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WO2009150910A1 - Procédé pour produire un film acrylique et film acrylique produit par le procédé de production - Google Patents

Procédé pour produire un film acrylique et film acrylique produit par le procédé de production Download PDF

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Publication number
WO2009150910A1
WO2009150910A1 PCT/JP2009/058562 JP2009058562W WO2009150910A1 WO 2009150910 A1 WO2009150910 A1 WO 2009150910A1 JP 2009058562 W JP2009058562 W JP 2009058562W WO 2009150910 A1 WO2009150910 A1 WO 2009150910A1
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WIPO (PCT)
Prior art keywords
acrylic
film
resin
mass
acrylic film
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2009/058562
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English (en)
Japanese (ja)
Inventor
正高 瀧本
伸夫 久保
隆 建部
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Konica Minolta Opto Inc
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Konica Minolta Opto Inc
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Priority to JP2010516797A priority Critical patent/JP5333447B2/ja
Priority to KR1020107027397A priority patent/KR101523804B1/ko
Publication of WO2009150910A1 publication Critical patent/WO2009150910A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/28—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on an endless belt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/08—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique transverse to the direction of feed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/08—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
    • C08B3/18—Aceto-butyrates
    • 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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2001/00—Use of cellulose, modified cellulose or cellulose derivatives, e.g. viscose, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of 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
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/10—Esters of organic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • 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
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate

Definitions

  • the present invention relates to a method for producing an acrylic film, and particularly to a method for improving the flexibility and brittleness of an acrylic film used as an optical film containing an acrylic resin.
  • PMMA polymethyl methacrylate film
  • Patent Document 1 As a countermeasure, it has been proposed to mix acrylic rubber or butyl-modified cellulose ester as a toughness improver with an acrylic resin (Patent Document 1).
  • Patent Document 2 a technique has been proposed in which the acrylic resin itself has a new structure and is subjected to a stretching treatment.
  • Patent Document 3 Also known is a method of imparting flexibility by adding elastic particles to a specific acrylic film and further heat-treating.
  • Patent Document 4 A technique of mixing a flexible resin having a glass transition temperature of 10 ° C. or lower instead of elastic particles has also been proposed (Patent Document 4).
  • the method of Patent Document 2 can be applied only to a specific acrylic resin, has a small effect, and lacks versatility.
  • Patent Document 3 has a problem that the time required for the heat treatment is very long and the surface properties of the produced acrylic film are inferior.
  • the heat resistance is remarkably lowered, and when such an acrylic film is used, for example, in a liquid crystal display device, the film is deformed by continuous use for a long time, and a clear image cannot be displayed. There was a thing.
  • Patent Document 4 is effective for a specific acrylic resin having a lactone ring structure, and since it is premised on melt casting, the surface property does not exceed the level of Patent Document 2. It was. Further, as in Patent Document 2, there is a problem that the heat resistance is remarkably lowered.
  • the acrylic resin (A) and the cellulose ester resin (B) are contained in a mass ratio of 95: 5 to 30:70, the acrylic resin (A) has a weight average molecular weight Mw of 80000 to 1000000, and the cellulose ester resin
  • the total substitution degree (T) of the acyl group in (B) is 2.0 or more and 3.0 or less, the substitution degree of the acyl group having 3 to 7 carbon atoms is 1.2 or more and 3.0 or less, and the weight average molecular weight Mw
  • a method for producing an acrylic film comprising producing a resin composition having a thickness of 75,000 or more and 300000 or less under the following conditions. (1) 10 ° C. ⁇ stretching temperature ⁇ tensile softening point of resin composition ⁇ 100 ° C.
  • the present invention provides a technique for imparting flexibility applicable to general-purpose acrylic resins such as PMMA.
  • the acrylic resin used in the present invention includes a methacrylic resin.
  • the resin is not particularly limited, but a resin comprising 50 to 99% by mass of methyl methacrylate units and 1 to 50% by mass of other monomer units copolymerizable therewith is preferable.
  • 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.
  • Unsaturated group-containing divalent carboxylic acids such as saturated acid, maleic acid, fumaric acid and itaconic acid, aromatic vinyl compounds such as styrene and ⁇ -methylstyrene, ⁇ , ⁇ -unsaturated nitriles such as acrylonitrile and methacrylonitrile, Examples thereof include maleic anhydride, maleimide, N-substituted maleimide, glutaric anhydride and the like, and these can be used alone or in combination of two or more monomers.
  • 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 film of the present invention has a weight average molecular weight (Mw) particularly from the viewpoint of improving brittleness as an acrylic film and improving transparency when it is compatible with the cellulose ester resin (B). Is 80,000 or more and 1,000,000 or less.
  • the weight average molecular weight (Mw) of the acrylic resin (A) is particularly preferably in the range of 100,000 to 600,000, and most preferably in the range of 150,000 to 400,000.
  • the weight average molecular weight of the acrylic resin of the present invention can be measured by gel permeation chromatography (GPC).
  • the measurement conditions are as follows.
  • the acrylic resin (A) in this invention can manufacture by a well-known method. Any known method such as suspension polymerization, emulsion polymerization, bulk polymerization, or solution polymerization may be used.
  • acrylic resins can be used as the acrylic resin according to 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.
  • Two or more acrylic resins can be used in combination.
  • the cellulose ester resin (B) of the present invention has a total acyl group substitution degree (T) of 2.0 to 3.3 from the viewpoint of transparency particularly when it is improved in brittleness and is compatible with the acrylic resin (A).
