WO2009150926A1 - Procédé de production de film acrylique, et film acrylique produit selon le procédé - Google Patents

Procédé de production de film acrylique, et film acrylique produit selon le procédé Download PDF

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Publication number
WO2009150926A1
WO2009150926A1 PCT/JP2009/059343 JP2009059343W WO2009150926A1 WO 2009150926 A1 WO2009150926 A1 WO 2009150926A1 JP 2009059343 W JP2009059343 W JP 2009059343W WO 2009150926 A1 WO2009150926 A1 WO 2009150926A1
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Prior art keywords
acrylic
film
solvent
mass
acrylic film
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PCT/JP2009/059343
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English (en)
Japanese (ja)
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隆 建部
正高 瀧本
伸夫 久保
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コニカミノルタオプト株式会社
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Priority to JP2010516803A priority Critical patent/JP5447374B2/ja
Publication of WO2009150926A1 publication Critical patent/WO2009150926A1/fr

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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
    • 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
    • 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
    • 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
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • 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
    • 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

Definitions

  • the present invention relates to a method for producing an optical acrylic film having excellent flexibility and surface properties.
  • An acrylic film typified by a polymethylmethacrylate film has been expected as an optical film because of its high transmittance in the visible light region, low intrinsic birefringence, and a small photoelastic coefficient.
  • Patent Document 1 As a countermeasure against cracking, a method of stretching an acrylic film has been proposed (Patent Document 1).
  • Patent Document 2 Also known is a method of imparting flexibility by adding elastic particles to a specific acrylic film and further heat-treating.
  • Patent Document 3 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 3). Since the method of Patent Document 1 is originally applied to an acrylic film that is easily cracked, it is difficult to establish production conditions and lacks versatility.
  • Patent Document 2 has a problem that the time required for the heat treatment is very long and the surface properties of the manufactured acrylic film are inferior. In addition, the heat resistance is remarkably lowered, and when such an acrylic film is used for, for example, 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 3 The method of Patent Document 3 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 film is a resin film containing an acrylic resin (A) and a cellulose ester resin (B) in a mass ratio of 95: 5 to 30:70 and in a compatible state, wherein the acrylic resin (A) 2.
  • the weight average molecular weight Mw is 80000 or more and 1000000 or less
  • the weight average molecular weight Mw of the cellulose ester resin (B) is 75000 or more and 280000 or less
  • the total substitution degree (T) of acyl group is 2.0 or more.
  • an acrylic film having excellent flexibility and surface properties can be produced with high productivity.
  • the present invention is a method for producing an acrylic film containing an acrylic resin (A) and less than 5% by mass of acrylic particles (C) by a solution casting method, wherein the following (1) and (2) are used as a solvent: Using a mixed solvent of solvents A and B satisfying the relationship, drying until the residual solvent becomes 5 to 50% by mass, and in the state where the residual solvent is 5 to 50% by mass, the acrylic film is applied to Tg + 10 ° C. to Tg + 90 It has the process of heat-processing in the range of ° C.
  • the acrylic film of the present invention is produced by dissolving at least an acrylic resin (A) and less than 5% by mass of acrylic particles (C) in a mixed solvent of a solvent A and a solvent B, and casting on a support such as a belt or a drum. It is what is filmed.
  • a Mixed solvent of solvent A and solvent B is a mixed solvent composed of at least the solvent A and the solvent B, and the combined amount of the solvents A and B is 70% by mass or more of the entire mixed solvent.
  • Solvent A and Solvent B satisfy the following relationship.
  • the boiling point of the solvent A is 40 to 95 ° C., preferably 50 to 90 ° C.
  • the boiling point of the solvent B is 70 to 155 ° C., preferably 75 to 150 ° C.
  • Solvents A include methanol (MeOH, 64 ° C.), ethanol (EtOH, 77 ° C.), methyl acetate (MeAc, 55 ° C.), ethyl acetate (EtAc, 75 ° C.), methylene chloride (MC 40 ° C.), acetone (AC, 55 ° C.) and methyl ethyl ketone (MEK, 77 ° C.).
  • () represents an abbreviation and a boiling point (abbreviation, boiling point).
  • solvent B ethanol (EtOH, 77 ° C.), toluene (TOL, 111 ° C.) n-butyl alcohol (nBuOH, 118 ° C.), isoamyl alcohol (iAmOH, 126 ° C.), cyclohexanol (CHOH, 152 ° C.), ethylene
  • examples include glycol monomethyl ether (EGMME, 124 ° C.), ethylene glycol monoethyl ether (EGMEE, 132 ° C.), cyclohexanone (CHNO, 150 ° C.), and the like.
  • Two or more kinds of solvents A and B may be used.
  • Solvent A alone has a solubility of 10% by mass or more with respect to the acrylic resin (A). Moreover, you may mix a solvent other than solvent A and B in the mixed solvent in the range of less than 30 mass% of a mixed solvent.
  • the heat treatment is performed in the range of Tg + 10 ° C. to Tg + 90 ° C. over the acrylic film.
