Classifications

• • 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
  • 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

Definitions

• the present invention relates to a graft copolymer capable of forming a resin film, a resin composition for producing a film containing the copolymer, a dope, and a resin film.
• Methacrylic resin is an excellent polymer that is used in large quantities in various fields in industry because it has excellent transparency, color tone, appearance, weather resistance, luster and processability.
• resin films molded from methacrylic resin take advantage of their excellent transparency, appearance, and weather resistance, and are used for interior and exterior materials for automobiles, exterior materials for electrical appliances such as mobile phones and smartphones, and floors, windows, and interior and exterior walls. It is used for various purposes such as interior and exterior materials for civil engineering and construction such as light collecting parts and road signs.
• methacrylic resins have been applied to optical members such as liquid crystal display devices and organic EL display devices by taking advantage of their excellent optical characteristics.
• a resin film molded from a general methacrylic resin has a drawback of low impact resistance. Therefore, for the purpose of improving impact resistance, a method of blending a graft copolymer containing a rubber component with a methacrylic resin is widely used.
• a core-shell type graft copolymer having a core layer made of rubber and a shell layer for improving compatibility with a methacrylic resin is known (for example, Patent Document 1). See).
• the strength of the methacrylic resin can be improved by blending the conventional core-shell type graft copolymer, there is a problem that the core-shell type graft copolymer tends to aggregate due to the contained rubber component and the storage stability is low. rice field. Further, when producing a resin film by the solution casting method, the dope tends to become turbid, especially after a lapse of time after the conventional core-shell type graft copolymer is dissolved in a solvent together with a methacrylic resin to prepare a dope. The resin film produced from the dope also has a problem that the haze is lowered. In addition, it is difficult to design a resin film formed by blending a core-shell type graft copolymer with a methacrylic resin so that the phase difference is further increased while achieving both high strength and low haze. rice field.
• the present invention comprises a graft copolymer having excellent heat resistance, high strength, low haze, a large phase difference, and good storage stability, and the graft. It is an object of the present invention to provide a resin film formed from a copolymer.
• the present inventors have contained a specific crosslinked (meth) acrylic polymer particle and a specific non-crosslinked methacrylic polymer component in a specific ratio, and said the non-crosslinked methacrylic.
• a graft copolymer obtained by graft-bonding a system polymer component to the crosslinked (meth) acrylic polymer particles, and have reached the present invention.
• the present invention comprises crosslinked (meth) acrylic polymer particles having an average particle diameter of 150 nm or less, a glass transition temperature of ⁇ 10 ° C. or less, and containing (meth) acrylic monomer units and styrene-based monomer units.
• a non-crosslinked methacrylic polymer component (b) having a weight average molecular weight of 250,000 or more and containing a methacrylic monomer unit and a styrene-based monomer unit, and a non-crosslinked methacrylic polymer component ( At least a part of b) is graft-bonded to the crosslinked (meth) acrylic polymer particles (a), and the crosslinked (meth) acrylic polymer particles (a) and the non-crosslinked methacrylic polymer component (b).
• the present invention relates to a graft copolymer in which the proportion of the crosslinked (meth) acrylic polymer particles (a) is 1% by weight or more and less than 50% by weight.
• the non-crosslinked methacrylic polymer component (b) contains 50% by weight or more and 90% by weight or less of the methyl methacrylate unit, and 10% by weight or more and 50% by weight or less of the styrene-based monomer unit.
• the non-bridged methacrylic polymer component (b) is an N-substituted maleimide-based monomer unit, and the ester moiety is a primary or secondary hydrocarbon group having 2 to 20 carbon atoms or an aromatic hydrocarbon group.
• the non-crosslinked methacrylic polymer component (b) is an N-substituted maleimide-based monomer unit and a methacrylic acid ester unit in which the ester moiety is a saturated hydrocarbon group having a condensed ring structure and having 7 to 16 carbon atoms. Further includes at least one of them.
• the non-crosslinked methacrylic polymer component (b) has a glass transition temperature of 110 ° C. or higher.
• the crosslinked (meth) acrylic polymer particles (a) contain 60 acrylic acid alkyl ester units having an alkyl group having 1 to 8 carbon atoms among the monomer components excluding the polyfunctional monomer. It contains 5% by weight or more and 95% by weight or less, and contains 5% by weight or more and 40% by weight or less of a styrene-based monomer unit.
• the crosslinked (meth) acrylic polymer particles (a) have 100 parts by weight of a monomer component excluding the polyfunctional monomer and 0.1 to 2.0 parts by weight of the polyfunctional monomer. Formed from.
• the present invention also comprises a resin composition for film production by a solution casting method containing a graft copolymer; a resin composition for film production and a dope containing a solvent; the dope is cast on the surface of a support.
• the present invention relates to a method for producing a resin film, which comprises a step of evaporating a solvent; or a resin film formed from the resin composition for producing a film by a solution casting method.
• the resin film has a thickness of 1 to 500 ⁇ m.
• the resin film is a retardation film.
• the present invention also relates to a polarizing plate formed by laminating a polarizing element and the resin film; and a display device including the polarizing plate.
• a graft copolymer having excellent heat resistance, high strength, low haze, and a large phase difference can be formed, and has good storage stability, and formed from the polymer.
• Resin film can be provided.
• the graft copolymer according to the present invention can form a high-strength resin film even if the resin component is only the copolymer. Further, since it is not necessary to mix and disperse the core-shell type graft copolymer in the methacrylic resin as in the conventional case, a resin film having a low haze can be easily formed.
• the graft copolymer has good storage stability even though it contains a rubber component, and has an advantage that the dope is less likely to become turbid when it is dissolved in a solvent to prepare a dope. There is also. As a result, the dope can be used to reduce the haze of the resin film produced by the solution casting method.
• the graft copolymer according to the present embodiment contains crosslinked (meth) acrylic polymer particles (a) and a non-crosslinked methacrylic polymer component (b). Since the crosslinked (meth) acrylic polymer particles (a) are rubber components, they can contribute to the improvement of strength. Further, excellent heat resistance can be achieved by the non-crosslinked methacrylic polymer component (b).
• the crosslinked (meth) acrylic polymer particles (a) correspond to the rubber component of the core in the core-shell type graft copolymer.