  • the substitution degree of the acyl group having 0 and 3 to 7 carbon atoms is preferably 1.2 to 3.0, and the substitution degree of the acyl group having 3 to 7 carbon atoms is preferably 2.0 to 3.0. .
  • the cellulose ester resin of the present invention is a cellulose ester resin substituted with an acyl group having 3 to 7 carbon atoms.
  • an acyl group having 3 to 7 carbon atoms Specifically, propionyl, butyryl and the like are preferably used, but a propionyl group is particularly preferably used. .
  • the acrylic ester When the total substitution degree of the acyl group of the cellulose ester resin (B) is less than 2.0, that is, when the residual degree of the hydroxyl groups at the 2, 3, and 6 positions of the cellulose ester molecule is more than 1.0, the acrylic ester When the resin (A) and the acrylic resin (B) are not sufficiently compatible and used as an optical film, haze becomes a problem.
  • the substitution degree of the acyl group having 2 carbon atoms that is, the acetyl group is high
  • the substitution degree of the acyl group having 3 to 7 carbon atoms is 1.
  • it is less than 2 the compatibility is lowered and the haze is increased.
  • the total substitution degree (T) is 2.0 to 3.0, and the substitution degree of the acyl group having 3 to 7 carbon atoms is 1.2 to 3. If it is 0.0, there is no problem, but the total degree of substitution of acyl groups other than those having 3 to 7 carbon atoms, that is, acetyl groups or acyl groups having 8 or more carbon atoms, is preferably 1.3 or less.
  • the total substitution degree (T) of the acyl group of the cellulose ester resin (B) is more preferably in the range of 2.5 to 3.0.
  • the acyl group may be an aliphatic acyl group or an aromatic acyl group.
  • an aliphatic acyl group it may be linear or branched and may further have a substituent.
  • the number of carbon atoms of the acyl group in the present invention includes an acyl group substituent.
  • the number of substituents X substituted on the aromatic ring is 0 to 3.
  • the substitution degree of the acyl group having 3 to 7 carbon atoms including the substituent is 1.2 to 3.0.
  • the benzoyl group has 7 carbon atoms, when it has a substituent containing carbon, the benzoyl group has 8 or more carbon atoms and is not included in the acyl group having 3 to 7 carbon atoms. Become.
  • 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.
  • a structure having at least one kind of an aliphatic acyl group having 3 to 7 carbon atoms is used as a structure used in the cellulose resin of the present invention.
  • the substitution degree of the cellulose ester resin (B) according to the present invention is such that the total substitution degree (T) of acyl groups is 2.0 to 3.0, and the substitution degree of acyl groups having 3 to 7 carbon atoms is 1.2 to 3.0. 3.0.
  • the total substitution degree of acyl groups other than an acyl group having 3 to 7 carbon atoms, that is, an acetyl group and an acyl group having 8 or more carbon atoms is 1.3 or less.
  • the cellulose ester resin (B) according to the present invention is preferably at least one selected from cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzoate, cellulose propionate, and cellulose butyrate, Those having an acyl group having 3 or 4 carbon atoms as a substituent are preferred.
  • particularly preferable cellulose ester resins are cellulose acetate propionate and cellulose propionate.
  • 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 according to the present invention is in the range of 75,000 to 300,000, particularly in the range of 100,000 to 24,000, from the viewpoint of improving compatibility with the acrylic resin (A) and improving brittleness. Are more preferable, and those of 160000 to 240000 are particularly preferable.
  • the important average molecular weight (Mw) of the cellulose ester resin is less than 75,000, the effect of improving the heat resistance and brittleness is not sufficient, and the effect of the present invention cannot be obtained.
  • Mw important average molecular weight
  • two or more kinds of cellulose resins can be mixed and used.
  • the acrylic resin (A) and the cellulose ester resin (B) are contained in a mass ratio of 95: 5 to 30:70 and in a compatible state, preferably 95: 5 to 50. : 50, more preferably 90:10 to 60:40.
  • the mass ratio of the acrylic resin (A) and the cellulose ester resin (B) is more than 95: 5
  • the effect of the cellulose ester resin (B) cannot be sufficiently obtained, and the mass ratio is
  • the amount of acrylic resin is less than 30:70, the moisture resistance becomes insufficient.
  • the acrylic resin (A) and the cellulose ester resin (B) must be contained in a compatible state.
  • the physical properties and quality required for an optical film are achieved by supplementing each other by dissolving different resins.
  • each resin When both resins are simply mixed, there are two glass transition temperatures for each resin because there is a glass transition temperature for each resin. However, when both resins are compatible, each glass has its own glass transition temperature. The temperature disappears and becomes one glass transition temperature, which becomes the glass transition temperature of the compatible resin.
  • the glass transition temperature referred to here is a nitrogen gas stream obtained by using a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer Co., Ltd.) for 24 hours in an atmosphere of 23 ° C. and 55% RH. Medium, measured at a heating rate of 20 ° C./min, and defined as the midpoint glass transition temperature (Tmg) determined according to JIS K7121 (1987).
  • DSC-7 differential scanning calorimeter
  • the acrylic resin (A) and the cellulose ester resin (B) are each preferably an amorphous resin, and either one may be a crystalline polymer or a partially crystalline polymer. In the present invention, the acrylic resin (A) and the cellulose ester resin (B) are preferably compatible with each other to become an amorphous resin.
  • containing acrylic resin (A) and cellulose ester resin (B) in a compatible state means mixing each resin (polymer) to result in a compatible state.
  • a state in which a precursor of acrylic resin such as monomer, dimer, or oligomer is mixed with cellulose ester resin (B) and then polymerized to be mixed resin is not included.
