WO2016157913A1 - Procédé de fabrication d'un film de résine acrylique étiré - Google Patents

Procédé de fabrication d'un film de résine acrylique étiré Download PDF

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Publication number
WO2016157913A1
WO2016157913A1 PCT/JP2016/001875 JP2016001875W WO2016157913A1 WO 2016157913 A1 WO2016157913 A1 WO 2016157913A1 JP 2016001875 W JP2016001875 W JP 2016001875W WO 2016157913 A1 WO2016157913 A1 WO 2016157913A1
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Prior art keywords
acrylic resin
resin film
weight
stretched
monomer
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English (en)
Japanese (ja)
Inventor
治規 小山
史延 北山
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Kaneka Corp
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Kaneka Corp
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Classifications

    • 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
    • B29C55/16—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial simultaneously
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to a method for producing a stretched acrylic resin film.
  • a liquid crystal display device usually two polarizing plates are arranged on both sides of a liquid crystal cell.
  • the polarizing plate generally has a polarizer protective film bonded to both sides of the polarizer, and a film made of a cellulose-based material is usually used as the polarizer protective film.
  • a polarizer protective film made of an acrylic resin has been proposed for the purpose of improving durability (see, for example, Patent Documents 1 and 2).
  • an acrylic resin film has a low strength, and thus a treatment such as biaxial stretching is performed to improve the strength.
  • a stretched acrylic resin film is desired to further increase the strength.
  • the use of a crosslinked elastic body in a stretched acrylic resin film has been studied.
  • the average particle diameter of the crosslinked elastic body needs to be 150 nm or more.
  • the stretched acrylic resin film has a high haze, and the film is not suitable for optical use such as a polarizer protective film.
  • an object of the present invention is to provide a method that enables production of a stretched acrylic resin film excellent in optical properties such as haze and toughness.
  • the present invention relates to 99 to 50% by weight of acrylic resin (A), 1 to 50% by weight of rubber-containing graft copolymer (B), and 100% by weight (total amount of acrylic resin and rubber-containing graft copolymer). %)) Of a stretched acrylic resin film comprising a composition comprising:
  • the rubber-containing graft copolymer (B) comprises an innermost layer made of a polymer containing methacrylic acid ester as a main monomer, and a polymer containing an alkyl acrylate ester having 4 to 12 carbon atoms in the alkyl group as a main monomer.
  • the innermost layer and the intermediate layer constitute a crosslinked elastic body, and the crosslinked elastic body has an average particle diameter of 150 to 400 nm, Under conditions where the stretching temperature is Tg + 5 to Tg + 50 ° C. (where Tg represents the glass transition temperature of the acrylic resin film made of the composition), the acrylic resin film made of the composition is stretched horizontally or simultaneously.
  • the present invention relates to a method for producing a stretched acrylic resin film including a step of axial stretching (hereinafter sometimes referred to as “the method for producing a stretched acrylic resin film of the present invention”).
  • the rubber-containing graft copolymer (B) is obtained by polymerizing the following monomer mixtures (B-1) to (B-4) in sequence: A polymer is preferred.
  • B-1) Methacrylic acid ester (b-1-1) 60 to 100% by weight, monomer (b-1-2) 40 to 0% by weight copolymerizable therewith, and polyfunctional monomer (B-1-3) A monomer mixture comprising 0.05 to 20 parts by weight (relative to 100 parts by weight of (b-1-1) + (b-1-2)).
  • (B-2) Acrylic ester (b-2-1) 50 to 100% by weight, monomer (b-2-2) 50 to 0% by weight copolymerizable therewith, and polyfunctional monomer (B-2-3) A monomer mixture comprising 0.05 to 20 parts by weight (relative to (b-2-1) + (b-2-2) 100 parts by weight).
  • (B-3) A monomer mixture comprising 50 to 100% by weight of methacrylic acid ester (b-3-1) and 50 to 0% by weight of monomer (b-3-2) copolymerizable therewith
  • (B -4) A monomer mixture comprising 0 to 70% by weight of methacrylic acid ester (b-4-1) and 100 to 30% by weight of monomer (b-4-2) copolymerizable therewith.
  • the glass transition temperature of the acrylic resin is preferably 110 ° C. or higher.
  • the number of times of bending the stretched acrylic resin film (width 15 mm, length 120 mm) measured according to JIS P8115 under a load of 200 g is 500 times or more. Preferably there is.
  • the retardation value of the stretched acrylic resin film is such that the in-plane retardation Re is 5.0 nm or less and the thickness direction retardation Rth is 20.0 nm or less. preferable.
  • the stretched acrylic resin film preferably has a photoelastic coefficient of ⁇ 10 ⁇ 10 ⁇ 12 to 10 ⁇ 10 ⁇ 12 Pa ⁇ 1 .
  • the total haze of the stretched acrylic resin film is preferably 2% or less.
  • the internal haze of the stretched acrylic resin film is preferably 1% or less.
  • the method for producing a stretched acrylic resin film of the present invention may further include a step of forming an adhesive layer.
  • the stretched acrylic resin film may be an optical film.
  • a stretched acrylic resin film having excellent optical properties and toughness can be produced.
  • the acrylic resin (A) is not particularly limited as long as it is a thermoplastic acrylic resin.
  • An acrylic resin is a resin generally having a (meth) acrylic acid ester unit and / or a (meth) acrylic acid unit, and is a structural unit derived from a (meth) acrylic acid ester or a derivative of (meth) acrylic acid. You may have.
  • (meth) acryl refers to “methacryl or acrylic”.
  • the total proportion of structural units derived from (meth) acrylic acid ester units, (meth) acrylic acid units and derivatives of these units in all structural units of the acrylic resin is usually 50% by weight or more, preferably It is 60% by weight or more, more preferably 70% by weight or more.
  • Examples of the (meth) acrylate unit include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and t- (meth) acrylate.