• the non-crosslinked methacrylic polymer component (b) can correspond to the methacrylic resin which is a matrix.
• At least a part of the non-crosslinked methacrylic polymer component (b) is graft-bonded to the crosslinked (meth) acrylic polymer particles (a).
• the graft bond can be realized by producing a graft copolymer by emulsion polymerization as described later. Due to this production method, the graft copolymer may also contain a non-crosslinked methacrylic polymer component (b) that is not graft-bonded to the crosslinked (meth) acrylic polymer particles (a).
• the graft copolymer according to the present embodiment has a configuration in which crosslinked (meth) acrylic polymer particles (a) having a small particle size are dispersed in a high-molecular-weight non-crosslinked methacrylic polymer component (b). Therefore, the aggregation of the crosslinked (meth) acrylic polymer particles (a) does not easily proceed in the graft copolymer. As a result, the stability is good both when the graft copolymer according to the present embodiment is stored in the form of powder and when it is stored as a dope dissolved in a solvent. Further, since the aggregation of the crosslinked (meth) acrylic polymer particles (a) is suppressed, the graft copolymer according to the present embodiment has an advantage that it is easily dissolved in a solvent.
• the crosslinked (meth) acrylic polymer particles (a) are (meth) acrylic rubber particles.
• high strength can be achieved, for example, when formed into a film.
• the crosslinked (meth) acrylic polymer particles (a) have a relatively small particle size, specifically, an average particle size of 150 nm or less.
• a relatively small particle size specifically, an average particle size of 150 nm or less.
• the average particle size is preferably 130 nm or less, more preferably 120 nm or less, further preferably 110 nm or less, still more preferably 100 nm or less.
• the lower limit of the average particle size is not particularly limited, but from the viewpoint of film strength or ease of particle production, 30 nm or more is preferable, 40 nm or more is more preferable, 45 nm is further preferable, and 50 nm or more is particularly preferable.
• the average particle size is the volume average particle size, and can be measured as described in the section of Examples. Further, the average particle size can be controlled by adjusting the conditions at the time of particle preparation (specifically, the type and amount of the emulsifier, the stirring conditions at the time of emulsion polymerization, etc.).
• the crosslinked (meth) acrylic polymer particles (a) show a glass transition temperature of ⁇ 10 ° C. or lower.
• the glass transition temperature can be controlled by adjusting the type and ratio of the monomers constituting the crosslinked (meth) acrylic polymer particles (a).
• the glass transition temperature of the crosslinked (meth) acrylic polymer particles (a) is preferably ⁇ 20 ° C. or lower, more preferably ⁇ 25 ° C. or lower.
• the lower limit of the glass transition temperature is not particularly limited, but for example, ⁇ 130 ° C. or higher is preferable, ⁇ 110 ° C. or higher is more preferable, ⁇ 100 ° C. or higher is further preferable, ⁇ 80 ° C. or higher is further preferable, and ⁇ 70 ° C. or higher. Is particularly preferable.
• the Fox formula was used using the values described in the Polymer Handbook [Polymer Hand Book (J. Brandrup, Interscience 1989)]. (For example, n-butyl polyacrylate is ⁇ 54 ° C.).
• the crosslinked (meth) acrylic polymer particles (a) are crosslinked (a) formed by polymerizing a monomer component containing a (meth) acrylic monomer and a styrene-based monomer, and a polyfunctional monomer. Meta) Particles formed from an acrylic polymer.
• the phase difference can be increased when the graft copolymer is formed into a film, for example.
• the monomer component excluding the polyfunctional monomer contains an acrylic monomer and / or a methacrylic monomer and a styrene-based monomer, but at least an acrylic-based monomer and a styrene-based monomer. It is preferable to include the body.
• an acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms is preferable. Specific examples thereof include ethyl acrylate, n-butyl acrylate, n-octyl acrylate, and 2-ethylhexyl acrylate.
• the acrylic acid alkyl ester only one kind may be used, or two or more kinds may be used in combination. Of these, n-butyl acrylate is preferable.
• a methacrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms is preferable. Specific examples thereof include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate and the like.
• the methacrylic acid alkyl ester only one kind may be used, or two or more kinds may be used in combination. Of these, a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferable. In particular, methyl methacrylate is preferable.
• styrene-based monomer contained in the crosslinked (meth) acrylic polymer particles (a) examples include styrene, ⁇ -methylstyrene, monochlorostyrene, dichlorostyrene and the like.
• a monomer other than the above-mentioned acrylic acid alkyl ester, methacrylic acid alkyl ester and styrene-based monomer may be used.
• examples of such a monomer include acrylic acid esters other than the acrylic acid alkyl ester, methacrylic acid esters other than the methacrylic acid alkyl ester, and other copolymerizable vinyl monomers.
• examples of the acrylic acid ester other than the acrylic acid alkyl ester include phenyl acrylate, benzyl acrylate, cyclohexyl acrylate, and isobornyl acrylate.
• methacrylic acid ester other than the methacrylic acid alkyl ester examples include phenyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate and the like.
• the other copolymerizable vinyl monomer examples include unsaturated nitrile-based monomers such as acrylonitrile and methacrylonitrile, ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, and acetic acid.
• Olefin monomers such as vinyl, ethylene and propylene, vinyl halide monomers such as vinyl chloride, vinylidene chloride and vinylidene fluoride, N-ethylmaleimide, N-propylmaleimide, N-cyclohexylmaleimide, N-phenyl Examples thereof include maleimide-based monomers such as maleimide and NO-chlorophenylmaleimide. All of these may be used alone or in combination of two or more.
• the monomer component constituting the crosslinked (meth) acrylic polymer particles (a) is an acrylic acid ester (particularly alkyl) among the monomer components excluding the polyfunctional monomer.
• Acrylic acid alkyl ester having 1 to 8 carbon atoms as a group is preferably contained in an amount of 50% by weight or more and 99% by weight or less, more preferably 55% by weight or more and 97% by weight or less, and 60% by weight or more and 95% by weight or less. It is more preferably contained below, and particularly preferably 65% by weight or more and 92% by weight or less.
• Cross-linked (meth) acrylic weight from the viewpoint of adjusting the refractive index between the cross-linked (meth) acrylic polymer particles (a) for ensuring transparency and the non-cross-linked methacrylic polymer component (b) and expressing the phase difference.