  • the process of obtaining a mixed resin by mixing a precursor of an acrylic resin such as a monomer, dimer or oligomer with the cellulose ester resin (B) and then polymerizing it is complicated by the polymerization reaction.
  • the resin is difficult to control the reaction, and it is difficult to adjust the molecular weight.
  • the acrylic film of the present invention may contain a resin and additives other than the acrylic resin (A) and the cellulose ester resin (B) as long as the function as an optical film is not impaired.
  • the resin to be added may be mixed without being dissolved even if it is in a compatible state.
  • the total mass of the acrylic resin (A) and the cellulose ester resin (B) in the acrylic film of the present invention is preferably 55% by mass or more of the acrylic film, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.
  • the acrylic film of the present invention preferably contains acrylic particles (C).
  • the acrylic particles (C) according to the present invention are present in a state of particles (also referred to as an incompatible state) in an acrylic film containing the acrylic resin (A) and the cellulose ester resin (B) in a compatible state. Represents an acrylic component.
  • the acrylic particles (C) are obtained, for example, by collecting a predetermined amount of the prepared acrylic film, dissolving in a solvent, stirring, and sufficiently dissolving / dispersing the acrylic particles (C) with a pore size less than the average particle size. It is preferable that the weight of the insoluble matter filtered and collected using a PTFE membrane filter is 90% by mass or more of the acrylic particles (C) added to the acrylic 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.
  • the multi-layer structure acrylic granular composite is a multi-layer structure acrylic granular composite including an innermost hard layer, a crosslinked soft layer, and an outermost hard layer from the center to the outer periphery.
  • This three-layer core-shell multilayer acrylic granular composite is preferably used.
  • Preferred embodiments of the multilayer structure acrylic granular composite used in the acrylic resin composition according to the present invention include the following.
  • a crosslinked soft layer polymer obtained by polymerizing a mixture of monomers comprising 0.01 to 5% by mass of a polyfunctional crosslinking agent and 0.5 to 5% by mass of a polyfunctional grafting agent, (c) In the presence of a polymer comprising an inner hard layer and a crosslinked soft layer, a monomer mixture comprising 80 to 99% by weight of methyl methacrylate and 1 to 20% by weight of alkyl acrylate having 1 to 8 carbon atoms in the alkyl group. Obtained by polymerizing A three-layer structure comprising a hard layer polymer, and the obtained three-layer structure polymer is an innermost hard layer polymer (a) 5 to 40% by mass, and a soft layer polymer (b) 30 to 60% by mass. And an outermost hard layer polymer (c) of 20 to 50% by mass, having an insoluble part when fractionated with acetone, and a methyl ethyl ketone swelling degree of the insoluble part being 1.5 to 4.0 Granular composites.
  • 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 mixture of monomers consisting of 0.01 to 0.3% by weight 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 proportion of the alkyl acrylate unit in the innermost hard layer polymer (a) is 1 to 20% by mass.
  • the thermal decomposability of the polymer is increased, while the unit is 20% by mass. If it exceeds 50%, the glass transition temperature of the innermost hard layer polymer (c) is lowered, and the impact resistance imparting effect of the three-layer structure acrylic granular composite is lowered.
  • 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 mixture of monomers comprising, by mass, 0.01 to 5% by mass of a polyfunctional crosslinking agent and 0.5 to 5% by mass of a polyfunctional 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.
  • styrene and substituted styrene derivatives Regarding the ratio of alkyl acrylate having 4 to 8 carbon atoms in the alkyl group and styrene, the more the former, the lower the glass transition temperature of the polymer (b), that is, the softer it is.
  • 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 contains 80 to 99 mass% of methyl methacrylate in the presence of the innermost hard layer polymer (a) and the soft layer polymer (b). % And a mixture of monomers consisting of 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 outermost hard layer is divided into two or more monomer mixtures for forming the outermost hard layer, and the amount of chain transfer agent to be added each time is increased sequentially. It is possible to decrease the molecular weight of the polymer forming the layer from the inside to the outside of the multilayer structure acrylic granular composite.
  • the molecular weight formed at this time can also be examined by polymerizing a mixture of monomers used each time under the same conditions, and measuring the molecular weight of the resulting polymer.
  • the particle diameter of the acrylic particles (C) 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. In particular, the thickness is most preferably from 50 nm to 400 nm.
  • 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.
  • the core layer here is an innermost hard layer.
  • 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. Mixtures of monomers consisting of acid ester monomers, unsaturated carboxylic acid monomers, aromatic vinyl monomers, and other vinyl monomers copolymerizable with these if necessary Examples thereof include a graft copolymer obtained by copolymerization.
  • 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.
  • polystyrene-butadiene copolymer block copolymer of styrene-butadiene, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, polyisoprene, butadiene-methyl methacrylate copolymer, Butyl acrylate-methyl methacrylate copolymer, butadiene-ethyl acrylate copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-isoprene copolymer, and ethylene-methyl acrylate copolymer A polymer etc. are mentioned.
  • Rubbery polymers can be used alone or in a mixture of two or more.
  • the refractive index of the mixture of an acrylic resin (A) and a cellulose-ester resin (B) and the refractive index of an acrylic particle (C) must be near. From the viewpoint of obtaining a film with high transparency.
  • the difference in refractive index 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), or the composition of the rubbery polymer or monomer used in the acrylic particles (C) The difference in refractive index can be reduced by a method of adjusting the ratio, and an acrylic film having excellent transparency can be obtained.