  • an acrylic resin having a methyl (meth) acrylate unit is preferable because thermal stability is improved, and in particular, 30 to 100% by weight of methyl methacrylate units among all the structural units, and copolymerized therewith.
  • Acrylic resins containing 70 to 0% by weight of possible monomer units are more preferred.
  • any structural units enumerated as a (meth) acrylic acid ester unit and a (meth) acrylic acid unit may have two or more types of any structural units enumerated as a (meth) acrylic acid ester unit and a (meth) acrylic acid unit.
  • styrene vinyl toluene, ⁇ -methyl styrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, vinyl acetate, methallyl alcohol, allyl alcohol, 2-hydroxymethyl-1-butene, ⁇ -hydroxymethylstyrene, ⁇ -hydroxy 2- (hydroxyalkyl) acrylic acid esters such as ethylstyrene, methyl 2- (hydroxyethyl) acrylate, 2- (hydroxyalkyl) acrylic acids such as 2- (hydroxyethyl) acrylic acid, maleic acid, fumaric acid and the like
  • Esters such as vinyl chloride, vinyl bromide and chloroprene; vinyl acetate; vinyl acetate; alkenes such as ethylene, propylene, butylene, butadiene and isobutylene: halogenated alkenes; allyl methacrylate; Diallyl phthalate, triallyl cyanurate, monoethylene glycol dimethacryl
  • An acrylic resin is preferable in terms of excellent optical properties, heat resistance, molding processability, and the like.
  • the acrylic resin preferably has a glass transition temperature of 110 ° C. or higher, more preferably 115 ° C. or higher, and further preferably 120 ° C. or higher.
  • the glass transition temperature is less than 110 ° C., the heat resistance of the film is inferior, so that the physical property change at high temperature becomes large, the application range becomes narrow, especially when used for optical applications, the film is used in a high temperature environment. Distortion tends to occur, and there is a tendency that stable optical characteristics cannot be obtained.
  • the glass transition temperature can be measured using a differential scanning calorimeter (DSC).
  • acrylic resin having a glass transition temperature of 120 ° C. or more specifically, a glutarimide structure, a glutaric anhydride structure, a maleic anhydride structure, a (meth) acrylic acid unit, a lactone ring, or a maleimide structure in the molecule
  • An acrylic resin is included.
  • acrylic polymers containing cyclic acid anhydride repeating units such as polyglutarimide acrylic resins, glutaric anhydride structure-containing acrylic resins and maleic anhydride structure-containing acrylic resins, lactone-cyclized acrylic resins, hydroxyl groups And / or an acrylic resin containing a carboxyl group, a methacrylic resin, a maleimide structure-containing acrylic resin, and the like.
  • resins with a glass transition temperature of 120 ° C or higher include partial hydrogenation of aromatic rings of styrene unit-containing acrylic polymers obtained by polymerizing styrene monomers and other monomers copolymerizable therewith.
  • styrene unit-containing acrylic polymer obtained by polymerizing styrene monomers and other monomers copolymerizable therewith.
  • a partially hydrogenated styrene unit-containing acrylic polymer can be used.
  • the rubber-containing graft copolymer (B) used in the present invention is an innermost layer made of a polymer having a methacrylic acid ester as a main monomer, and a heavy polymer having an alkyl acrylate having 4 to 12 carbon atoms as the main monomer.
  • An intermediate layer made of a combination and one or more outermost layers made of a polymer having a methacrylic acid ester as a monomer are included.
  • the rubber-containing graft copolymer (B) of the present invention is preferably a multistage polymer obtained by sequentially polymerizing the monomer mixtures (B-1) to (B-4) described below from the viewpoint of strength. .
  • the monomer mixture (B-1) is polymerized to obtain the innermost layer polymer.
  • the monomer mixture (B-1) used in the present invention is 60 to 100% by weight of a methacrylic acid ester (b-1-1), an ethylenically unsaturated monomer (b-1-2) copolymerizable therewith. 40 to 0% by weight, and 0.05 to 20 parts by weight of the polyfunctional monomer (b-1-3) ((b-1-1) + (b-1-2) 100 parts by weight) ). All the monomers may be mixed and used, or may be used in two or more stages by changing the monomer composition.
  • a methacrylic acid alkyl ester is preferable in view of polymerizability and cost.
  • the alkyl group having 1 to 4 carbon atoms is more preferable, and the alkyl group may be linear or branched. Specific examples thereof include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, octyl acrylate, ⁇ -hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate. These monomers may be used in combination of two or more.
  • the content of the methacrylic acid ester (b-1-1) is preferably 60 to 100% by weight, more preferably 70 to 100% by weight of the total amount of (b-1-1) and (b-1-2). 80 to 100% by weight is most preferable. If it is less than 60% by weight, the surface hardness and transparency of the film may deteriorate.
  • an ethylenically unsaturated monomer (b-1-2) copolymerizable with the methacrylic acid ester (b-1-1) may be copolymerized.
  • these copolymerizable ethylenically unsaturated monomers include acrylic esters, and alkyl acrylates are preferred from the viewpoint of polymerization reactivity and cost.
  • the alkyl group having 1 to 12 carbon atoms is more preferable, and the alkyl group may be linear or branched.
  • ethylenically unsaturated monomers include vinyl halides such as vinyl chloride and vinyl bromide, vinyl cyanides such as acrylonitrile and methacrylonitrile, vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate.
  • Aromatic vinyl derivatives such as styrene, vinyltoluene, ⁇ -methylstyrene, vinylidene halides such as vinylidene chloride and vinylidene fluoride, acrylic acid such as acrylic acid, sodium acrylate, calcium acrylate and salts thereof, methacrylic acid, Examples thereof include methacrylic acid such as sodium methacrylate and calcium methacrylate, and salts thereof, and two or more of these monomers may be used in combination.