• the monomer component constituting the coalesced particles (a) preferably contains 1% by weight or more and 50% by weight or less of the styrene-based monomer among the monomer components excluding the polyfunctional monomer, and is preferably 3% by weight.
• the crosslinked (meth) acrylic polymer particles (a) are formed by polymerizing the monomer component in the presence of a polyfunctional monomer.
• the polyfunctional monomer is also known as a cross-linking agent or a cross-linking monomer, and has an unsaturated bond in one molecule that can be copolymerized with the (meth) acrylic monomer and the styrene-based monomer. It is a compound having two or more of them.
• allyl methacrylate allyl acrylate, diallyl maleate, diallyl fumarate, diallyl itaconate, monoallyl maleate, monoallyl fumarate, butadiene, divinylbenzene, triallyl isocyanurate, alkylene glycol dimethacrylate, alkylene glycol.
• diacrylate Only one kind of these may be used, or two or more kinds may be used. Preferred is allyl methacrylate.
• the amount of the polyfunctional monomer used can be appropriately set from the viewpoint of strength, but specifically, the monomer component constituting the crosslinked (meth) acrylic polymer particles (a) (provided that it is used).
• Monomer component excluding polyfunctional monomer It may be about 0.1 parts by weight or more and 5.0 parts by weight or less with respect to 100 parts by weight.
• the amount of the polyfunctional monomer used is preferably 0.2 to 3.5 parts by weight, more preferably 0.2 to 3.0 parts by weight, and 0. .3 to 2.0 parts by weight is more preferable, and 0.4 to 1.5 parts by weight is particularly preferable.
• Non-crosslinked methacrylic polymer component (b) The non-crosslinked methacrylic polymer component (b) is composed of at least a methacrylic monomer and a styrene-based monomer polymerized and does not have a crosslinked structure (that is, by polymerization without using a polyfunctional monomer). It is a polymer (obtained). At least a part of the non-crosslinked methacrylic polymer component (b) is graft-bonded to the crosslinked (meth) acrylic polymer particles (a), whereby the crosslinked (meth) acrylic polymer particles (a). Is less likely to aggregate, the graft copolymer according to the present embodiment has good storage stability, and low haze can be achieved when formed into a film.
• the non-crosslinked methacrylic polymer component (b) is a polymer having a high molecular weight, and specifically, has a weight average molecular weight of 250,000 or more. Since the non-crosslinked methacrylic polymer component (b) has a high molecular weight, the graft copolymer according to the present embodiment can achieve high heat resistance and can be formed into a film by a solution casting method. Become.
• the weight average molecular weight is preferably 300,000 or more, more preferably 350,000 or more, further preferably 400,000 or more, and particularly preferably 450,000 or more, from the viewpoint of facilitating film formation by the solution casting method.
• the upper limit of the weight average molecular weight is not particularly limited, but is preferably 1 million or less, more preferably 900,000 or less, for example, from the viewpoint of facilitating film formation by the solution casting method.
• the weight average molecular weight of the non-crosslinked methacrylic polymer component (b) can be measured according to the description in the section of Examples.
• the non-crosslinked methacrylic polymer component (b) preferably has a glass transition temperature of 105 ° C. or higher, more preferably 110 ° C. or higher, from the viewpoint of heat resistance of the graft copolymer.
• the upper limit of the glass transition temperature is not particularly limited, but may be, for example, 160 ° C. or lower, or 150 ° C. or lower.
• the glass transition temperature can be controlled by adjusting the type and ratio of the monomers constituting the non-crosslinked methacrylic polymer component (b).
• the glass transition temperature of the non-crosslinked methacrylic polymer component (b) can be measured as described in the section of Examples, but it is described in the Polymer Handbook [Polymer Hand Book (J. Brandrup, Interscience 1989)]. The values described can also be calculated using Fox's equation (eg, polymethylmethacrylate is 105 ° C.).
• the non-crosslinked methacrylic polymer component (b) is a polymer composed of at least a methacrylic monomer unit and a styrene monomer unit. From the viewpoint of heat resistance of the graft copolymer and film formation, the methyl methacrylate unit is preferable as the methacrylic monomer unit. In particular, among the monomer components constituting the non-crosslinked methacrylic polymer component (b), it is preferable that the methyl methacrylate unit is contained in an amount of 50% by weight or more and 90% by weight or less. As a result, the heat resistance can be improved and film formation by the solution casting method can be more easily realized.
• the content of the methyl methacrylate unit is more preferably 53 to 85% by weight, further preferably 55 to 80% by weight, further preferably 58 to 75% by weight, and particularly preferably 60 to 70% by weight.
• the non-crosslinked methacrylic polymer component (b) contains a styrene-based monomer unit. From this point of view, among the monomer components constituting the non-crosslinked methacrylic polymer component (b), it is preferable that the styrene-based monomer unit is contained in an amount of 10% by weight or more and 50% by weight, more preferably 15 to 45% by weight. It is preferable, 20 to 40% by weight is more preferable, and 25 to 35% by weight is particularly preferable.
• the styrene-based monomer include styrene, ⁇ -methylstyrene, monochlorostyrene, dichlorostyrene and the like, and styrene is preferable.
• the non-crosslinked methacrylic polymer component (b) is a primary unit having an N-substituted maleimide-based monomer unit and an ester moiety having 2 to 20 carbon atoms as a monomer unit other than the methyl methacrylate unit and the styrene-based monomer.
• a methacrylic acid ester unit which is a secondary hydrocarbon group or an aromatic hydrocarbon group a methacrylic acid ester unit which is a saturated hydrocarbon group having 7 to 16 carbon atoms whose ester moiety has a fused ring structure, and an ester moiety.
• the heat resistance of the graft copolymer is not significantly reduced, and the solvent is used when the solvent is evaporated from the cast film when the film is produced by the solution casting method. It is possible to increase the volatilization rate.
• the above-mentioned monomer unit is also referred to as "drying-promoting comonomer unit" below.
• N-substituted maleimide-based monomer examples include N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, and N-methylmaleimide.
• maleimide-based monomer units having a cyclic substituent on the N atom are preferable, that is, N-phenylmaleimide, N-benzylmaleimide, and N-cyclohexylmaleimide are preferable.