  • Tg + 50 to Tg + 90 ° C. is preferable.
  • the heat treatment time is 15 to 90 seconds, preferably 30 to 60 seconds.
  • the present invention by using a mixed solvent, rapid volatilization of the solvent at the initial stage of drying in the drying step can be prevented, and as a result, the surface shape of the film can be kept good.
  • the boiling point of the solvent B is relatively high, the content ratio of the solvent B is higher than the initial solvent ratio when the residual solvent amount is 5 to 50% by mass, and the solvent B has an absolute boiling point.
  • the solvent can remain even during the heat treatment because it is high, that is, where the residual solvent is as large as 5 to 50% by mass, the Tg of the acrylic film is apparently lowered, and the effect of the heat treatment is amplified and the heating is performed. It is thought that the effect of the treatment was expressed efficiently.
  • the apparent Tg of the acrylic film in the present invention indicates a state in which a phenomenon such as softening occurs at a temperature lower than the actual glass transition temperature by including a solvent. Specifically, it can be measured by the following procedure.
  • a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer) was used in advance under an atmosphere of 23 ° C. and 55% RH.
  • the time-conditioned sample is measured in a nitrogen stream at a heating rate of 20 ° C./min, and the glass transition temperature (Tg) is determined according to JIS K7121 (1987).
  • the elastic modulus of this film is measured at a temperature of at least 5 points (with an interval of 10 ° C. or more) from 30 ° C. to 100 ° C., and an approximate curve (calibration curve) is created. Furthermore, the elastic modulus of the acrylic film containing the residual solvent is measured at 30 ° C., and the value at this time is defined as Ea (GPa). A temperature corresponding to Ea (GPa) is calculated from a calibration curve prepared in advance, and this value is defined as Ta (° C.).
  • the acrylic film of the present invention comprises at least an acrylic resin (A) and less than 5% by mass of acrylic particles (C), and contains other additives.
  • the acrylic film is a resin film containing an acrylic resin (A) and a cellulose ester resin (B) in a mass ratio of 95: 5 to 30:70 and in a compatible state
  • the acrylic resin (A ) Has a weight average molecular weight Mw of 80000 or more and 1000000 or less
  • the weight average molecular weight Mw of the cellulose ester resin (B) is 75000 or more and 280000 or less
  • the total substitution degree (T) of the acyl group is 2.0 or more
  • the substitution degree of the acyl group having 3.0 or less and 3 to 7 carbon atoms is 1.2 or more and 3.0 or less.
  • the acrylic particle (C) is contained in an amount of 0.1 to less than 5% by mass based on the total mass of the resin constituting the acrylic film.
  • the acrylic resin (A) used in the present invention includes a methacrylic resin.
  • the resin is preferably composed of 50 to 100% by mass of methyl methacrylate units and 0 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 for the acrylic film of the present invention has a weight average molecular weight (Mw) of 80,000 to 1,000,000, preferably 150,000 from the viewpoint of mechanical strength as a film and fluidity when producing the film. ⁇ 400000.
  • the weight average molecular weight of the acrylic resin (A) 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 can be used, 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.
  • a commercially available thing can also be used as an acrylic resin (A) of this invention.
  • Delpet 60N, 80N (Asahi Kasei Chemicals Co., Ltd.), Dianal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Electrochemical Industry Co., Ltd.) and the like can be mentioned.
  • ⁇ Acrylic particles (C)> The acrylic particles (C) of the present invention are characterized by existing in the form of particles in the acrylic film containing the acrylic resin (A).
  • a PTFE membrane having a pore diameter smaller than the average particle diameter of the acrylic particles (C) when a predetermined amount of the prepared acrylic film is collected, dissolved in a solvent, stirred, and sufficiently dissolved and dispersed. It is preferable that the weight of the insoluble matter filtered and collected using a 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 preferably acrylic particles (C) having a layer structure of two or more layers, and particularly preferably the following multilayered acrylic granular composite.
  • 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 examples 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 of
  • 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 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 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 (A), and the ratio between the two 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 to the outside by a method of sequentially increasing the amount of chain transfer agent to be added each time. It is possible to make it smaller.
  • 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 (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. , More preferably 500 nm or less, and 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.
  • acrylic particles that are graft copolymers preferably used as acrylic particles (C) preferably used in the present invention include unsaturated carboxylic acid ester-based monomers in the presence of a rubbery polymer.
  • a polymer is mentioned.
  • the rubbery polymer used for the acrylic particle (C) which is a graft copolymer Diene type rubber, acrylic type rubber, ethylene type rubber, etc.
  • 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 film of the present invention can be obtained.
  • 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 here means that the acrylic film of the present invention is sufficiently dissolved in a solvent in which the acrylic resin (A) is soluble to obtain a cloudy solution, and this is subjected to an operation such as centrifugation. After separating the solvent-soluble part and the insoluble part and purifying the soluble part (acrylic resin (A)) and the insoluble part (acrylic particles), the difference in the measured refractive index (23 ° C., measurement wavelength: 550 nm) Indicates.