  • the refractive index difference referred to here is a solution in which the acrylic film of the present invention is sufficiently dissolved under a suitable condition in a solvent in which the acrylic resin (A) is soluble. After separating the solvent-soluble part and the insoluble part and purifying the soluble part (acrylic resin (A)) and insoluble part (acrylic particles (C)), the measured refractive index (23 ° C., measuring wavelength: 550 nm). ) Difference.
  • 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 method in which 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 according to the present invention.
  • Metabrene W-341 C2 (Mitsubishi Rayon Co., Ltd.), Chemisnow MR-2G (C3), MS-300X (C4) (Soken Chemicals Co., Ltd.), Kaneka Chemical Co., Ltd. "Paraloid” manufactured by Kureha Chemical Co., Ltd., "Acryloid” manufactured by Rohm and Haas, "Staffyroid” manufactured by Gantz Kasei Kogyo Co., and "Parapet SA” manufactured by Kuraray.
  • the acrylic film of the present invention preferably contains 0.5 to 30% by mass of acrylic particles (C) with respect to the total mass of the resin constituting the film, and is in the range of 1.0 to 15% by mass. It is more preferable to contain.
  • the acrylic film of this invention in order to improve the fluidity
  • the plasticizer 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. These 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 10,000, and preferably in the range of 600 to 3000, which has a large plasticizing effect.
  • 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.
  • polyesters described in paragraphs 0103 to 0116 of JP-A-2007-231157 and the above-described polyester plasticizers can be preferably used.
  • a sugar ester plasticizer obtained by esterifying a hydroxyl group of a sugar compound in which at least one type of structure of a selective extruder is bonded from a furanose structure and a pyranose structure.
  • sugar ester compound used in the present invention examples include glucose, galactose, mannose, fructose, xylose, arabinose, lactose, sucrose, cellobiose, cellotriose, maltotriose, raffinose, etc., particularly both furanose structure and pyranose structure. What has is preferable.
  • An example is sucrose.
  • Examples of commercially available products include Monopet SB (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
  • 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 acrylic film of the present invention. If the added amount of the plasticizer exceeds 30 parts by mass, the surface becomes sticky, which is not preferable for practical use.
  • the acrylic film 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.
  • 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.
  • 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 film of the present invention in order to improve the thermal decomposability and thermal colorability during molding. It is also possible to add an antistatic agent to impart antistatic performance to the acrylic 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.
  • the acrylic film of the present invention it is possible to simultaneously achieve improvements in low hygroscopicity, transparency, high heat resistance and brittleness that could not be achieved with conventional resin films.
  • the brittleness index is determined based on the criterion of whether or not it is “an acrylic film that does not cause ductile fracture”.
  • an acrylic film with improved brittleness that does not cause ductile fracture even when creating a polarizing plate for a large-sized liquid crystal display device, it does not break or crack during production and has excellent handling properties. It can be an acrylic film.
  • the ductile fracture is a fracture that occurs due to a stress that is greater than the strength of a certain material, and is defined as a fracture that involves significant elongation or drawing of the material before the final fracture.
  • the fracture surface is characterized by numerous indentations called dimples.
  • the film is an “acrylic film that does not cause ductile fracture” is evaluated based on the fact that no breakage or the like is observed even when a large stress is applied such that the film is folded in two. .
  • the tension softening point is used as an index of heat resistance.
  • the tension softening point is 105 ° C. to 145 ° C., it can be determined that sufficient heat resistance is exhibited. In particular, it is more preferable to control at 110 ° C. to 130 ° C.
  • the acrylic film is cut into 120 mm (length) ⁇ 10 mm (width).
  • the temperature can be raised at a rate of 30 ° C./min while pulling with a tension of 10 N, and the temperature at the time when the pressure reaches 9 N is measured three times, and the average value can be obtained.
  • the acrylic film preferably has a glass transition temperature (Tg) of 110 ° C. or higher. More preferably, it is 120 ° C. or higher. Especially preferably, it is 150 degreeC or more.
  • Tg glass transition temperature
  • Haze value (turbidity) is used as an index for judging the transparency of the acrylic film in the present invention.
  • the haze value is required to be 1.0% or less, and 0.5% or less. More preferably.
  • the acrylic film of the present invention containing the acrylic resin (A) and the cellulose ester resin (B), high transparency can be obtained, but when using acrylic particles for the purpose of improving another physical property.
  • acrylic particles for the purpose of improving another physical property.
  • the particle diameter and addition amount of acrylic particles (C) should be kept within the above range, and the surface roughness of the film contact portion during film formation should be reduced. Is also effective.
  • the hygroscopicity of the acrylic film in the present invention is evaluated by a dimensional change with respect to a humidity change.
  • the following method is used as an evaluation method of dimensional change with respect to humidity change.
  • the dimensional change rate (%) is expressed by the following formula.
  • Dimensional change rate (%) [(a1-a2) / a1] ⁇ 100 a1: Distance before heat treatment a2: Distance after heat treatment
  • a1 Distance before heat treatment
  • a2 Distance after heat treatment
  • the above-mentioned problem becomes remarkable if it is a polarizing plate protective film used for a liquid crystal display device used outdoors.
  • the dimensional change rate (%) under the above conditions is less than 0.5%, it can be evaluated that the acrylic film exhibits sufficiently low hygroscopicity. Furthermore, it is preferable that it is less than 0.3%.
  • the acrylic film of the present invention preferably has a defect with a diameter of 5 ⁇ m or more in the film plane of 1 piece / 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 surface shape, such as a transfer of a roll flaw or a scratch
  • the film When the number of defects is more than 1/10 cm square, for example, when a tension is applied to the film during processing in a later process, the film may be broken with the defect as a starting point and productivity may be reduced.