• methacrylic acid ester in which the ester moiety is a primary or secondary hydrocarbon group having 2 to 20 carbon atoms or an aromatic hydrocarbon group
• examples of the methacrylic acid ester in which the ester moiety is a primary or secondary hydrocarbon group having 2 to 20 carbon atoms or an aromatic hydrocarbon group include ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate.
• ethyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, and benzyl methacrylate are preferable.
• Examples of the methacrylic acid ester in which the ester moiety is a saturated hydrocarbon group having 7 to 16 carbon atoms having a condensed ring structure include dicyclopentanyl methacrylate and isobornyl methacrylate.
• the saturated hydrocarbon group preferably has 8 to 14 carbon atoms, more preferably 9 to 12 carbon atoms.
• the fused ring structure is not particularly limited, but is preferably a structure in which two five-membered rings are fused by three consecutive carbon atoms.
• Examples of the methacrylic acid ester in which the ester moiety is a linear or branched group containing an ether bond include 2-methoxyethyl methacrylate.
• the drying-promoting comonomer unit is an N-substituted maleimide-based unit. It is preferable to contain at least one of a monomer unit and a methacrylic acid ester unit in which the ester moiety is a saturated hydrocarbon group having 7 to 16 carbon atoms having a condensed ring structure.
• drying-promoting comonomer unit at least one of an N-substituted maleimide-based monomer unit and a methacrylic acid ester unit which is a saturated hydrocarbon group having 7 to 16 carbon atoms whose ester moiety has a condensed ring structure. Only seeds may be used, but at least one of an N-substituted maleimide-based monomer unit and a methacrylic acid ester unit which is a saturated hydrocarbon group having 7 to 16 carbon atoms and whose ester moiety has a condensed ring structure.
• Other drying-promoting comonomer units may be used in combination. By such a combined use, it is possible to adjust the heat resistance of the graft copolymer and the volatilization rate of the solvent to improve both in a well-balanced manner.
• the ester moiety as described above is carbon.
• the proportion of the drying-promoting comonomer unit is preferably 1% by weight or more and 30% by weight or less, more preferably 2 to 25% by weight.
• 3 to 20% by weight is still more preferable, 4 to 18% by weight is further preferable, 4 to 15% by weight is further preferable, 4 to 12% by weight is further preferable, and 5 to 10% by weight is particularly preferable.
• the ratio of the drying-promoting comonomer units means the ratio of the total amount of all the drying-promoting comonomer units contained in the total monomer units. By setting such a weight ratio, the volatilization rate of the solvent in the solution casting method can be increased while the graft copolymer has excellent heat resistance.
• the weight ratio of each of these units can be determined by proton nuclear magnetic resonance spectroscopy.
• the non-crosslinked methacrylic polymer component (b) may be a copolymer that does not contain other comonomer units that do not correspond to the drying-promoting comonomer unit, or may contain other comonomer units that do not correspond to the drying-promoting comonomer unit. It may be a copolymer containing. Examples of such other comonomers include glycidyl methacrylate, epoxycyclohexylmethyl methacrylate, dimethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2,2,2-trifluoroethyl.
• Methacrylic acid esters such as methacrylate, 2,2,2-trichloroethyl methacrylate, methacrylic acid, N-methylol methacrylic acid; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate.
• Acrylic acid esters such as benzyl acrylate, octyl acrylate, glycidyl acrylate, epoxycyclohexylmethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, acrylamide, N-methylol acrylamide; methacrylic acid , Acrylic acid and other carboxylic acids and salts thereof; vinyl cyanides such as acrylonitonyl and methacrylic acid; maleic acid, fumaric acid and their esters, etc .; vinyl halides such as vinyl chloride, vinyl bromide, chloroprene; , Vinyl acetate, vinyl ester such as vinyl propionate; alkenes such as ethylene, propylene, butylene, butadiene, isobutylene and the like.
• the ratio of such other comonomer units to the monomer components constituting the non-crosslinked methacrylic polymer component (b) is preferably 10% by weight or less, more preferably 8% by weight or less. It is preferably 5% by weight or less, and more preferably 5% by weight or less.
• the crosslinked (meth) acrylic polymer particles (a) out of the total of the crosslinked (meth) acrylic polymer particles (a) and the non-crosslinked methacrylic polymer component (b).
• the proportion of the non-crosslinked methacrylic polymer component (b) is 99% by weight or less and more than 50% by weight.
• the ratio of the crosslinked (meth) acrylic polymer particles (a) is preferably 3% by weight or more and 45% by weight or less, more preferably 4 to 40% by weight, further preferably 5 to 35% by weight, and 6 to 30%. % By weight is particularly preferred.
• the crosslinked (meth) acrylic polymer particles (meth) among the total of the crosslinked (meth) acrylic polymer particles (a) and the non-crosslinked methacrylic polymer component (b) (
• the proportion of a) is preferably 5% by weight or more, more preferably 6% by weight or more, still more preferably 7% by weight or more.
• the upper limit of the ratio is preferably 25% by weight or less, more preferably 20% by weight or less, further preferably 15% by weight or less, still more preferably 12% by weight or less, and 10%. Weight% or less is particularly preferable.
• 6% by weight or more is preferable, 7% by weight or more is more preferable, 20% by weight or less is preferable, 15% by weight or less is more preferable, and 12% by weight is preferable. % Or less is more preferable, and 10% by weight or less is particularly preferable.
• the graft copolymer according to the present embodiment can be produced by ordinary emulsion polymerization using an emulsifier and a polymerization initiator. Specifically, after forming crosslinked (meth) acrylic polymer particles (a) by emulsion polymerization, a monomer component constituting the non-crosslinked methacrylic polymer component (b) is added to the polymerization system. Subsequently, emulsion polymerization is carried out to form the non-crosslinked methacrylic polymer component (b).
• the emulsifier is not particularly limited, but for example, sodium alkylsulfonate, sodium alkylbenzenesulfonate, sodium dioctylsulfocuccinate (sodium sulfosuccinate (2-ethylhexyl)), sodium lauryl sulfate, sodium fatty acid, polyoxyethylene lauryl.
• Anionic surfactants such as phosphate ester salts such as ether sodium phosphate, nonionic surfactants and the like are shown. These surfactants may be used alone or in combination of two or more.