  • 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 kneading with a single screw or twin screw extruder while adding acrylic particles is preferably used.
  • a solution in which acrylic particles are dispersed in advance is added to and mixed with a solution (dope solution) in which acrylic resin (A) is dissolved, and acrylic particles (C) and other optional additives are dissolved and mixed.
  • a method such as adding the solution in-line can be used.
  • acrylic particles (C) of the present invention commercially available ones can be used.
  • METABRENE W-341 (C2), Chemisnow MR-2G (C3), MS-300X (C4) manufactured by Mitsubishi Rayon Co., Ltd.
  • Parapet SA ′′ and the like can be mentioned, and these can be used alone or in combination of two or more.
  • the acrylic film of the present invention preferably contains 0.1 to 5% by mass of acrylic particles (C) based on the total mass of the resin constituting the film.
  • ⁇ Cellulose ester resin (B)> The acrylic film of the present invention preferably contains a cellulose ester resin (B) from the viewpoint of transparency, particularly when improved with brittleness and heat resistance, and when mixed with the acrylic resin (A).
  • the cellulose ester resin (B) has a total substitution degree (T) of acyl groups of 2.0 to 3.0 and a substitution degree of acyl groups of 3 to 7 carbon atoms of 1.2 to 3.0. Is preferred. That is, the cellulose ester resin (B) is a cellulose ester resin substituted with an acyl group having 3 to 7 carbon atoms.
  • propionyl, butyryl and the like are preferably used, and a propionyl group is particularly preferably used. .
  • the acrylic ester The resin (A) is not sufficiently compatible with the haze.
  • the substitution degree of the acyl group having 3 to 7 carbon atoms is less than 1.2, still sufficient compatibility cannot be obtained, Brittleness will decrease.
  • the substitution degree of the acyl group having 2 carbon atoms, that is, the acetyl group is high, and the substitution degree of the acyl group having 3 to 7 carbon atoms is 1.
  • 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. .0 is fine, It is preferable that the total degree of substitution of acyl groups having 3 to 7 carbon atoms, that is, acetyl groups or acyl groups having 8 or more carbon atoms is 1.3 or less.
  • acyl group is meant to include those further having a substituent.
  • the carbon number of the acyl group includes a substituent of the acyl group.
  • the number of substituents X substituted on the aromatic ring is preferably 0 to 5. Also in this case, it is necessary to pay attention so that the degree of substitution of the acyl group having 3 to 7 carbon atoms including the substituent is 1.2 to 3.0. For example, since the benzyl group has 7 carbon atoms, when it has a substituent containing carbon, the benzyl 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.
  • cellulose ester resin (B) a structure having at least one kind of a substituted or unsubstituted 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) of the present invention is such that the total substitution degree (T) of the acyl group is 2.00 to 3.00, the substitution degree of the acyl group having 3 to 7 carbon atoms is 1.2 to 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) of the present invention is preferably at least one selected from cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate benzoate, cellulose propionate, and cellulose butyrate, particularly cellulose acetate. Propionate and cellulose propionate are more preferable.
  • cellulose ester resins (B) are cellulose acetate propionate and cellulose acetate butyrate, and those having an acyl group having 3 or 4 carbon atoms as a substituent are preferable.
  • 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 (B) of the present invention is 75,000 or more, particularly from the viewpoint of improving compatibility with the acrylic resin (A) and brittleness, and is preferably in the range of 75,000 to 300,000. More preferably, it is within the range of 100,000 to 240,000, particularly preferably 160000 to 240000.
  • the acrylic resin (A) and the cellulose ester resin (B) are preferably contained in a compatible state at a mass ratio of 100: 0 to 30:70.
  • It is preferably 95: 5 to 50:50, and more preferably 90:10 to 60:40.
  • 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 acrylic 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 T g1,2 of the mixture in this compatible state is approximated by the Gordon-Taylor equation (M. Gordon and JS Taylor, 2 J. of Applied Chem. 493-500 (1952)). It is known that it can be done.
  • T g1,2 (w 1 T g1 + Kw 2 T g2 ) / (w 1 + Kw 2 )
  • T g1 and T g2 are component 1
  • Tg1,2 is the glass transition temperature of the mixture of components 1 and 2
  • K is a constant for the free volume of the two resins.
  • 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.
  • the acrylic resin (A) and the cellulose ester resin (B) are preferably compatible with each other to become an amorphous resin.
  • the mixed resin obtained by polymerizing the precursor of acrylic resin (A) such as monomer, dimer or oligomer with cellulose ester resin (B) undergoes graft polymerization, crosslinking reaction or cyclization reaction. In many cases, it does not dissolve in a solvent or cannot be melted by heating, and does not correspond to the resin contained in the compatible state of the present invention.
  • 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 can contain an ultraviolet absorber, a retardation control agent, a matting agent, and an antioxidant as other additives.
  • a ultraviolet absorber can also be used individually or in combination.
  • 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.
  • 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.
  • a conventionally known ultraviolet absorbing polymer can also be used.