  • the diameter of the defect is 5 ⁇ m or more, it can be visually confirmed by polarizing plate observation or the like, and a bright spot may be generated when used as an optical member.
  • 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 film of the present invention preferably has a breaking elongation in at least one direction of 10% or more, more preferably 20% or more in the measurement based on 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 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 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 film of the present invention can be particularly preferably used as a polarizing plate protective film for a large-sized liquid crystal display device or a liquid crystal display device for outdoor use as long as the above physical properties are satisfied.
  • Such physical properties include an acrylic film containing an acrylic resin (A) and a cellulose ester resin (B) in a mass ratio of 95: 5 to 30:70, and the acrylic resin (A) has a weight average molecular weight Mw of 80000.
  • the total substitution degree (T) of the acyl group of the cellulose ester resin (B) is 2.00 to 3.00, and the substitution degree of the acyl group having 3 to 7 carbon atoms is 1.2 to 3.0.
  • the weight average molecular weight (Mw) is 75000 or more.
  • 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 standpoint of suppressing optical defects such as die lines and optical defects such as die lines, solution casting by casting is preferred.
  • Organic solvent useful for forming the dope when the acrylic film of the present invention is produced by the solution casting method is one that simultaneously dissolves the acrylic resin (A), the cellulose ester resin (B), and other additives. It can be used without any 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).
  • acrylic resin (A), cellulose ester resin (B), and acrylic particles (C) 3 A dope composition in which at least 15 to 45% by mass of the seed is dissolved is preferable.
  • 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.
  • a method carried out at normal pressure a method carried out below the boiling point of the main solvent, a method carried out under pressure above the boiling point of the main solvent, JP-A-9-95544
  • Various dissolution methods such as a method of performing a cooling dissolution method as described in JP-A-9-95557 or JP-A-9-95538, a method of performing at a high pressure as described in JP-A-11-21379, and the like.
  • a method in which pressure is applied at a temperature equal to or higher than the boiling point of the main solvent is particularly preferable.
  • the acrylic resin (A) and cellulose ester resin (B) in the dope are preferably in the range of 15 to 45% by mass in total.
  • 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.
  • the aggregate remaining at the time of particle dispersion and the aggregate generated when the main dope is added are 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 only be removed.
  • the concentration of particles is sufficiently thinner than that of the additive solution, so that aggregates do not stick together at the time of filtration and the filtration pressure does not increase suddenly.
  • FIG. 1 is a diagram schematically showing an example of a dope preparation step, a casting step, and a drying step of a solution casting film forming method preferable for the present invention.
  • 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.
  • the return material may contain acrylic particles. In that case, it is preferable to control the addition amount of the acrylic particle addition liquid in accordance with the addition amount of the return material.
  • the additive liquid containing acrylic particles preferably contains 0.5 to 10% by mass of acrylic particles, more preferably 1 to 10% by mass, and more preferably 1 to 5% by mass. Most preferably.
  • the additive solution is preferable because it has a low viscosity and is easy to handle and can be easily added to the main dope.
  • Recycled material is a finely pulverized acrylic film, which is generated when the acrylic film is formed, and is cut off on both sides of the film, or the original acrylic film that has been speculated out of scratches is used. .
  • acrylic resin cellulose ester resin, and in some cases, acrylic particles kneaded into pellets can be preferably used.
  • An endless metal belt 31 such as a stainless steel belt or a rotating metal drum that feeds the dope to a pressure die 30 through a liquid feed pump (for example, a pressurized metering gear pump) and transfers it indefinitely.
  • 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 back side liquid heat transfer method has a drying efficiency.
  • a method of combining them is also preferably used.
  • the web on the support after casting is preferably dried on the support in an atmosphere of 40 to 100 ° C. In order to maintain the atmosphere at 40 to 100 ° C., it is preferable to apply hot air at this temperature to the upper surface of the web or heat by means such as infrared rays.
  • 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 amount of residual solvent at the time of peeling of the web on the metal support at the time of peeling is preferably 50 to 120% by mass depending on the strength of drying conditions, the length of the metal support, and the like. If the web is peeled off at a time when the amount of residual solvent is larger, if the web is too soft, the flatness at the time of peeling will be lost, and slippage and vertical stripes are likely to occur due to the peeling tension. The amount of 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 and 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.
  • 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. Rapid drying tends to impair the flatness of the finished film. Drying at a high temperature is preferably performed from about 8% by mass or less of the residual solvent. Throughout, drying is generally performed at 40-250 ° C. In particular, drying at 40 to 160 ° C. is preferable.
  • the stretching is preferably performed with a clip tenter, but a pin tenter can also be used.
  • stretching is preferably performed under the following conditions.
  • the stretching temperature is too low, the brittleness deteriorates. In this case, an unnecessarily stress is generated at the time of stretching, and the polymer molecules are excessively oriented, and this orientation is not preferable because it is easy to tear in the direction parallel to the stretching.
  • the temperature is too high, polymer entanglement will not occur, which is not preferable. In addition, when the temperature is too high, the polymer may flow or deteriorate.
  • voids may be partially generated, and this void is not preferable because it causes haze increase, cracking, and tearing and deteriorates brittleness.
  • tenter apparatus When using a tenter apparatus for stretching, it is preferable to use an apparatus that can independently control 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. In the tenter process, it is also preferable to intentionally create sections having different temperatures in order to improve planarity.