• phosphoric acid such as sodium dioctyl sulphosuccinate (di (2-ethylhexyl) sulfosuccinate), sodium polyoxyethylene lauryl ether phosphate, etc. It is preferable to polymerize using an ester salt (alkali metal or alkaline earth metal), and in particular, using a phosphate ester salt (alkali metal or alkaline earth metal) such as polyoxyethylene lauryl ether sodium phosphate. It is preferable to polymerize.
• the polymerization initiator is not particularly limited, but from the viewpoint of improving the thermal stability of the film, a polymerization initiator having a 10-hour half-life temperature of 100 ° C. or less is preferable.
• the polymerization initiator is not particularly limited, but a persulfate is preferable. Specific examples thereof include potassium persulfate, sodium persulfate, ammonium persulfate and the like.
• the polymerization initiator is preferably added at least at the stage of forming the crosslinked (meth) acrylic polymer particles (a), and may be additionally added at the stage of forming the non-crosslinked methacrylic polymer component (b). good.
• polymerization may be carried out in the presence of a chain transfer agent in order to control the molecular weight of the polymer component (b).
• the chain transfer agent that can be used at that time is not particularly limited, and is, for example, a primary alkyl mercaptan such as n-butyl mercaptan, n-octyl mercaptan, n-hexadecyl mercaptan, n-dodecyl mercaptan, and n-tetradecyl mercaptan.
• Secondary alkyl mercaptan chain transfer agent such as s-butyl mercaptan, s-dodecyl mercaptan, tertiary alkyl mercaptan chain transfer agent such as t-dodecyl mercaptan, t-tetradecyl mercaptan, 2-ethylhexylthio.
• Glycolate ethylene glycol dithioglycolate, trimethylolpropanetris (thioglycolate), thioglycolic acid esters such as pentaerythritol tetrakis (thioglycolate), thiophenols, tetraethylthium disulfide, pentanphenylethane, achlorine, metachlorine, Examples thereof include allyl alcohol, carbon tetrachloride, ethylene bromide, styrene oligomers such as ⁇ -methylstyrene dimer, and terpinolene. These may be used alone or in combination of two or more.
• the latex of the graft copolymer obtained by the emulsion polymerization is subjected to heat drying or spray drying, or a water-soluble electrolyte such as a salt or an acid is added to solidify the latex, and the aqueous phase is further subjected to heat treatment.
• a solid or powdery graft copolymer can be obtained by subjecting the resin component to a known method such as separating the resin component from the polymer and drying the polymer. Above all, a method of coagulating with a salt is preferable.
• the salt is not particularly limited, but a divalent salt is preferable, and specific examples thereof include calcium salts such as calcium chloride and calcium acetate, and magnesium salts such as magnesium chloride and magnesium sulfate. Of these, magnesium salts such as magnesium chloride and magnesium sulfate are preferable.
• commonly added additives such as an antiaging agent and an ultraviolet absorber may be added.
• the latex Before the solidification operation, it is preferable to filter the latex with a filter, mesh, etc. to remove fine polymerization scale.
• a filter, mesh, etc. to remove fine polymerization scale.
• the graft copolymer according to the present embodiment can form a resin composition for film production by a solution casting method.
• the resin composition may contain only the graft copolymer according to the present embodiment as a resin component, but may contain other resins in addition to the graft copolymer according to the present embodiment. May be good.
• Such resins are not particularly limited, and are, for example, styrene resins such as methacrylic resins, acrylonitrile styrene resins, and styrene anhydride maleic acid resins, polycarbonate resins, polyvinyl acetal resins, cellulose acylate resins, polyvinylidene fluorides, and polyfluorides.
• Examples thereof include fluororesins such as alkyl (meth) acrylate resins, silicone resins, polyolefin resins, polyethylene terephthalate resins, and polybutylene terephthalate resins.
• the content of the other resin is not particularly limited, but may be, for example, about 0 to 50 parts by weight with respect to 100 parts by weight of the graft copolymer according to the present embodiment. Further, it may be 0 to 30 parts by weight, 0 to 10 parts by weight, 0 to 5 parts by weight, or 0 to 1 part by weight.
• the resin composition for film production includes a light stabilizer, an ultraviolet absorber, a heat stabilizer, a matting agent, a light diffusing agent, a colorant, a dye, a pigment, an antioxidant, a heat ray reflecting material, a lubricant, and a plasticizing agent.
• a light stabilizer an ultraviolet absorber, a heat stabilizer, a matting agent, a light diffusing agent, a colorant, a dye, a pigment, an antioxidant, a heat ray reflecting material, a lubricant, and a plasticizing agent.
• UV absorbers, stabilizers, fillers and other known additives may be further contained.
• a conventionally known core-shell type graft copolymer may be further contained.
• Dope By dissolving or dispersing the resin composition for film production in a solvent, it is possible to form a dope used when producing a resin film by a solution casting method.
• the solvent is a solvent capable of dissolving or dispersing the resin composition for film production, and is not particularly limited, but a solvent (c-1) having a hydrogen bond term ⁇ H of 1 or more and 12 or less in the Hansen solubility parameter. It is preferable to include it. By constructing the dope using such a solvent, good solubility or dispersibility of the graft copolymer according to the present embodiment in the solvent can be realized.
• a solvent having the hydrogen bond term ⁇ H of 3 or more and 10 or less is preferable, and a solvent having 5 or more and 8 or less is more preferable.
• solubility parameter has been known as an index indicating the solubility of a substance, and the term of the aggregation energy of the SP value is the type of interaction energy acting between molecules (London dispersion force, between bipolars).
• a Hansen solubility parameter has been proposed, which is divided by force (force, hydrogen bond force) and expressed as a London dispersion force term, an intramolecular force term, and a hydrogen bond force term, respectively.
• the hydrogen bond term ⁇ H in this Hansen solubility parameter is used as an index showing the solubility of the graft copolymer when it is dissolved in a solvent.