  • the conventionally known UV-absorbing polymer is not particularly limited, and examples thereof include a polymer obtained by homopolymerizing RUVA-93 (manufactured by Otsuka Chemical) and a polymer obtained by copolymerizing RUVA-93 with other monomers. .
  • PUVA-30M obtained by copolymerizing RUVA-93 and methyl methacrylate in a ratio (mass ratio) of 3: 7, and PUVA-50M copolymerized in a ratio of 5: 5 (mass ratio). It is done.
  • Phase difference control agent compounds described in JP-A No. 2002-296421 and various ester plasticizers can be used. Hereinafter, preferred ester compounds will be described in detail.
  • a compound having a structure in which aromatic rings are arranged in a plane when added as an additive and stretched is preferable.
  • the polyester polyol used in the present invention includes a dehydration condensation reaction between a glycol having an average carbon number of 2 to 3.5 and a dibasic acid having an average carbon number of 4 to 5.5, or the glycol. It is preferably one produced by a conventional method by addition of a dibasic anhydride having an average carbon number of 4 to 5.5 and a dehydration condensation reaction.
  • glycol and dibasic acid constituting the polyester polyol used in the present invention a combination in which the average of the carbon number of glycol and the average of the carbon number of dibasic acid is 6 to 7.5 is preferable.
  • the polyester polyol obtained from the glycol and the dibasic acid may have a number average molecular weight in the range of 1,000 to 200,000, more preferably a hydroxyl-terminated polyester having a number average molecular weight of 1200 to 1000. Those having a molecular weight of ⁇ 4000 are particularly preferred.
  • a phase difference control agent (a modifier for cellulose ester) excellent in compatibility with the cellulose ester can be obtained by a solid phase reaction.
  • the polyester polyol having a number average molecular weight of 1000 or more is contained in the film in an amount of 2 to 30% by mass. More preferably, it is 10 to 20% by mass.
  • the content of the polymer in the film depends on the type of polymer and the weight average molecular weight. It is decided accordingly.
  • the content of the carboxyl group terminal in the polyester polyol used in the present invention is preferably 1/20 or less of the number of hydroxyl groups from the viewpoint of the effect of the present invention. It is more preferable to stop at 40 or less.
  • an aromatic terminal ester plasticizer represented by the following general formula (I) can be used.
  • B is a benzene monocarboxylic acid residue
  • G is an alkylene glycol residue having 2 to 12 carbon atoms, an aryl glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms
  • A represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an aryl dicarboxylic acid residue having 6 to 12 carbon atoms
  • n represents an integer of 1 or more.
  • benzene monocarboxylic acid component of the aromatic terminal ester plasticizer of the present invention examples include, for example, benzoic acid, para-tert-butylbenzoic acid, orthotoluic acid, metatoluic acid, p-toluic acid, dimethylbenzoic acid, ethylbenzoic acid, normal propyl
  • benzoic acid, aminobenzoic acid, acetoxybenzoic acid, etc. can be used as 1 type, or 2 or more types of mixtures, respectively.
  • the content of the aromatic terminal ester plasticizer of the present invention is preferably 1 to 20% by mass, particularly preferably 3 to 11% by mass in the cellulose ester film.
  • a polyhydric alcohol ester plasticizer can be further used as the retardation control agent.
  • the polyhydric alcohol ester used in the present invention is preferably an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule.
  • the polyhydric alcohol used in the present invention is represented by the following general formula (1).
  • R1- (OH) n represents an n-valent organic group, n represents a positive integer of 2 or more, and the OH group represents an alcoholic or phenolic hydroxyl group.
  • Examples of preferable polyhydric alcohols include the following.
  • triethylene glycol triethylene glycol
  • tetraethylene glycol dipropylene glycol
  • tripropylene glycol tripropylene glycol
  • sorbitol trimethylolpropane
  • xylitol trimethylolpropane
  • the monocarboxylic acid used in the polyhydric alcohol ester of the present invention is not particularly limited, and known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid and the like can be used.
  • alicyclic monocarboxylic acid or aromatic monocarboxylic acid is preferable in terms of improving moisture permeability and retention.
  • preferred monocarboxylic acids include the following, but the present invention is not limited thereto.
  • aliphatic monocarboxylic acid a fatty acid having a straight chain or a side chain having 1 to 32 carbon atoms can be preferably used.
  • acetic acid More preferably, it has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.
  • the use of acetic acid is preferred because the compatibility with the cellulose ester is increased, and it is also preferred to use a mixture of acetic acid and another monocarboxylic acid.
  • Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid, tridecylic acid , Saturated fatty acids such as myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, undecylenic acid, Examples thereof include unsaturated fatty acids such as oleic acid, sorbic acid, linoleic acid, linolenic acid and arachidonic acid.
  • Examples of preferable alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, and derivatives thereof.
  • aromatic monocarboxylic acids examples include those in which an alkyl group is introduced into the benzene ring of benzoic acid such as benzoic acid and toluic acid, and two or more benzene rings such as biphenyl carboxylic acid, naphthalene carboxylic acid, and tetralin carboxylic acid.
  • benzoic acid which has, or those derivatives can be mentioned.