  • a polyfunctional monomer (b-1-3) having two or more non-conjugated reactive double bonds per molecule is copolymerized. Therefore, the polymer obtained becomes a crosslinked elastic body.
  • the polyfunctional monomer (b-1-3) used here include allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl malate, divinyl adipate, divinylbenzene ethylene glycol -Dimethacrylate, divinylbenzene ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, Tetramethylol methane tetramethacrylate, tetramethylol methane tetraacrylate,
  • the addition amount of the polyfunctional monomer (b-1-3) in the monomer mixture (B-1) is 100 parts by weight of (b-1-1) + (b-1-2). 0.05 to 20 parts by weight is preferable, and 0.1 to 10 parts by weight is more preferable. If the addition amount of the polyfunctional monomer is less than 0.05 parts by weight, there is a tendency that a crosslinked elastic body cannot be formed, and if it exceeds 20 parts by weight, the crack resistance of the film tends to be lowered.
  • the monomer mixture (B-2) is polymerized in the presence of the innermost layer polymer (polymer of (B-1)) to obtain a crosslinked elastic body.
  • the monomer mixture (B-2) used in the present invention is 50 to 100% by weight of the acrylic ester (b-2-1), an ethylenically unsaturated monomer (b-2-2) copolymerizable therewith. ) 50 to 0% by weight, and 0.05 to 20 parts by weight of the polyfunctional monomer (b-2-3) ((b-2-1) + (b-2-2) 100 parts by weight) ). All the monomers may be mixed and used, or may be used in two or more stages by changing the monomer composition.
  • the acrylic ester (b-2-1) used here is preferably an alkyl acrylate in view of polymerization reactivity and cost.
  • the alkyl group having 1 to 12 carbon atoms is more preferable, and the alkyl group may be linear or branched.
  • acrylate ester (b-2-1) is preferably 50 to 100% by weight, more preferably 60 to 100% by weight of the total amount of (b-2-1) and (b-2-2). 70 to 100% by weight is most preferable. If it is less than 50% by weight, the crack resistance of the film may deteriorate.
  • an ethylenically unsaturated monomer (b-2-2) copolymerizable with the acrylate ester (b-2-1) may be copolymerized.
  • these copolymerizable ethylenically unsaturated monomers include methacrylic acid esters, and methacrylic acid alkyl esters are preferred from the viewpoint of polymerizability and cost.
  • the alkyl group having 1 to 12 carbon atoms is more preferable, and the alkyl group may be linear or branched.
  • ethylenically unsaturated monomers include vinyl halides such as vinyl chloride and vinyl bromide, vinyl cyanides such as acrylonitrile and methacrylonitrile, vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate.
  • Aromatic vinyl derivatives such as styrene, vinyltoluene, ⁇ -methylstyrene, vinylidene halides such as vinylidene chloride and vinylidene fluoride, acrylic acid such as acrylic acid, sodium acrylate, calcium acrylate and salts thereof, methacrylic acid, Examples thereof include methacrylic acid such as sodium meacrylate and calcium methacrylate and salts thereof, and two or more of these monomers may be used in combination.
  • a polyfunctional monomer (b-2-3) having two or more non-conjugated reactive double bonds per molecule is copolymerized. Therefore, the polymer obtained becomes a crosslinked elastic body.
  • the polyfunctional monomer (b-2-3) used here include allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl malate, divinyl adipate, divinylbenzene ethylene glycol -Dimethacrylate, divinylbenzene ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, Tetramethylol methane tetramethacrylate, tetramethylol methane tetraacrylate,
  • the addition amount of the polyfunctional monomer (b-2-3) in the monomer mixture (B-2) is 100 parts by weight of (b-2-1) + (b-2-2). 0.05 to 20 parts by weight is preferable, and 0.1 to 10 parts by weight is more preferable. If the addition amount of the polyfunctional monomer is less than 0.05 parts by weight, there is a tendency that a crosslinked elastic body cannot be formed, and if it exceeds 20 parts by weight, the crack resistance of the film tends to be lowered.
  • the monomer mixture (B-3) is polymerized in the presence of a crosslinked elastic body (polymer of (B-1) + (B-2)) to obtain a graft copolymer.
  • the monomer mixture (B-3) used in the present invention is 50 to 100% by weight of the methacrylic acid ester (b-3-1), and the monomer (b-3-2) 50 to 0 copolymerizable therewith. It consists of weight percent. All the monomers may be mixed and used, or may be used in two or more stages by changing the monomer composition.
  • the methacrylic acid ester (b-3-1) used here is preferably an alkyl methacrylic acid ester from the viewpoint of polymerizability and cost.
  • the alkyl group having 1 to 4 carbon atoms is more preferable, and the alkyl group may be linear or branched. Specific examples thereof include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, octyl acrylate, ⁇ -hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate. These monomers may be used in combination of two or more.
  • the content of the methacrylic acid ester (b-3-1) is preferably 50 to 100% by weight, more preferably 70 to 100% by weight of the total amount of (b-3-1) and (b-3-2). 80 to 100% by weight is most preferable. If it is less than 50% by weight, the surface hardness and transparency of the film may deteriorate.
  • an ethylenically unsaturated monomer (b-3-2) copolymerizable with the methacrylic acid ester (b-3-1) may be copolymerized.
  • these copolymerizable ethylenically unsaturated monomers include acrylic esters, and alkyl acrylates are preferred from the viewpoint of polymerization reactivity and cost.
  • the alkyl group having 1 to 12 carbon atoms is more preferable, and the alkyl group may be linear or branched.
  • ethylenically unsaturated monomers include vinyl halides such as vinyl chloride and vinyl bromide, vinyl cyanides such as acrylonitrile and methacrylonitrile, vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate.
  • Aromatic vinyl derivatives such as styrene, vinyltoluene, ⁇ -methylstyrene, vinylidene halides such as vinylidene chloride and vinylidene fluoride, acrylic acid such as acrylic acid, sodium acrylate, calcium acrylate and salts thereof, methacrylic acid, Examples thereof include methacrylic acid such as sodium meacrylate and calcium methacrylate and salts thereof, and two or more of these monomers may be used in combination.
