし、斜め45°の角度から観察した際の色変化を23℃、55%RHの環境下、下記基準で評価した。
○:色変化が僅かに認められる
△:色変化が認められる
×:色変化が非常に大きい
以上の評価の結果を表2~表4に示す。
Claims (6)
- アクリル樹脂(A)およびセルロースエステル樹脂(B)の一種類ずつ、並びに、(A)、(B)および(A)、(B)以外であってガラス転移温度Tgが120℃以上300℃以下の樹脂(D)から選択される少なくとも1種類以上の樹脂からなるアクリル樹脂含有フィルムであって、該アクリル樹脂含有フィルムのヘーズが2%未満、張力軟化点が120~150℃で延性破壊を起こさないことを特徴とするアクリル樹脂含有フィルム。
- 前記アクリル樹脂含有フィルムが、アクリル樹脂(A)を30~90質量%、セルロースエステル樹脂(B)を5~65質量%、(A)、(B)以外であってガラス転移温度Tgが120℃以上300℃以下の樹脂(D)を0~50質量%含有することを特徴とする請求の範囲第1項に記載のアクリル樹脂含有フィルム。
- 前記アクリル樹脂(A)の重量平均分子量(Mw)が80000~1000000であり、前記セルロースエステル樹脂(B)の少なくとも一種が、アシル基の総置換度(T)が2.00~2.99であり、アセチル基置換度(ac)が0.10~1.89であって、アセチル基以外の部分が、3~7の炭素数で構成されるアシル基で置換されており、その置換度(r)が1.10~2.89で、重量平均分子量(Mw)が75000~250000であることを特徴とする請求の範囲第1項に記載のアクリル樹脂含有フィルム。
- ヘーズ値が1%未満であることを特徴とする請求の範囲第1項または第2項に記載のアクリル樹脂含有フィルム。
- 請求の範囲第1項乃至第3項のいずれか1項に記載のアクリル樹脂含有フィルムを少なくとも一方の面に用いたことを特徴とする偏光板。
- 請求の範囲第1項乃至第3項のいずれか1項に記載のアクリル樹脂含有フィルムを使用したことを特徴とする液晶表示装置。
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JP2009179731A (ja) * | 2008-01-31 | 2009-08-13 | Konica Minolta Opto Inc | アクリル樹脂含有フィルム、それを用いた偏光板及び表示装置 |
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JP2013538931A (ja) * | 2010-10-06 | 2013-10-17 | インヴィスタ テクノロジーズ エスアエルエル | セルロースエステルを含むポリマー組成物 |
JP2016172867A (ja) * | 2010-10-06 | 2016-09-29 | インヴィスタ テクノロジーズ エスアエルエル | セルロースエステルを含むポリマー組成物 |
JP2012215688A (ja) * | 2011-03-31 | 2012-11-08 | Fujifilm Corp | 光学フィルムとその製造方法、偏光板および液晶表示装置 |
JP2013174851A (ja) * | 2011-04-21 | 2013-09-05 | Fujifilm Corp | 偏光板および液晶表示装置 |
JPWO2015064732A1 (ja) * | 2013-11-01 | 2017-03-09 | 富士フイルム株式会社 | 偏光板保護フィルム、ドープ組成物、偏光板保護フィルムの製造方法、偏光板ならびに液晶表示装置 |
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JP2022153396A (ja) * | 2016-09-27 | 2022-10-12 | エルジー エムエムエー コープ. | 光学フィルム製造用のドープ溶液およびこれを用いた光学フィルム |
Also Published As
Publication number | Publication date |
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KR20100105741A (ko) | 2010-09-29 |
CN101925641B (zh) | 2012-11-21 |
KR101497753B1 (ko) | 2015-03-02 |
CN101925641A (zh) | 2010-12-22 |
US20100292368A1 (en) | 2010-11-18 |
JPWO2009096070A1 (ja) | 2011-05-26 |
US8168702B2 (en) | 2012-05-01 |
JP5521552B2 (ja) | 2014-06-18 |
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