  • benzoic acid is preferred.
  • the molecular weight of the polyhydric alcohol ester is not particularly limited, but is preferably in the range of 300 to 1500, and more preferably in the range of 350 to 750.
  • a larger molecular weight is preferable because it is less likely to evaporate, and a smaller one is preferable in terms of moisture permeability and compatibility with cellulose ester.
  • the carboxylic acid used for the polyhydric alcohol ester may be one kind or a mixture of two or more kinds. Moreover, all the OH groups in the polyhydric alcohol may be esterified, or a part of the OH groups may be left as they are.
  • the retardation control agent of the present invention is preferably an acrylic film containing a sugar ester compound obtained by esterifying a hydroxyl group of a sugar compound in which 1 to 12 at least one structure selected from a furanose structure and a pyranose structure is bonded.
  • sugar compound of the present invention examples include glucose, galactose, mannose, fructose, xylose, arabinose, lactose, sucrose, cellobiose, cellotriose, maltotriose, raffinose, etc., particularly those having both a furanose structure and a pyranose structure. preferable.
  • the ester compound is a monosaccharide ( ⁇ -glucose, ⁇ -fructose) benzoate, or a monosaccharide represented by the following general formula (A): —OR 12 , —OR 15 , —OR 22 , —OR 25
  • the sugar ester compound of the present invention is one in which part or all of the hydroxyl groups of the sugar compound are esterified or a mixture thereof.
  • the benzoic acid in the above general formula may further have a substituent, for example, an alkyl group, an alkenyl group, an alkoxyl group, and a phenyl group, and these alkyl group, alkenyl group, and phenyl group have a substituent. You may have.
  • the acrylic film of the present invention preferably contains a sugar ester compound in an amount of 1 to 30% by mass of the total resin constituting the acrylic film in order to suppress the fluctuation of the retardation value and stabilize the display quality.
  • the sugar ester compound of the present invention is commercially available as Monopet SB (Daiichi Kogyo Seiyaku Co., Ltd.).
  • phase difference controlling agent of the present invention those containing bisphenol A in the molecule are also preferred.
  • a compound in which ethylene oxide or propylene oxide is added to both ends of bisphenol A can be used.
  • BP series such as New Paul BP-2P, BP-3P, BP-23P, BP-5P, BPE-20 (F), BPE-20NK, BPE-20T, BPE-40, BPE-60, BPE-100
  • BPE series manufactured by Sanyo Chemical Co., Ltd.
  • BPX series manufactured by Adeka Co., Ltd.
  • Adeka Polyether BPX-11, BPX-33, BPX-55 Adeka Polyether BPX-11, BPX-33, BPX-55.
  • Diallyl bisphenol A dimethallyl bisphenol A, tetrabromobisphenol A in which bisphenol A is substituted with bromine, oligomers and polymers obtained by polymerizing this, bisphenol A bis (diphenyl phosphate) substituted with diphenyl phosphate, etc. Can be used.
  • Polycarbonate obtained by polymerizing bisphenol A polyarylate obtained by polymerizing bisphenol A with a dibasic acid such as terephthalic acid, and an epoxy oligomer or polymer polymerized with an epoxy-containing monomer can also be used.
  • Modiper CL130D or L440-G obtained by graft polymerization of bisphenol A and styrene or styrene acrylic can also be used.
  • the acrylic film of the present invention can contain two or more retardation control agents. In this case, by optimizing the combination, elution of the phase difference controlling agent can be reduced.
  • lactone, sulfur, phenol, double bond, hindered amine and phosphorus compounds can be preferably used.
  • the phenolic compound preferably has a 2,6-dialkylphenol structure.
  • trade names of Ciba Japan Co., Ltd. “Irganox 1076”, “Irganox 1010”, and ADEKA “ADEKA STAB AO-50” And those commercially available.
  • the phosphorus compounds are, for example, from Sumitomo Chemical Co., Ltd., “Sumizer GP”, from ADEKA Co., Ltd., “ADK STAB PEP-24G”, “ADK STAB PEP-36” and “ADK STAB 3010”, from Ciba Japan Co., Ltd. “IRGAFOS P-EPQ”, commercially available from Sakai Chemical Industry Co., Ltd. under the trade name “GSY-P101” is preferable.
  • the hindered amine compound is preferably commercially available from Ciba Japan Co., Ltd. under the product names “Tinuvin 144” and “Tinvin 770”, and from ADEKA Co., Ltd. as “ADK STAB LA-52”.
  • the above sulfur compounds are preferably those commercially available from Sumitomo Chemical Co., Ltd. under the trade names “Sumilizer TPL-R” and “Sumilizer TP-D”.
  • the above-mentioned double bond compound is preferably commercially available from Sumitomo Chemical Co., Ltd. under the trade names of “Sumilizer GM” and “Sumilizer GS”.
  • the amount of these antioxidants and the like to be added is appropriately determined in accordance with the process for recycling and use, but generally 0.05 to 20% by mass, preferably with respect to the resin as the main raw material of the film Is added in the range of 0.1 to 1% by mass.