  • the monomer mixture (B-3) preferably does not contain a polyfunctional monomer having two or more non-conjugated reactive double bonds per molecule.
  • the monomer mixture (B-4) is polymerized in the presence of the graft copolymer (polymer of (B-1) + (B-2) + (B-3)) to obtain a rubber-containing graft copolymer.
  • a polymer (B) is obtained.
  • the monomer mixture (B-4) used in the present invention is a methacrylic acid ester (b-4-1) 0 to 70% by weight, and a monomer (b-4-2) 100 to 30 copolymerizable therewith. It consists of weight percent. All the monomers may be mixed and used, or may be used in two or more stages by changing the monomer composition.
  • methacrylic acid ester (b-4-1) used here those exemplified in the above (B-3) can be used in the same manner, and preferable examples are also preferable.
  • the content of the methacrylic acid ester (b-4-1) is preferably 0 to 70% by weight, more preferably 20 to 70% by weight of the total amount of (b-4-1) and (b-4-2). 30 to 70% by weight is most preferable. When it exceeds 70% by weight, it becomes a fine powder when the latex is powdered after the polymerization, and the transparency may be deteriorated because the dispersibility deteriorates at the time of molding.
  • the monomer (b-4-2) copolymerizable with the methacrylic acid ester (b-4-1) those exemplified above for the monomer (b-3-2) can be used as well. Preferred examples are also preferred. Two or more of these monomers may be used in combination. It is preferable that the monomer mixture (B-4) does not contain a polyfunctional monomer having two or more non-conjugated reactive double bonds per molecule.
  • the average particle size of a crosslinked elastic body (hereinafter also referred to as “rubber particles”) composed of an innermost layer and an intermediate layer is 150 to 400 nm. If the thickness is less than 150 nm, the toughness of the obtained stretched acrylic resin film is insufficient. When it exceeds 400 nm, the haze of a film will become high. From the viewpoint of strength, 200 nm or more is preferable. On the other hand, 350 nm or less is preferable and 300 nm or less is more preferable.
  • the average particle diameter of the cross-linked elastic body here is measured in the latex state of the cross-linked elastic body and is 546 nm using MICROTRAC UPA150 manufactured by Nikkiso Co., Ltd., which is a laser diffraction / scattering particle size distribution measuring apparatus. It is a value measured by wavelength.
  • the acrylic resin film of the present invention has an acrylic resin of 99 to 50% by weight and a rubber-containing graft copolymer of 1 to 50% by weight (based on the total amount of the acrylic resin and the rubber-containing graft copolymer of 100% by weight). Containing. From the viewpoint of haze, 99 to 60% by weight of acrylic resin and 1 to 40% by weight of rubber-containing graft copolymer are more preferable.
  • the acrylic resin film of the present invention may contain other thermoplastic resins in addition to the acrylic resin.
  • other thermoplastic resins include olefin polymers, halogenated vinyl polymers, styrene polymers, ester polymers, amide polymers, and the like.
  • the content ratio of the other thermoplastic resin in the acrylic resin film of the present invention is preferably 0 to 50% by weight (when the total amount of the acrylic resin, the rubber-containing graft copolymer, and the other thermoplastic resin is 100% by weight). 0 to 30% by weight is more preferable.
  • the acrylic resin film of the present invention may contain any additive as necessary.
  • additives include stabilizers such as antioxidants, light-resistant stabilizers, weather-resistant stabilizers, and heat stabilizers, ultraviolet absorbers, flame retardants, antistatic agents, fillers, plasticizers, and lubricants.
  • Examples of a method for forming the obtained mixture into a film include any suitable film forming methods such as a solution casting method, a melt extrusion method, a calendar method, and a compression molding method. Of these molding methods, the melt extrusion method is preferred from the balance between cost and performance.
  • melt extrusion method examples include a T-type die method and an inflation method.
  • the molding temperature is preferably 150 to 350 ° C, more preferably 200 to 300 ° C.
  • the T-type die can be attached to the tip of a single screw extruder or a twin screw extruder.
  • a stretched acrylic resin film can be obtained by stretching the acrylic resin film obtained by the above molding method.
  • the stretching process may be performed continuously with the molding process, or after the molding process, the film may be wound into a roll and then the stretching process may be performed.
  • stretching methods generally, a longitudinal stretching method using a roll or a hot air channel, a transverse stretching method using a tenter, a sequential biaxial stretching method in which longitudinal stretching and transverse stretching are performed sequentially, and simultaneous stretching in which longitudinal stretching and transverse stretching are performed simultaneously.
  • Axial stretching is known.
  • at least transverse stretching or simultaneous biaxial stretching is performed.
  • sequential biaxial stretching can be performed by longitudinal stretching before and after transverse stretching.
  • the stretched acrylic resin film of the present invention may be a uniaxially stretched film or a biaxially stretched film.
  • stretching conditions such as temperature and magnification may be the same in longitudinal stretching and lateral stretching, and these conditions may be intentionally changed in longitudinal stretching and lateral stretching.
  • the preheating temperature is preferably Tg + 5 to Tg + 50 ° C. From the viewpoint of breaking and haze during stretching, Tg + 10 to Tg + 40 ° C. is more preferable, Tg + 10 to Tg + 35 ° C. is more preferable, Tg + 14 to Tg + 35 ° C. is still more preferable, and Tg + 14 to Tg + 30 ° C. is particularly preferable. If the preheating temperature is less than Tg + 5 ° C., the film may be easily broken during the stretching process and may not be sufficiently stretched, and even if it does not break, the resulting stretched film has a high haze and excellent optical properties. A stretched film cannot be obtained. On the other hand, if it exceeds Tg + 50 ° C., it becomes close to the melting temperature of the film and cannot be stretched.