  • 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 stretching speed is preferably 10% to 500% / min depending on the web conveyance speed. If the stretching speed is too slow, no stress is applied when the molecular chain of the polymer is moved, so that the molecular chain slides and entanglement hardly occurs, and brittleness has little improvement effect. If the stretching speed is too high, stress is applied too much and the movement of the molecular chain of the polymer cannot catch up, and voids may be partially generated.
  • the heat transfer coefficient may be constant or may be changed.
  • the heat transfer coefficient preferably has a heat transfer coefficient in the range of 41.9 to 419 ⁇ 103 J / m 2 hr. More preferably, the range is 41.9 to 209.5 ⁇ 10 3 J / m 2 hr, and the most preferable range is 41.9 to 126 ⁇ 10 3 J / m 2 hr.
  • the cellulose ester resin is hardly effective with little improvement in brittleness.
  • the tension softening point of the resin is relatively high, it is necessary to stretch the resin at a high temperature.
  • the resin may decompose and the strength may decrease.
  • the compatibility of the resin to be blended with the acrylic resin is very important. If the resin is not uniformly compatible, there is almost no effect of improving brittleness.
  • the total substitution degree (T) of the acyl group of cellulose-ester resin shall be 2.0 or more and 3.0 or less, and the substitution degree of the acyl group whose carbon number is 3 or more and 7 or less shall be 1.2 or more and 3.0 or less.
  • the weight average molecular weight Mw of the acrylic resin is preferably 80000 or more, and the cellulose ester resin weight average molecular weight Mw is 75000 or more. preferable.
  • the weight average molecular weight Mw of the acrylic resin is preferably 1000000 or less, and the weight average molecular weight Mw of the cellulose ester resin is preferably 300000 or less.
  • the amount of residual solvent in the web is preferably 20 to 100% by mass at the start of the tenter, and drying is performed while applying a tenter until the amount of residual solvent in the web is 10% by mass or less. Is more preferable, and more preferably 5% by mass or less.
  • 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 the step of winding the acrylic film as an acrylic film by the winder 37 after the residual solvent amount in the web is 2% by mass or less.
  • the dimensional stability is achieved by setting the residual solvent amount to 0.4% by mass or less.
  • a film having good properties can be obtained. It is particularly preferable to wind up at 0.00 to 0.10% by mass.
  • 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 film of the present invention is preferably a long film.
  • the acrylic film has a thickness of about 100 m to 5000 m and is usually provided in a roll shape.
  • the film width is preferably 1.3 to 4 m, more preferably 1.4 to 2 m.
  • the thickness of the acrylic film of the present invention is not particularly limited, but when used for the 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.
  • a polarizing plate When using the acrylic film of this invention as a protective film for polarizing plates, a polarizing plate can be produced by a general method. It is preferable that an adhesive layer is provided on the back side of the acrylic 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.
  • the acrylic film of the present invention may be used for the other surface, or another polarizing plate protective film may be used.
  • a commercially available cellulose ester film for example, Konica Minoltack KC8UX, KC4UX, KC5UX, KC8UY, KC4UY, KC12UR, KC8UCR-3, KC8UCR-4, KC8UCR-5, KC8UE, KC4FR-4, KC4FR-3, KC4FR-3, KC4FR-4 -1, KC8UY-HA, KC8UX-RHA, manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used.
  • 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.
  • a pressure-sensitive adhesive 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 pressure-sensitive adhesive layer is used. It is preferable to use a curable pressure-sensitive adhesive that forms a high molecular weight body or a crosslinked structure by various chemical reactions after the pressure-sensitive adhesive 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-curing urethane adhesives, polyether methacrylate types
  • curable adhesives such as thermosetting acrylic adhesives, moisture-curing urethane adhesives, polyether methacrylate types
  • anaerobic pressure-sensitive adhesives such as ester-based methacrylate type and oxidized polyether methacrylate, cyanoacrylate-based instantaneous pressure-sensitive adhesives, and acrylate-peroxide-based two-component instantaneous pressure-sensitive adhesives.
  • the above-mentioned pressure-sensitive adhesive may be a one-component type or a type in which two or more components are mixed before use.
  • the pressure-sensitive 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.
  • concentration of the pressure-sensitive adhesive liquid may be appropriately determined depending on the film thickness after adhesion, the coating method, the coating conditions, and the like, and is usually 0.1 to 50% by mass.
  • polarizing plate By incorporating the polarizing plate bonded with the acrylic film of the present invention into a liquid crystal display device, it is possible to produce various liquid crystal display devices with excellent visibility, but particularly outdoors such as large liquid crystal display devices and digital signage. It is preferably used for a liquid crystal display device for use.
  • 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 includes a reflective type, a transmissive type, a transflective type LCD or a TN type, an STN type, an OCB type, a HAN type, a VA type (PVA type, MVA type), an IPS type (including an FFS type), and the like. It is preferably used in LCDs of various driving methods.
  • Example 1 [Preparation of acrylic resin] The following acrylic resins A1-A7 and MS1,2 were prepared by known methods.
  • the above is charged into the reactor and the reactor is replaced with nitrogen gas.
  • the reaction was allowed to proceed at 70 ° C. until converted to.
  • the obtained aqueous solution was used as a suspending agent.
  • a solution in which 0.05 part by mass of the above suspending agent is dissolved in 165 parts by mass of ion-exchanged water is supplied to a stainless steel autoclave having a capacity of 5 liters and equipped with a baffle and a foudra-type stirring blade, and the system is filled with nitrogen gas. It stirred at 400 rpm, replacing.