  • antioxidants can obtain a synergistic effect by using several different types of compounds in combination rather than using only one kind.
  • the combined use of lactone, phosphorus, phenol and double bond compounds is preferred.
  • the acrylic film of the present invention preferably contains fine particles as a matting agent.
  • examples of inorganic compounds include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, calcium carbonate, talc, clay, calcined kaolin, calcined calcium silicate, and hydrated silicic acid. Mention may be made of calcium, aluminum silicate, magnesium silicate and calcium phosphate. Further, fine particles of an organic compound can also be preferably used.
  • organic compounds include polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, acrylic styrene resin, silicone resin, polycarbonate resin, benzoguanamine resin, melamine resin Also, pulverized and classified products of organic polymer compounds such as polyolefin-based powders, polyester-based resins, polyamide-based resins, polyimide-based resins, polyfluorinated ethylene-based resins, and starches.
  • a polymer compound synthesized by a suspension polymerization method a polymer compound made spherical by a spray dry method or a dispersion method, or an inorganic compound can be used.
  • Fine particles containing silicon are preferable in terms of low turbidity, and silicon dioxide is particularly preferable.
  • the average primary particle size of the fine particles is preferably 5 to 400 nm, and more preferably 10 to 300 nm.
  • These may be mainly contained as secondary aggregates having a particle size of 0.05 to 0.3 ⁇ m, and may be contained as primary particles without being aggregated if the particles have an average particle size of 100 to 400 nm. preferable.
  • the content of these fine particles in the film is preferably 0.01 to 1% by mass, particularly preferably 0.05 to 0.5% by mass.
  • Silicon dioxide fine particles are commercially available, for example, under the trade names Aerosil R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.). it can.
  • Zirconium oxide fine particles are commercially available, for example, under the trade names Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.).
  • Examples of the polymer include silicone resin, fluororesin and acrylic resin. Silicone resins are preferable, and those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, 105, 108, 120, 145, 3120, and 240 (manufactured by Toshiba Silicone Co., Ltd.) It is marketed by name and can be used.
  • Aerosil 200V and Aerosil R972V are particularly preferably used because they have a large effect of reducing the friction coefficient while keeping the turbidity of the polarizing plate protective film low.
  • the dynamic friction coefficient of at least one surface is 0.2 to 1.0.
  • additives may be batch-added to the dope that is a solution before film formation, or an additive solution may be separately prepared and added in-line.
  • an in-line mixer such as a static mixer (manufactured by Toray Engineering), SWJ (Toray static type in-tube mixer Hi-Mixer) or the like is preferably used.
  • 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.
  • phosphate ester plasticizers triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, etc.
  • phthalate ester plasticizers diethyl phthalate, dimethoxy Ethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate and the like can be used.
  • 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 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.
  • These plasticizers may be used alone or in combination of two or more.
  • antioxidants can be added to the acrylic resin (A) used in the acrylic film of the present invention in order to improve the thermal decomposability and thermal coloring during molding. It is also possible to add an antistatic agent to impart antistatic performance to the acrylic film.
  • acrylic resin (A) composition of the present invention 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.
  • Organic solvent An organic solvent useful for forming a dope when the acrylic film of the present invention is produced by a solution casting method is a mixed solvent containing solvents A and B.
  • a dope composition is prepared by dissolving at least 15 to 45% by mass in total of three types of acrylic resin (A), acrylic particles (C), and optionally cellulose ester resin (B) in this mixed solvent.
  • Dissolution step Dissolution is performed at normal pressure, at a temperature lower than the boiling point of the main solvent, at a pressure higher than the boiling point of the main solvent, disclosed in JP-A-9-95544, JP-A-9-95557, Alternatively, various dissolution methods such as a cooling method as described in JP-A-9-95538 and a high-pressure method as described in JP-A-11-21379 can be used. A method in which pressure is applied at a boiling point or higher is preferred.
  • the dope After adding or dissolving in the dope during or after dissolution, the dope is dissolved and dispersed, filtered through a filter medium, defoamed, and sent to the next process 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.
  • 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.
  • 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.
  • 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. .
  • 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 indefinitely.
  • a liquid feed pump for example, a pressurized metering gear pump
  • ⁇ Pressure dies that can adjust the slit shape of the die base and make the film thickness uniform are preferred.
  • Examples of the pressure die include 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 overlaid. Or it is also preferable to obtain the film of a laminated structure by the co-casting method which casts several dope simultaneously.
  • a web (dope is cast on a casting support, and the formed dope film is called a web) is heated on the casting support to evaporate the solvent to produce a film shape. It is a process.
  • the web on the support after casting is preferably dried on the support in an atmosphere of 40 to 100 ° C.
  • 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 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.
  • the amount of residual solvent is determined.
  • the amount of residual solvent of the web that is the residual solvent of the present invention 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 140 ° C. for 2 hours.
  • 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.
  • Drying step After peeling, using the drying device 35 that alternately conveys the web through a plurality of rolls arranged in the drying device, and / or the tenter stretching device 34 that clips and conveys both ends of the web with a clip, 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.