  • the transverse stretching step or the simultaneous biaxial stretching step is performed under the conditions where the stretching temperature is Tg + 5 to Tg + 50 ° C.
  • the stretching temperature refers to a temperature measured in the atmosphere around the film when the film is stretched in the stretching step.
  • Tg is the glass transition temperature (° C.) of the acrylic resin film.
  • the stretching temperature is more preferably Tg + 10 to Tg + 40 ° C., further preferably Tg + 10 to Tg + 35 ° C., still more preferably Tg + 14 to Tg + 35 ° C., and particularly preferably Tg + 14 to Tg + 30 ° C.
  • the stretching temperature is less than Tg + 5 ° C.
  • the film may be easily broken during the stretching process and may not be sufficiently stretched, and even if it does not break, the resulting stretched film has a high haze and excellent optical properties.
  • a stretched film cannot be obtained.
  • Tg + 50 ° C. it becomes close to the melting temperature of the film and cannot be stretched.
  • heat treatment may be performed after stretching.
  • the heat treatment temperature after stretching is preferably Tg + 5 to Tg + 50 ° C.
  • Tg + 10 to Tg + 40 ° C. is more preferable
  • Tg + 10 to Tg + 35 ° C. is more preferable
  • Tg + 14 to Tg + 35 ° C. is still more preferable
  • Tg + 14 to Tg + 30 ° C. is particularly preferable. If the heat treatment temperature is lower than Tg + 5 ° C., the film may be rapidly cooled to break the film. On the other hand, if it exceeds Tg + 50 ° C., the film is close to the melting temperature of the film, and the film may adhere to the heat treatment roll or tenter and break.
  • the stretching ratio of the film and the stretching temperature in other stretching steps are optical characteristics required for the stretched film. , Strength, surface properties, and thickness accuracy can be appropriately adjusted as indices.
  • the stretching temperature during transverse stretching is as described above, but the stretching temperature during longitudinal stretching is not particularly limited and may be set as appropriate.
  • the stretching temperature during the longitudinal stretching is preferably in the vicinity of the glass transition temperature of the acrylic resin film, specifically Tg to Tg + 30 ° C. From the viewpoint of preventing sticking to the substrate, Tg + 10 to Tg + 30 ° C. is more preferable.
  • Tg here is the glass transition temperature of an acrylic resin film as described above.
  • the stretching ratio is not particularly limited, but is preferably 1.1 to 10 times, more preferably 1.4 to 5 times in the transverse direction. If the draw ratio is less than 1.1 times, the effect of improving the strength by drawing is not sufficient.
  • the stretching ratio in the longitudinal direction is preferably the same.
  • the stretched acrylic resin film of the present invention is excellent in toughness and has a characteristic that it is not easily broken even when bent. Specifically, as an index indicating such bending resistance, the number of bendings was measured in accordance with JIS P8115 under the condition of a load of 200 g for the stretched acrylic resin film of the present invention having a width of 15 mm and a length of 120 mm. The folding number is preferably 500 times or more.
  • the in-plane retardation Re is preferably 5.0 nm or less
  • the thickness direction retardation Rth is preferably 20.0 nm or less
  • Re is 4.0 nm or less
  • Rth is 15.0 nm or less is more preferable, and when the value of the retardation exceeds these values, the optical characteristics may be deteriorated.
  • the photoelastic coefficient of the stretched acrylic resin film of the present invention is preferably ⁇ 10 ⁇ 10 ⁇ 12 to + 10 ⁇ 10 ⁇ 12 Pa ⁇ 1, more preferably ⁇ 7 ⁇ 10 ⁇ 12 to + 7 ⁇ 10 ⁇ 12 Pa ⁇ 1 .
  • the range of ⁇ 5 ⁇ 10 ⁇ 12 to + 5 ⁇ 10 ⁇ 12 Pa ⁇ 1 is most preferable. If the photoelastic constant is within the above range, even if the film is used in a liquid crystal display device, the birefringence generated is small even when stress is applied to the molded body in an environment such as high temperature and high humidity, and phase difference unevenness occurs And the contrast at the periphery of the display screen does not decrease and light leakage does not occur.
  • the thickness of the stretched acrylic resin film of the present invention is preferably 5 to 100 ⁇ m, more preferably 10 to 80 ⁇ m. If the thickness is less than 5 ⁇ m, sufficient strength cannot be obtained, and if the thickness exceeds 100 ⁇ m, the cost may increase or the thickness of the polarizing plate may increase.
  • the film surface may be subjected to corona discharge treatment, plasma treatment, ozone treatment, ultraviolet irradiation, flame treatment, chemical treatment, and the like. Of these, corona discharge treatment and plasma treatment are preferred.
  • the total haze is preferably 2% or less, and preferably 1.5% or less, from the viewpoint that the glossiness peculiar to the acrylic resin film is maintained and the appearance is good. More preferred.
  • the stretched acrylic resin film of the present invention preferably has an internal haze of 1% or less, more preferably 0.7% or less, and 0.5% or less from the viewpoint of brightness and polarization degree. Is most preferred.
  • an internal haze is a haze value resulting from scattering inside a film.
  • the stretched acrylic resin film of the present invention preferably has an external haze of 1.5% or less, more preferably 1.2% or less, from the viewpoint of brightness and appearance when used as a printing film. Most preferably, it is 1.0% or less.
  • the external haze is a haze value resulting from scattering on the film surface.
  • the stretched acrylic resin film of the present invention is suitable for optical applications and can also be used as a polarizer protective film for polarizing plates.
  • a polarizing plate can be produced as follows, for example.
  • any polarizer may be used as long as it has a function of transmitting only light having a specific vibration direction.
  • a PVA (polyvinyl alcohol) polarizer is preferably used.
  • the PVA polarizer examples include a uniaxially stretched film obtained by adsorbing a dichroic substance such as iodine or a dichroic dye on a hydrophilic polymer film such as a PVA film.