• Examples of the solvent (c-1) having the hydrogen bond term ⁇ H of 1 or more and 12 or less include 1,4-dioxane (9.0), 2-phenylethanol (11.2), and acetone (7.0). , Acetonitrile (6.1), chloroform (5.7), dibasic acid ester (8.4), diacetone alcohol (10.8), N, N-dimethylformamide (11.3), dimethyl sulfoxide (10) .2), Ethyl acetate (7.2), ⁇ -butyrolactone (7.4), Methyl ethyl ketone (5.1), Methyl isobutyl ketone (4.1), Methylene chloride (7.1), n-butyl acetate (7.1) 6.3), N-methyl-2-pyrrolidone (7.2), propylene carbonate (4.1), 1,1,2,2-tetrachloroethane (5.3), acetonitrile (8.0), toluene (2.0) and the like can be mentioned.
• methyl ethyl ketone, chloroform, and methylene chloride are preferable, and methylene chloride is more preferable because the graft copolymer according to the present embodiment has excellent solubility and a high volatilization rate.
• the solvent contained in the dope may be composed only of the solvent (c-1) having the hydrogen bond term ⁇ H of 1 or more and 12 or less.
• Examples of the solvent (c-2) having ⁇ H of 14 or more and 24 or less include methanol (22.3), ethanol (19.4), isopropanol (16.4), butanol (15.8), and ethylene glycol. Examples thereof include monoethyl ether (14.3). Only one kind of these solvents may be used, or two or more kinds of these solvents may be mixed and used.
• the content of the solvent (c-1) having a hydrogen bond term ⁇ H of 1 or more and 12 or less is applied to the entire solvent contained in the dope.
• 55% by weight or more and 95% by weight or less is preferable, 60% by weight or more and 90% by weight or less is more preferable, 65% by weight or more and 85% by weight or less is further preferable, and 70% by weight or more and 85% by weight or less is further preferable.
• the ratio of the graft copolymer in the dope is not particularly limited, and is appropriately determined in consideration of the solubility or dispersibility of the graft copolymer in the solvent used, the conditions for carrying out the solution casting method, and the like. However, it is preferably 5 to 50% by weight, more preferably 10 to 45% by weight, still more preferably 15 to 40% by weight.
• the dope is used to produce a resin film by the solution casting method.
• the resin film can be produced by casting the dope on the surface of the support and then evaporating the solvent.
• the graft copolymer according to the present embodiment and in some cases, pellets containing other components are prepared, and then the pellets are mixed with a solvent to prepare a dope in which each component is dissolved or dispersed in the solvent.
• the graft copolymer according to the present embodiment and other components are mixed with a solvent simultaneously or sequentially to prepare a dope in which each component is dissolved or dispersed in the solvent.
• the step of dissolving or dispersing can be carried out by appropriately adjusting the temperature and pressure. After the above dissolution or dispersion step, the obtained dope can be filtered or defoamed.
• the dope is sent to the pressure die by a liquid feed pump, and the dope is poured from the slit of the pressure die onto the surface (mirror surface) of a support such as an endless belt or a drum made of metal or synthetic resin. To form a dope film.
• the formed dope film is heated on the support to evaporate the solvent to form a film.
• the conditions for evaporating the solvent can be appropriately determined according to the boiling point of the solvent used.
• the film thus obtained is peeled off from the surface of the support. After that, the obtained film may be appropriately subjected to a drying step, a heating step, a stretching step, or the like.
• the resin film according to the present embodiment is composed of the resin composition for film production, and can be formed by the above-mentioned dope solution casting method.
• the thickness of the resin film is not particularly limited, but is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, still more preferably 200 ⁇ m or less. Further, it is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, further preferably 10 ⁇ m or more, and particularly preferably 30 ⁇ m or more.
• the resin film according to the present embodiment preferably has a total light transmittance of 85% or more, more preferably 88% or more, still more preferably 90% or more when measured at a film thickness of 80 ⁇ m.
• the resin film can be suitably used for optical members, decorative applications, interior applications, and vacuum forming applications where light transmittance is required.
• the resin film according to the present embodiment preferably has a glass transition temperature of 100 ° C. or higher, more preferably 105 ° C. or higher, further preferably 110 ° C. or higher, and particularly preferably 115 ° C. or higher.
• the resin film according to the present embodiment preferably has a haze of 0.8% or less, more preferably 0.6% or less, still more preferably 0.5% or less, and 0. 4% or less is even more preferable, and 0.3% or less is particularly preferable.
• the internal haze of the resin film is preferably 0.5% or less, more preferably 0.4% or less, still more preferably 0.3% or less, and 0.2% when measured at a film thickness of 50 ⁇ m. The following are particularly preferred.
• the resin film can be suitably used for optical members requiring light transmission, decorative applications, interior applications, and vacuum forming applications.
• the haze consists of the haze inside the film and the haze on the surface of the film (outside), and each is expressed as an internal haze and an external haze.
• the resin film according to this embodiment preferably has a large optical anisotropy.
• the absolute value of the in-plane phase difference is preferably 10 nm or more, more preferably 15 nm or more, further preferably 20 nm or more, and particularly preferably 25 nm or more.
• the absolute value of the phase difference in the thickness direction is preferably 15 nm or more, more preferably 20 nm or more, further preferably 25 nm or more, and particularly preferably 30 nm or more.
• the upper limit is not particularly limited, but may be, for example, 150 nm or less.
• Such a resin film having a large retardation can be suitably used as a retardation film included in a polarizing plate of a liquid crystal display device.
• phase difference is an index value calculated based on birefringence
• in-plane phase difference (Re) and the thickness direction phase difference (Rth) can be calculated by the following equations, respectively.
• both the in-plane phase difference Re and the thickness direction phase difference Rth are 0.
• nx, ny, and nz have an in-plane extension direction (polymer chain orientation direction) as the X-axis, a direction perpendicular to the X-axis as the Y-axis, and a film thickness direction as the Z-axis, respectively.
• d represents the thickness of the film
• nx-ny represents the orientation birefringence.
• the MD direction of the film is the X-axis, but in the case of a stretched film, the stretching direction is the X-axis.
• the resin film according to the present embodiment has high toughness and high flexibility, and may be an unstretched film or a stretched film. By stretching, the mechanical strength of the resin film can be improved and the film thickness accuracy can be improved.
• a step of forming a film and degassing the solvent by performing uniaxial stretching or biaxial stretching after producing an unstretched film, or during film molding a step of forming a film and degassing the solvent by performing uniaxial stretching or biaxial stretching after producing an unstretched film, or during film molding.