  • the whole is dried at 40 to 160 ° C., and the residual solvent is adjusted to 5 to 50% by mass in this step.
  • Heat treatment step It is preferable to heat-treat the film whose residual solvent is adjusted to 5 to 50% by mass in the drying step at an apparent Tg + 10 to 90 ° C., and further to treat at an apparent Tg + 40 to 90 ° C. preferable. Specifically, the temperature is 80 to 160 ° C.
  • the treatment may be performed in stages, such as treatment at about 120 ° C. at the beginning and heating at 140 ° C. at the end.
  • the heat treatment time is preferably 15 to 60 minutes, particularly preferably 20 to 40 minutes.
  • a stretching step may be provided after the heat treatment.
  • tenter stretching apparatus When using a tenter stretching apparatus, 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) left and right 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 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 temperature condition at the time of stretching it is preferable to carry out at an acrylic film over Tg + 10 to 50 ° C. Specifically, it is preferable to carry out at 80 to 160 ° 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 film by the winder 37 after the residual solvent amount in the web is 2% by mass or less, and 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.
  • 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.
  • ⁇ Physical properties of acrylic film> Hereafter, the characteristic about the physical property etc. of the acrylic film of this invention is demonstrated.
  • the acrylic film of the present invention is preferably adjusted so that the photoelastic coefficient is ⁇ 6.0 ⁇ 10 ⁇ 12 to 6.0 ⁇ 10 ⁇ 12 / Pa, and ⁇ 2.0 ⁇ 10 ⁇ 12 to 2. It is particularly preferable to control within the range of 0 ⁇ 10 ⁇ 12 / Pa.
  • the ratio of the acrylic resin (A) to the cellulose ester resin (B) and other resins is adjusted, and the phase difference control agent is adjusted according to this resin ratio. This is done by adjusting the combination and the amount to be added to optimize the composition of the acrylic film.
  • the acrylic film of the present invention is measured under conditions of a temperature of 40 ° C. and a humidity of 90% RH based on JIS Z 0208, and the moisture permeability value converted to a film thickness proportional to a film thickness of 60 ⁇ m is 50 to 600 g / m 2 ⁇ 24 h. It is particularly preferably 200 to 450 g / m 2 ⁇ 24 h.
  • the acrylic film of the present invention is used for at least one of the polarizing plates, by setting the moisture permeability to the above range, even if the liquid crystal display device is used in a high humidity environment, light leakage and image quality due to deterioration of the polarizer are prevented.
  • the acrylic film of the present invention has a defect of 5 ⁇ m or more in diameter 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 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 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 is characterized by having a haze value (turbidity), which is one of the indices indicating transparency, of 1.0% or less.
  • a haze value which is one of the indices indicating transparency
  • the luminance and contrast when incorporated in a liquid crystal display device are characteristic. From the point, it is preferably 0.5% or less.
  • the smoothness of the surface is expressed as surface haze, and it is also effective to reduce the particle diameter and addition amount of the acrylic particles within the above range, or to reduce the surface roughness of the film contact portion during film formation.
  • the total light transmittance and haze value of the acrylic film are values measured according to JIS-K7361-1-1997 and JIS-K7136-2000.
  • the acrylic film of the present invention can be preferably used as an optical acrylic film as long as the above physical properties are satisfied.
  • the acrylic film of the present invention can be used as a polarizing plate protective film.
  • the polarizing plate can be produced by a general method.
  • 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 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 Etc.
  • 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 Etc.
  • a polarizer which is a main component of a polarizing plate, is an element that allows only light of a plane of polarization in a certain direction to pass.
  • a typical polarizer currently known is a polyvinyl alcohol-based polarizing film, which is polyvinyl alcohol.
  • 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.
  • liquid crystal display device By incorporating the polarizing plate bonded with the acrylic film of the present invention into a liquid crystal display device using at least one surface of the liquid crystal cell, liquid crystal display devices having various durability can be manufactured.
  • the polarizing plate of the present invention is bonded to a liquid crystal cell via the adhesive layer or the like.
  • the polarizing plate of the present invention is preferably a reflective, transmissive, transflective LCD or LCD of various drive systems such as TN, STN, OCB, HAN, VA (PVA, MVA) and IPS. Used.
  • Mw 480000 80N manufactured by Asahi Kasei Chemicals Corporation
  • the ratio of the MMA unit in the molecule of the above-mentioned commercially available acrylic resin (A) is about 30% by mass for Dialal BR50, about 70% by mass for Dialal BR52, and 90% to 99% by mass for all of Dialal BR80 to 80N. It was the following.
  • 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.
  • a small amount of the polymer latex thus obtained was collected, and the average particle size was determined by the absorbance method, which was 0.10 ⁇ m and 100 nm.
  • the remaining latex was put into a 3% by mass sodium sulfate warm aqueous solution, salted out and coagulated, and then dried after repeated dehydration and washing to obtain acrylic particles (C1) having a three-layer structure.