  • Methacrylic acid 27 parts by weight Methyl methacrylate 73 parts by weight t-dodecyl mercaptan 1.2 parts by weight 2,2′-azobisisobutyronitrile 0.4 part by weight
  • the temperature was raised to 70 ° C. and the internal temperature was 70 ° C.
  • the time at which the polymerization was reached was set as the polymerization start time, and the polymerization was continued for 180 minutes.
  • the reaction system was cooled, the polymer was separated, washed, and dried according to the usual method to obtain a bead-shaped copolymer.
  • the polymerization rate of this copolymer was 97%, and the weight average molecular weight was 130,000.
  • an additive NaOCH3
  • an intramolecular cyclization reaction was performed at a screw rotation speed of 100 rpm, a raw material supply rate of 5 kg / hour, and a cylinder temperature of 290 ° C. to produce pellets, which were then vacuum-dried at 80 ° C. for 8 hours for acrylic resin A8
  • the acrylic resin A8 had a weight average molecular weight (Mw) of 130000 and a Tg of 140 ° C.
  • Example acrylic film 48 The acrylic resin described in Example 1 of Patent Document 3 (WO2005 / 105918) was prepared by the same method as that described in Patent Document 3, and used as a comparative acrylic film * 1 (sample acrylic film 48). .
  • Polymer 1A of Example 1 of Patent Document 4 Japanese Patent Application Laid-Open No. 2007-100044 was prepared by a method similar to the method described in Patent Document 4 and used as a comparative acrylic film * 2 (sample acrylic film 50). .
  • 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 until the amount of residual solvent reached 100%, and peeling was performed from the stainless steel band support with a peeling tension of 162 N / m.
  • the solvent was evaporated from the peeled acrylic resin web at 35 ° C., slit to 1.6 m width, and then stretched to 40% in the width direction (TD direction) while heating to 140 ° C. 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 40%.
  • the residual solvent amount of the acrylic film 1 described in Table 1 was 0.1%, the film thickness was 60 ⁇ m, and the winding length was 4000 m.
  • acyl groups of the cellulose ester resin described in Table 1 are as follows: ac is an acetyl group, pr is a propionyl group, bu is a butyryl group, pen is a pentanoyl group, bz is a benzoyl group, hep is a heptanoyl group, oct is an octanoyl group, ph represents a phthalyl group.
  • an acrylic film 51 which is an acrylic resin film, was produced in the same manner except that the dope composition was changed to the following.
  • the acrylic film was cut out at 120 mm (length) ⁇ 10 mm (width), and heated at a rate of temperature increase of 30 ° C./min while being pulled with a tension of 10 N, and the temperature at the time when it reached 9 N was measured three times. Averaged.
  • ⁇ Cannot be folded 5 times
  • ⁇ Can be folded 1 time out of 5 times
  • ⁇ Can be folded at least 2 times out of 5 times (Film deformation: heat resistance evaluation for long-term use)
  • Each acrylic film was left in an atmosphere of 90 ° C. and DRY (relative humidity 5% RH or less) for 1000 hours, and then the degree of film deformation was visually observed and evaluated according to the following criteria.
  • Dimensional change rate (%) [(a1-a2) / a1] ⁇ 100
  • a1 represents a distance before heat treatment
  • a2 represents a distance after heat treatment.
  • slitting property Less than 0.3% ⁇ : 0.3% or more, less than 0.5% ⁇ : 0.5% or more (slitting property)
  • the evaluation of slitting was performed by measuring the number of ruptures during slitting using a slit width of 50 mm, a slit speed of 10 m / min, a tension of 5 kg, and an upper blade / lower blade method as a slit method.
  • ⁇ The number of breaks is 10 or less; almost no breakage occurs in the actual process, and preferable ⁇ : The number of breaks is 11 to 20; breakage sometimes occurs in the actual process, but somehow practical level ⁇ : the breakage described above Number of times 21 or more: It was found that breakage frequently occurred in an actual process and was not practical, and this was evaluated.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Polarising Elements (AREA)

Abstract