  • the thickness of the polarizer is not particularly limited, and is generally about 1 to 100 ⁇ m.
  • an adhesive layer may be provided on the surface in contact with the polarizer to improve the adhesion with the polarizer, thereby improving the adhesion.
  • the adhesive forming the adhesive layer urethane resin, acrylic resin, epoxy resin, silicone resin, and cellulose resin are preferable from the viewpoint of adhesion.
  • the thickness of the adhesive layer is preferably 0.1 ⁇ m to 10 ⁇ m, and more preferably 0.2 to 5 ⁇ m. If it is less than 0.1 ⁇ m, the adhesion cannot be secured, and if it exceeds 10 ⁇ m, the drying time becomes long and the productivity is lowered.
  • the adhesive composition includes a one-pack type and a two-pack type, and both can be suitably used.
  • Adhesiveness with polyvinyl alcohol varies depending on the type of polyvinyl alcohol and the type of adhesive, and the required adhesion also varies depending on the application. There are uses that can be used if the adhesion is 1 N / 25 mm or more, but in the case of use in a wider range of applications, the adhesion is preferably 3 N / 25 mm or more.
  • Any appropriate application method can be adopted as a method for forming the adhesive layer. Examples thereof include a bar coating method, a roll coating method, a gravure coating method, a rod coating method, a slot orifice coating method, a curtain coating method, and a fountain coating method.
  • the drying temperature of the adhesive is preferably 50 ° C. or higher, and more preferably 80 ° C. or higher.
  • the adhesive may further contain any appropriate additive.
  • additives include anti-blocking agents, dispersion stabilizers, thixotropic agents, antioxidants, ultraviolet absorbers, antifoaming agents, thickeners, dispersants, surfactants, catalysts, fillers, lubricants, and antistatic agents. Agents and the like.
  • the polarizer protective film can be provided on at least one surface of the polarizer.
  • a polarizing plate formed by laminating a polarizer protective film and a polarizer can be further laminated on a substrate such as glass via an adhesive, a pressure-sensitive adhesive or the like.
  • an adhesive layer can be provided on the polarizer protective film and bonded.
  • Arbitrary appropriate adhesives can be used for the adhesive agent used for a contact bonding layer.
  • an adhesive composition containing a polyvinyl alcohol resin is preferred, and an adhesive composition containing an acetoacetyl group-containing polyvinyl alcohol resin is particularly preferred.
  • the average degree of polymerization of the polyvinyl alcohol resin is not particularly limited, but is preferably about 100 to 5000, and more preferably 1000 to 4000.
  • the above adhesive composition may contain a crosslinking agent as required.
  • a crosslinking agent a compound having a functional group having reactivity with the polyvinyl alcohol resin is preferable.
  • Examples of functional groups reactive with polyvinyl alcohol resins include amine groups, isocyanate groups, epoxy groups, aldehyde groups, and methylol groups. Among them, a methylol group is preferable, and a methylol melamine is particularly preferable as a compound having a methylol group.
  • the amount of the crosslinking agent is not particularly limited, but is preferably about 10 to 60 parts by weight, more preferably 20 to 50 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin.
  • various coupling agents and tackifiers may be added to the adhesive composition.
  • a silane coupling agent is preferable.
  • an ultraviolet absorber, an antioxidant, a heat stabilizer, a hydrolysis stabilizer, and the like may be added.
  • the above adhesive composition is usually used as an aqueous solution.
  • concentration of the resin is preferably from 0.1 to 30% by weight, more preferably from 0.5 to 25% by weight, from the balance between coatability and stability.
  • the thickness of the adhesive layer formed from the adhesive composition is set according to the composition of the adhesive composition.
  • the thickness is preferably 10 to 300 nm, and particularly preferably 20 to 150 nm from the viewpoint of adhesiveness.
  • the polarizing plate using the stretched acrylic resin film of the present invention can be suitably used for image display devices such as liquid crystal display devices and self-luminous display devices.
  • the imidation ratio was calculated as follows using IR.
  • the product pellets were dissolved in methylene chloride, and the IR spectrum of the solution was measured at room temperature using a TravelIR manufactured by SensIR Technologies. From the obtained IR spectrum, and the absorption intensity attributable to the ester carbonyl group of 1720cm -1 (Absester), the imidization ratio from the ratio of the absorption intensity attributable to the imide carbonyl group of 1660cm -1 (Absimide) (Im% ( IR)).
  • the “imidation rate” refers to the ratio of the imide carbonyl group in the total carbonyl group.
  • the film thickness was measured using a Digimatic Indicator (manufactured by Mitutoyo Corporation).
  • Glass-transition temperature For the glutarimide acrylic resin (A1) obtained in Production Example 1 and the unstretched films obtained in Examples and Comparative Examples, a differential scanning calorimeter (DSC) SSC-5200 manufactured by Seiko Instruments Inc. was used. The sample was heated up to 200 ° C. at a rate of 25 ° C./minute, held for 10 minutes, and subjected to a preliminary adjustment for lowering the temperature to 50 ° C. at a rate of 25 ° C./minute. The measurement was performed while the temperature was raised to 200 ° C., the integral value was determined from the obtained DSC curve (DDSC), and the glass transition temperature was determined from the maximum point.
  • DSC differential scanning calorimeter
  • Total light transmittance / haze value The total light transmittance and the total haze value of the stretched films obtained in Examples and Comparative Examples were measured by the method described in JIS K7105 using Nippon Denshoku Industries NDH-300A. The internal haze value was measured under the same conditions as for all haze values except that pure water was added to the quartz cell. The external haze value was calculated by subtracting the internal haze value from the total haze value.
  • the average particle size of the rubber particles was measured in a latex state of the rubber particles. The measurement was performed using light scattering at a wavelength of 546 nm using a U-5100 type ratio beam spectrophotometer manufactured by Hitachi High-Technologies Corporation.