• a stretched film (uniaxially stretched film or biaxially stretched film) can be produced by appropriately adding a stretching operation along with the progress of the above. Further, stretching during film molding and stretching after film molding may be appropriately combined.
• the draw ratio of the stretched film is not particularly limited, and may be determined according to the mechanical strength, surface properties, thickness accuracy, etc. of the stretched film to be manufactured. Although it depends on the stretching temperature, the stretching ratio is generally preferably selected in the range of 1.1 times to 5 times, more preferably in the range of 1.3 times to 4 times. It is more preferable to select in the range of 1.5 times to 3 times. When the draw ratio is within the above range, the mechanical properties such as the elongation rate, the tear propagation strength, and the kneading resistance of the film can be significantly improved.
• the resin film according to the present embodiment can reduce the gloss of the film surface by a known method, if necessary.
• a method of adding an inorganic filler or crosslinkable polymer particles include a method of adding an inorganic filler or crosslinkable polymer particles.
• embossing the obtained film it is possible to form a surface uneven layer such as a prism shape, a pattern, a design, and knurling, and to reduce the gloss of the film surface.
• the resin film according to the present embodiment may be laminated with another film by using a dry laminating method and / or a thermal laminating method using an adhesive, an adhesive or the like, or may be hard-coated on the front surface or the back surface of the film, if necessary. It can be used by forming a functional layer such as a layer, an antireflection layer, an antifouling layer, an antistatic layer, a printing decoration layer, a metallic gloss layer, a surface uneven layer, and a matte layer.
• a functional layer such as a layer, an antireflection layer, an antifouling layer, an antistatic layer, a printing decoration layer, a metallic gloss layer, a surface uneven layer, and a matte layer.
• the resin film according to this embodiment can be used for various purposes by utilizing properties such as heat resistance, transparency, and flexibility.
• Lens field such as pickup lens for optical disk in CD player, DVD player, MD player, optical recording field for optical disk such as CD, DVD, MD, organic EL film, light guide plate for liquid crystal, diffuser plate, back sheet, reflection Sheets, polarizing element protective films, polarizing film transparent resin sheets, retardation films, light diffusion films, films for liquid crystal displays such as prism sheets, information equipment fields such as surface protective films, optical fibers, optical switches, optical connectors, etc.
• Communication field automobile headlight, tail lamp lens, inner lens, instrument cover, sun roof and other vehicle fields, eyeglasses, contact lenses, endoscope lenses, medical equipment fields such as medical supplies that require sterilization, road signs, bathrooms Equipment, floor materials, road translucent plates, lenses for paired glass, light windows, carports, lenses for lighting, lighting covers, sizing for building materials, and other construction and building materials fields, microwave cooking containers (tableware), housings for home appliances , Can be used for toys, sunglasses, stationery, etc. It can also be used as a substitute for a molded product using a transfer foil sheet.
• the resin film according to this embodiment can be used by laminating it on a base material such as metal or plastic.
• Resin film laminating methods include laminating molding, wet laminating in which an adhesive is applied to a metal plate such as a steel plate, and then the film is placed on the metal plate and dried and bonded, dry laminating, extraction laminating, and hot melt laminating. And so on.
• the film is placed in a mold, insert molding or laminate injection press molding in which resin is filled by injection molding, or placement in the mold after preforming the film.
• In-mold molding in which resin is filled by injection molding, can be mentioned.
• the laminate of the resin film according to the present embodiment is used as a substitute for painting such as automobile interior materials and automobile exterior materials, and civil engineering such as window frames, bathroom equipment, wallpaper, floor materials, light collection / dimming members, soundproof walls, and road signs.
• civil engineering such as window frames, bathroom equipment, wallpaper, floor materials, light collection / dimming members, soundproof walls, and road signs.
• housings for furniture and electronic and electrical equipment housings for OA equipment such as facsimiles, laptop computers, and copy machines, front panels of LCD screens for terminals such as mobile phones, smartphones, and tablets, and lighting.
• the resin film according to this embodiment is suitable for an optical film in that it is excellent in heat resistance and optical characteristics, and can be used for various optical members.
• the front plate of the liquid crystal screen of terminals such as mobile phones, smartphones, and tablets, lighting lenses, automobile headlights, optical lenses, optical fibers, optical fibers, light guide plates for liquid crystal, diffuser plates, back sheets, reflective sheets, and polarizing films.
• Example 1 Manufacturing of graft copolymer (A1)> The following substances were charged into an 8L polymerization apparatus equipped with a stirrer. Deionized water 142 parts Sodium hydroxide 0.004 parts Di (2-ethylhexyl) sulfosuccinate 0.2 parts After sufficiently replacing the inside of the polymer with nitrogen gas, the internal temperature was set to 80 ° C. and sodium persulfate 0.03. Add 0.0005 parts of sodium formaldehyde sulfoxylate in a 0.5% aqueous solution, and then add 10 parts of the monomer (a) for crosslinked (meth) acrylic polymer particles shown in Table 1 to 0.523 parts / minute. Added continuously at a rate.
• the polymerization conversion was 100.0%.
• the average particle size is shown in Table 2.
• the obtained latex was dried at 75 ° C. for 12 hours to obtain a white powdery graft copolymer (A1).
• the weight average molecular weight of the non-crosslinked methacrylic polymer component (b) was 670,000.
• Example 2-3 and Comparative Example 1 The graft copolymers (A2) to (A4) were produced in the same manner as in Example 1 except that the types and amounts of the raw materials used were changed as shown in Table 1.
• Weight average molecular weight of non-crosslinked methacrylic polymer component (b) Among the graft copolymers obtained by polymerization, the weight average molecular weight of the non-crosslinked methacrylic polymer component (b) was calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC), and is shown in Table 2. Described. However, a GPC column packed with polystyrene cross-linked gel (model: TSK gel Super HZM-H, manufactured by Tosoh Corporation) was used, and tetrahydrofuran (THF) was used as the GPC solvent.
• GPC gel permeation chromatography
• sample solution a clear supernatant obtained by centrifuging a polymer solution consisting of 20 mg of graft copolymer powder and 10 ml of THF at 43,000 G for 30 minutes was used.
• the column temperature of GPC was set to 40 ° C.