La présente invention concerne un procédé pour produire efficacement un film acrylique ayant d'excellentes flexibilité et propriétés de surface, et un film acrylique produit par le procédé. Le procédé pour produire un film acrylique est caractérisé en ce qu'une composition de résine contenant une résine acrylique (A) et une résine d'ester de cellulose (B) à un rapport en masse de 95:5 à 30:70 est étirée dans les conditions définies ci-dessous. La résine acrylique (A) a un poids moléculaire moyen en poids Mw de pas moins de 80 000 mais pas plus de 1 000 000 ; et la résine d'ester de cellulose (B) a un degré de substitution total (T) de groupes acyle de pas moins de 2,0 mais pas plus de 3,0, un degré de substitution de groupes acyle ayant de 3 à 7 atomes de carbone de pas moins de 1,2 mais pas plus de 3,0, et un poids moléculaire moyen en poids Mw de pas moins de 75 000 mais pas plus de 300 000. 1. 10 °C = température d'étirage - point de ramollissement sous tension de la composition de résine = 100 °C 2. 20 % = taux d'étirage d'au moins l'une de la direction machine ou la direction transversale = 100 % 3. 40 % = taux d'étirage de la direction machine + taux d'étirage de la direction transversale = 200 %
PCT/JP2009/058562 2008-06-10 2009-05-01 Procédé pour produire un film acrylique et film acrylique produit par le procédé de production Ceased WO2009150910A1 (fr)

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JP2010516797A JP5333447B2 (ja) 2008-06-10 2009-05-01 アクリルフィルムの製造方法およびその製造方法によって製造したアクリルフィルム
KR1020107027397A KR101523804B1 (ko) 2008-06-10 2009-05-01 아크릴 필름의 제조 방법 및 그 제조 방법에 의해 제조한 아크릴 필름

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Cited By (10)

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JP2011046768A (ja) * 2009-08-25 2011-03-10 Nippon Shokubai Co Ltd 光学フィルムの製造方法
JP2011141353A (ja) * 2010-01-06 2011-07-21 Konica Minolta Opto Inc 光学フィルムの製造方法、光学フィルム
WO2011118145A1 (fr) * 2010-03-24 2011-09-29 コニカミノルタオプト株式会社 Procédé de production de film optique, film optique, plaque de polarisation et dispositif d'affichage à cristaux liquides
JP2012016844A (ja) * 2010-07-06 2012-01-26 Konica Minolta Opto Inc 光学フィルムの製造方法、光学フィルム、偏光板及び液晶表示装置
JP2013064813A (ja) * 2011-09-16 2013-04-11 Konica Minolta Advanced Layers Inc 偏光板保護フィルム、偏光板保護フィルムの製造方法、偏光板及び液晶表示装置
JP2013148848A (ja) * 2012-01-23 2013-08-01 Konica Minolta Inc 光学フィルムおよびその製造方法、並びにこれを用いた偏光板
US9557463B2 (en) 2013-03-08 2017-01-31 Fujifilm Corporation Optical film, polarizing plate and liquid crystal display device
JP2017097352A (ja) * 2016-12-05 2017-06-01 コニカミノルタ株式会社 光学フィルムおよびその製造方法、並びにこれを用いた偏光板
JP2017219863A (ja) * 2013-01-08 2017-12-14 コニカミノルタ株式会社 セルロースアシレートフィルムの製造方法
EP3680281A4 (fr) * 2017-09-04 2021-06-02 Hyosung Chemical Corporation Film acrylique

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JP7606489B2 (ja) * 2022-06-13 2024-12-25 日東電工株式会社 フィルムの製造システム、および、フィルムの製造方法

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WO2009047924A1 (fr) * 2007-10-13 2009-04-16 Konica Minolta Opto, Inc. Film optique
WO2009081607A1 (fr) * 2007-12-25 2009-07-02 Konica Minolta Opto, Inc. Film contenant une résine acrylique, plaque de polarisation, et afficheur à cristaux liquides utilisant ledit film
WO2009084295A1 (fr) * 2007-12-28 2009-07-09 Konica Minolta Opto, Inc. Film contenant une résine acrylique, plaque polarisante l'utilisant et dispositif d'affichage

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JPH10316767A (ja) * 1997-05-15 1998-12-02 Asahi Chem Ind Co Ltd セルロースとアクリル系重合体とのブレンド成形体及びその製造方法
JP2002356658A (ja) * 2001-05-31 2002-12-13 Nippon Carbide Ind Co Inc アクリル系オーバーレイフィルム
JP2007231157A (ja) * 2005-03-10 2007-09-13 Konica Minolta Opto Inc 光学フィルム、光学フィルムの製造方法、光学補償フィルム、光学補償フィルムの製造方法、偏光板及び液晶表示装置
WO2009047924A1 (fr) * 2007-10-13 2009-04-16 Konica Minolta Opto, Inc. Film optique
WO2009081607A1 (fr) * 2007-12-25 2009-07-02 Konica Minolta Opto, Inc. Film contenant une résine acrylique, plaque de polarisation, et afficheur à cristaux liquides utilisant ledit film
WO2009084295A1 (fr) * 2007-12-28 2009-07-09 Konica Minolta Opto, Inc. Film contenant une résine acrylique, plaque polarisante l'utilisant et dispositif d'affichage

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011046768A (ja) * 2009-08-25 2011-03-10 Nippon Shokubai Co Ltd 光学フィルムの製造方法
JP2011141353A (ja) * 2010-01-06 2011-07-21 Konica Minolta Opto Inc 光学フィルムの製造方法、光学フィルム
WO2011118145A1 (fr) * 2010-03-24 2011-09-29 コニカミノルタオプト株式会社 Procédé de production de film optique, film optique, plaque de polarisation et dispositif d'affichage à cristaux liquides
JP2012016844A (ja) * 2010-07-06 2012-01-26 Konica Minolta Opto Inc 光学フィルムの製造方法、光学フィルム、偏光板及び液晶表示装置
JP2013064813A (ja) * 2011-09-16 2013-04-11 Konica Minolta Advanced Layers Inc 偏光板保護フィルム、偏光板保護フィルムの製造方法、偏光板及び液晶表示装置
JP2013148848A (ja) * 2012-01-23 2013-08-01 Konica Minolta Inc 光学フィルムおよびその製造方法、並びにこれを用いた偏光板
JP2017219863A (ja) * 2013-01-08 2017-12-14 コニカミノルタ株式会社 セルロースアシレートフィルムの製造方法
US9557463B2 (en) 2013-03-08 2017-01-31 Fujifilm Corporation Optical film, polarizing plate and liquid crystal display device
US9885907B2 (en) 2013-03-08 2018-02-06 Fujifilm Corporation Optical film, polarizing plate and liquid crystal display device
JP2017097352A (ja) * 2016-12-05 2017-06-01 コニカミノルタ株式会社 光学フィルムおよびその製造方法、並びにこれを用いた偏光板
EP3680281A4 (fr) * 2017-09-04 2021-06-02 Hyosung Chemical Corporation Film acrylique

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