  • Polymerization conversion rate (%) [(Total weight of charged raw material x solid component ratio-total weight of raw materials other than water and monomer) / weight of charged monomer] x 100 (Production Example 1) ⁇ Manufacture of glutarimide acrylic resin (A1)> A glutarimide acrylic resin (A1) was produced using polymethyl methacrylate as a raw material and monomethylamine as an imidizing agent.
  • a tandem type reaction extruder in which two extrusion reactors were arranged in series was used.
  • the meshing type co-directional twin-screw extruder having a diameter of 75 mm for both the first and second extruders and L / D (ratio of the length L to the diameter D of the extruder) of 74.
  • the raw material was supplied to the raw material supply port of the first extruder using a low-weight feeder (manufactured by Kubota Corporation).
  • the degree of vacuum of each vent in the first extruder and the second extruder was ⁇ 0.095 MPa.
  • the pressure control mechanism in the part connects the first extruder and the second extruder with a pipe having a diameter of 38 mm and a length of 2 m, and connects the resin discharge port of the first extruder and the raw material supply port of the second extruder. Used a constant flow pressure valve. The resin discharged from the second extruder was cooled with a cooling conveyor, and then cut into pellets with a pelletizer.
  • the discharge port of the first extruder, the first extruder and the first extruder Resin pressure gauges were provided at the center of the connecting parts between the two extruders and at the outlet of the second extruder.
  • a polymethyl methacrylate resin (Mw: 105,000) was used as a raw material resin, and an imide resin intermediate 1 was produced using monomethylamine as an imidizing agent.
  • the temperature of the highest temperature part of the extruder was 280 ° C.
  • the screw rotation speed was 55 rpm
  • the raw material resin supply amount was 150 kg / hour
  • the addition amount of monomethylamine was 2.0 parts relative to 100 parts of the raw material resin.
  • the constant flow pressure valve was installed immediately before the raw material supply port of the second extruder, and the monomethylamine press-fitting portion pressure of the first extruder was adjusted to 8 MPa.
  • the imidizing agent and by-products remaining in the rear vent and vacuum vent were degassed, and then dimethyl carbonate was added as an esterifying agent to produce an imide resin intermediate 2.
  • the barrel temperature of the extruder was 260 ° C.
  • the screw rotation speed was 55 rpm
  • the addition amount of dimethyl carbonate was 3.2 parts with respect to 100 parts of the raw resin.
  • it was extruded from a strand die, cooled in a water tank, and then pelletized with a pelletizer to obtain a glutarimide acrylic resin (A1).
  • the imidization rate, the content of glutarimide units, the acid value, and the glass transition temperature were measured according to the above methods.
  • the imidation ratio was 13%
  • the content of glutarimide units was 7% by weight
  • the acid value was 0.4 mmol / g
  • the glass transition temperature was 124 ° C.
  • the obtained innermost layer polymer latex was kept at 80 ° C. in a nitrogen stream, 0.1 parts of potassium persulfate was added, and then a single unit consisting of 41 parts of n-butyl acrylate, 9 parts of styrene, and 1 part of allyl methacrylate.
  • the monomer mixture ((B-2) of Production Example 1 in Table 1) was continuously added over 5 hours. During this time, 0.1 part of potassium oleate was added in three portions. After completing the addition of the monomer mixture, 0.05 part of potassium persulfate was further added and held for 2 hours to complete the polymerization, thereby obtaining a rubber particle latex.
  • the polymerization conversion rate of the obtained rubber particles was 99%.
  • graft copolymer The obtained rubber particle latex was kept at 80 ° C., 0.02 part of potassium persulfate was added, and then a monomer mixture of 14 parts of methyl methacrylate and 1 part of n-butyl acrylate (of Production Example 1 in Table 1). (B-3)) was continuously added over 1 hour. After completion of the addition of the monomer mixture, the mixture was held for 1 hour to obtain a graft copolymer latex. The polymerization conversion rate was 99%.
  • Example 1 Manufacture of stretched acrylic resin film
  • 80 parts by weight of glutarimide acrylic resin (A1) and 20 parts by weight of rubber-containing graft copolymer (B1) were pelletized by a twin screw extruder at a resin temperature of about 255 ° C.
  • the obtained pellets were supplied to a biaxial extruder and melt-extruded into a sheet at about 260 ° C. to obtain an unstretched film having a thickness of 125 ⁇ m.
  • This unstretched film is preheated at 132 ° C. for 5 minutes, stretched at a stretching speed of 120 mm / min and stretched at 132 ° C., and simultaneously biaxially stretched 1.8 times in length and 1.8 times in width.
  • a resin film (thickness 40 ⁇ m) was prepared.
  • Example 2 Manufacture of stretched acrylic resin film
  • Pellets of 80 parts by weight of glutarimide acrylic resin (A1) and 20 parts by weight of rubber-containing graft copolymer (B1) are fed to a biaxial extruder and melt extruded into a sheet at about 260 ° C. to obtain a thickness.
  • An unstretched film of 125 ⁇ m was obtained.
  • This unstretched film was preheated at 136 ° C. for 5 minutes, and simultaneously biaxially stretched 1.8 times in length and 1.8 times in width under the stretching temperature condition of 120 mm / min and 136 ° C.
  • a resin film (thickness 40 ⁇ m) was prepared.
  • Example 3 Manufacture of stretched acrylic resin film
  • Pellets of 80 parts by weight of glutarimide acrylic resin (A1) and 20 parts by weight of rubber-containing graft copolymer (B1) are fed to a biaxial extruder and melt extruded into a sheet at about 260 ° C. to obtain a thickness.
  • An unstretched film of 125 ⁇ m was obtained.
  • This unstretched film is preheated at 140 ° C. for 5 minutes, stretched at 120 mm / min, at a stretching temperature of 140 ° C. and simultaneously biaxially stretched 1.8 times in length and 1.8 times in width, and then stretched acrylic.