  • Formation of acrylic film 1 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 residual solvent amount reached 100%, and the film was peeled from the stainless steel band support with a peeling tension of 162 N / m.
  • the peeled acrylic resin web was slit to a width of 1.6 m, then conveyed to a drying step having a tenter function, and dried at 135 ° C. while being stretched 1.1 times in the width direction.
  • the residual solvent amount when starting stretching with a tenter was 30% by mass.
  • the amount of residual solvent after stretching with a tenter was 20% by mass.
  • the solvent was transported to a heat treatment step, and heat treatment was performed at 120 ° C. for 15 minutes and then at 140 ° C. for 15 minutes.
  • the residual solvent amount of the acrylic film 1 described in Table 2 was 0.1% by mass, the film thickness was 60 ⁇ m, and the winding length was 4000 m.
  • 15-2 to 15-47 were prepared with the same solvent composition and amount as 15-1 (88 parts by mass of methylene chloride, 6 parts by mass of n-butanol, 6 parts by mass of ethanol).
  • ac represents an acetyl group
  • pr represents a propionyl group
  • bu represents a butyryl group
  • pen represents a pentanoyl group
  • bz represents a benzoyl group
  • hep represents a heptanoyl group
  • oct represents an octanoyl group
  • ph represents a phthalyl group.
  • “Amount” described in Table 2 represents parts by mass.
  • films according to 1-A described in Example 1 of JP-A-2007-10044 and a film described in Example 1 of WO2005 / 105918 were prepared.
  • the surface haze of the acrylic film of the present invention was measured by the following procedure. (1) The total haze (H) is measured as described above. (2) A polyethylene terephthalate film with an adhesive having an acrylic adhesive applied on one side is attached to the surface of the acrylic film of the present invention, and the total haze value H0 is measured for the whole attached film. (3) Separately, the total haze value Ht of only the polyethylene terephthalate film with pressure-sensitive adhesive to which the acrylic pressure-sensitive adhesive was applied was measured, and the value obtained by subtracting Ht from the previously measured H0 was defined as the internal haze value Hi.
  • ⁇ The tear surface is very smooth and is torn straight.
  • ⁇ The tear surface has some burrs, but is torn straight.
  • 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 produce a polarizer.
  • Example 1 the acrylic film 1 produced in Example 1 was subjected to corona treatment using an acrylic adhesive on one side of the polarizer, and then bonded.
  • KC8UCR-5 manufactured by Konica Minolta Opto Co., Ltd., which is an alkali saponified retardation film, was bonded to the other surface of the polarizer and dried to prepare a polarizing plate P1.
  • polarizing plates P2 to P-17 and 15-1 to 15-47 were prepared using acrylic films 2 to 17 and 15-1 to 15-47.
  • the polarizing plate using the acrylic 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 above polarizing plate treated at 60 ° C. and 90% RH for 500 hours was measured in the same manner, and evaluated in three stages according to the following criteria.
  • the acrylic film of the present invention exhibited low hygroscopic properties, transparency, high heat resistance, and excellent brittleness improvement. Moreover, the polarizing plate and the liquid crystal display device produced using the acrylic film of the present invention exhibited excellent properties in visibility and color shift.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polarising Elements (AREA)
  • Moulding By Coating Moulds (AREA)

Abstract

L’invention concerne un procédé de production d’un film acrylique présentant une excellente flexibilité et d’excellentes propriétés de surface ainsi qu’une productivité élevée. L’invention concerne également un film acrylique produit selon le procédé. L’invention concerne spécifiquement un procédé de production d’un film acrylique comprenant (A) une résine acrylique et (C) des particules acryliques dans une quantité inférieure à 5 % en masse au moyen d'un procédé de production de coulée de films en solution. Le procédé est caractérisé en ce qu'il comprend les étapes de : séchage du film acrylique jusqu'à ce que la teneur résiduelle en un solvant dans le film acrylique soit réduite de 5 à 50 % en masse, le solvant étant une solution mélangée de solvants A et B qui satisfont une relation représentée par les équations (1) et (2) représentées ci-dessous ; chauffage du film acrylique à une température comprise dans la gamme de températures allant d’une température supérieure de 10°C à la température de transition vitreuse du film acrylique à une température supérieure de 40°C à la température de transition vitreuse du film acrylique tout en maintenant la teneur résiduelle en solvant dans le film acrylique à 5 à 50 % en masse. (1) Point d’ébullition du solvant A + 35°C < point d’ébullition du solvant B. (2) Le rapport entre la quantité du solvant A et la quantité du solvant B dans la solution mélangée (c’est-à-dire A:B) est de 98:2 à 70:30 en masse.
PCT/JP2009/059343 2008-06-13 2009-05-21 Procédé de production de film acrylique, et film acrylique produit selon le procédé WO2009150926A1 (fr)

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JP2010516803A JP5447374B2 (ja) 2008-06-13 2009-05-21 アクリルフィルムの製造方法およびその製造方法で作製したアクリルフィルム

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JP2019535872A (ja) * 2017-09-04 2019-12-12 ヒョスン ケミカル コーポレーション アクリルフィルム
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