  • a resin film (thickness 40 ⁇ m) was prepared.
  • Example 4 Manufacture of stretched acrylic resin film
  • Pellets of 90 parts by weight of glutarimide acrylic resin (A1) and 10 parts by weight of rubber-containing graft copolymer (B1) are fed to a biaxial extruder and melt extruded into a sheet at about 260 ° C. to obtain a thickness.
  • An unstretched film of 125 ⁇ m was obtained.
  • This unstretched film is preheated at 132 ° C. for 5 minutes, stretched at a stretching speed of 120 mm / min and stretched at 132 ° C., and simultaneously biaxially stretched 1.8 times in length and 1.8 times in width.
  • a resin film (thickness 40 ⁇ m) was prepared.
  • Example 5 Manufacture of stretched acrylic resin film
  • Pellets of 80 parts by weight of glutarimide acrylic resin (A1) and 20 parts by weight of rubber-containing graft copolymer (B1) are fed to a biaxial extruder and melt extruded into a sheet at about 260 ° C. to obtain a thickness.
  • An unstretched film of 125 ⁇ m was obtained.
  • This unstretched film was preheated at 136 ° C. for 5 minutes, first stretched at a length of 1.8 times, and stretched 1.8 times as it was after the lengthwise stretching. Both longitudinal stretching and lateral stretching were successively biaxially stretched 1.8 times in length and 1.8 times in width under a stretching temperature condition of 136 ° C. to prepare a stretched acrylic resin film (40 ⁇ m thickness).
  • Example 6 Manufacture of stretched acrylic resin film
  • pellets of 95 parts by weight of rubber-containing graft copolymer (B1) are fed to a twin screw extruder. Then, it was melt extruded into a sheet at about 260 ° C. to obtain an unstretched film having a thickness of 125 ⁇ m.
  • This unstretched film was simultaneously biaxially stretched 1.8 times in length and 1.8 times in width under a stretching temperature condition of 130 ° C. to produce a stretched acrylic resin film (40 ⁇ m thickness).
  • Comparative Example 1 Manufacture of stretched acrylic resin film
  • Pellets of 80 parts by weight of glutarimide acrylic resin (A1) and 20 parts by weight of rubber-containing graft copolymer (B1) are fed to a biaxial extruder and melt extruded into a sheet at about 260 ° C. to obtain a thickness.
  • An unstretched film of 125 ⁇ m was obtained.
  • This unstretched film was simultaneously biaxially stretched 1.8 times in length and 1.8 times in width under a stretching temperature condition of 115 ° C., but the film broke during stretching.
  • Comparative Example 2 Manufacture of stretched acrylic resin film
  • Pellets of 80 parts by weight of glutarimide acrylic resin (A1) and 20 parts by weight of rubber-containing graft copolymer (B1) are fed to a biaxial extruder and melt extruded into a sheet at about 260 ° C. to obtain a thickness.
  • An unstretched film of 125 ⁇ m was obtained.
  • This unstretched film was simultaneously biaxially stretched 1.8 times in length and 1.8 times in width under a stretching temperature condition of 122 ° C. to prepare a stretched acrylic resin film (40 ⁇ m thickness).
  • Table 2 shows the results of measuring various physical properties of the stretched acrylic resin films obtained in Examples and Comparative Examples.

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Abstract

L'invention concerne un procédé de production d'un film de résine acrylique étiré constitué d'une composition qui comprend 99-50% en poids de résine acrylique (A) et 1-50% en poids d'un copolymère greffé contenant du caoutchouc (B) (la somme des deux est de 100% en poids), où le composant (B) comprend une couche la plus interne comprenant un polymère obtenu à l'aide d'un ester méthacrylique en tant que monomère principal, une couche intermédiaire comprenant un polymère obtenu à l'aide d'un acrylate d'alkyle ayant un groupe alkyle en C4-12 en tant que monomère principal, et une ou plusieurs couches les plus externes comprenant un polymère obtenu à l'aide d'un ester méthacrylique comme monomère, la couche la plus interne et la couche intermédiaire constituant un élastomère réticulé, l'élastomère réticulé ayant un diamètre moyen de particule de 150-400 nm, le procédé comprenant une étape dans laquelle un film de résine acrylique constitué de la composition est soumis à l'étirage transversal ou à l'étirage biaxial simultané, dans les conditions d'une température d'étirage de (Tg+5)°C à (Tg+50)°C (Tg est la température de transition vitreuse du film de résine acrylique constitué de la composition).
PCT/JP2016/001875 2015-03-31 2016-03-31 Procédé de fabrication d'un film de résine acrylique étiré Ceased WO2016157913A1 (fr)

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JP2022010998A (ja) * 2020-06-29 2022-01-17 株式会社クラレ 熱可塑性樹脂フィルム
JP7441743B2 (ja) 2020-06-29 2024-03-01 株式会社クラレ 熱可塑性樹脂フィルム
CN114075362A (zh) * 2020-08-11 2022-02-22 藤森工业株式会社 (甲基)丙烯酸类树脂组合物及(甲基)丙烯酸类树脂膜
TWI868385B (zh) * 2020-08-11 2025-01-01 日商藤森工業股份有限公司 （甲基）丙烯酸類樹脂組合物及（甲基）丙烯酸類樹脂膜
CN116761840A (zh) * 2020-12-25 2023-09-15 株式会社钟化 层叠体及其利用
WO2022145436A1 (fr) * 2021-01-04 2022-07-07 株式会社カネカ Procédé de production d'un film étiré
JPWO2022145436A1 (fr) * 2021-01-04 2022-07-07
JP7829499B2 (ja) 2021-01-04 2026-03-13 株式会社カネカ 延伸フィルムの製造方法
CN117925136A (zh) * 2023-12-20 2024-04-26 广东桑泰科技有限公司 一种折叠手机保护膜的制备工艺及其产品

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