• the average particle size is the volume average particles measured in the state of the respective latex obtained at the time of completion of the polymerization of the crosslinked (meth) acrylic polymer particles (a) and the graft copolymers (A1) to (A4).
• the diameter As a measuring device, Microtrac UPA150 manufactured by Nikkiso Co., Ltd. was used, and the measured volume average particle diameter is shown in Table 2 as the average particle diameter. The measurement was carried out at room temperature, and the refractive index of the measured particles was the weight average value of the refractive index of the homopolymer composed of the monomers used for the polymerization. For the refractive index of the homopolymer, the values described in the Polymer Handbook [Polymer Hand Book (J. Brandrup, Interscience 1989)] were used.
• ADEKA PLRONIC F-68 polyoxyethylene-polyoxypropylene block copolymer manufactured by ADEKA Corporation
• ADEKA PLRONIC F-68 polyoxyethylene-polyoxypropylene block copolymer manufactured by ADEKA Corporation
• the weight average molecular weight of the suspended polymer is the same as the weight average molecular weight of the non-crosslinked methacrylic polymer component (b) except that a polymer solution consisting of 20 mg of suspended polymer beads and 10 ml of THF was used as a sample solution. It was calculated in the same manner.
• the polymerization conversion was 99.5%. Then, 0.08 part of potassium persulfate is added in a 2% aqueous solution, and then the mixture (II) (41 parts of BA, 9 parts of St, 0.75 parts of ALMA, 0.2 parts of sodium polyoxyethylene lauryl ether phosphate) is added for 150 minutes. It was added continuously over. After completion of the addition, 0.015 part of pure potassium persulfate was added in a 2% aqueous solution, and the polymerization was continued for 120 minutes to obtain the polymer of (II). The polymerization conversion was 99.7% and the average particle size was 220 nm.
• the average particle size of the graft copolymer (A6) up to the rubber intermediate layer was measured in the state of the latex obtained by the polymerization up to the polymerization step (II). It was calculated in the same manner as the average particle size of (A4).
• Weight average molecular weight of the outermost layer of the graft copolymer (A6) The weight average molecular weight of the outermost layer of the graft copolymer (A6) is calculated in the same manner as the weight average molecular weight of the non-crosslinked methacrylic polymer component (b) except that the graft copolymer (A6) is used. did.
• the resin dope having a solid content concentration of 10% for the graft copolymers (A1) to (A4) alone and the suspension polymer (A5) alone was added to 41.5 g of a mixed solvent consisting of 92% methylene chloride and 8% ethanol. It was prepared by adding 4.5 g of coalesced powder or beads and stirring with a magnetic stirrer until completely dissolved.
• the resin dope having a solid content concentration of 10% containing the suspension polymer (A5) and the graft polymer (A6) was prepared by adding 41.5 g of the mixed solvent to the powder of the graft polymer (A6). Add 68 g and stir with a magnetic stirrer until uniform, and disperse the obtained dispersion in an ultrasonic bath (Branson Nick 1510J manufactured by Yamato Scientific Co., Ltd.) for another 15 minutes, and then suspend the weight in the dispersion. 3.82 g of the combined (A5) bead was added little by little and stirred until completely dissolved.
• an ultrasonic bath Branson Nick 1510J manufactured by Yamato Scientific Co., Ltd.
• the above resin dope was cast on a PET film (Cosmo Shine A4100 manufactured by Toyobo Co., Ltd.) and applied in a uniform film form with an applicator. The clearance was adjusted so that the thickness after drying was about 70 ⁇ m.
• the coating film was dried in a dry atmosphere at 40 ° C. for 1 hour and then peeled off from the PET film.
• the obtained film was fixed to a stainless steel frame and dried in a drying atmosphere at 140 ° C. for 90 minutes to remove residual solvent to obtain a cast film.
• the film thickness was measured using a digital indicator (manufactured by Mitutoyo Co., Ltd.).
• MIT The repeated bending strength of the uniaxially stretched film was measured using a MIT-DA type MIT tester manufactured by Toyo Seiki Seisakusho Co., Ltd.
• the test piece was cut out with a width of 1.5 cm, a load of 200 g was applied under the conditions of a bending radius of 0.4 mm and a bending angle of 135 °, and the test was performed in a direction in which a crease was formed perpendicular to the stretching direction.
• the test was performed 3 times each, and the average value is shown in Table 2.
• the uniaxially stretched film was quickly cut with a cutter blade (Quick Knife Q-100P manufactured by NT Cutter) in a direction parallel to the stretching direction with a ruler, and the appearance of the cut surface was evaluated on a 5-point scale according to the following criteria.
• the test was performed 5 times for each uniaxially stretched film, and the average of the 5 evaluation points is shown in Table 2. It can be evaluated that the trimming property is good when the average of the evaluation points of 5 times is 3 points or more.
• Glass-transition temperature The glass transition temperature of the crosslinked (meth) acrylic polymer particles (a) is calculated using the Fox formula using the values described in the Polymer Handbook [Polymer Hand Book (J. Brandrup, Interscience 1989)]. did.
• the glass transition temperature of the beads of the non-crosslinked methacrylic polymer component (b) or the suspended polymer was measured using a differential scanning calorimeter DSC7000X manufactured by Hitachi High-Tech Science Co., Ltd.
• the sample graft copolymer powder or suspended polymer beads are placed under a nitrogen stream, heated to 190 ° C. at a heating rate of 10 ° C./min, and then held at 190 ° C. for 3 minutes before 40. It was rapidly cooled to ° C. and heated again to 190 ° C. at a heating rate of 10 ° C./min.
• the average of the extra glass transition start temperature and the extra glass transition end temperature was calculated, and this value was taken as the glass transition temperature.
• Table 2 The results are shown in Table 2.
• the glass transition temperature of the film was measured as a sample of a cast film dried at 140 ° C. and further dried at 175 ° C. for 1 hour, except that the above-mentioned non-crosslinked methacrylic polymer component (b) or suspended weight was measured. It was determined in the same manner as the glass transition temperature of the coalesced beads. The results are shown in Table 2.
• the storage stability of the graft copolymer in the powder state was evaluated by the time course of the particle size distribution using a laser diffraction type particle size distribution meter (Mastersizer 3000 manufactured by Malvern). A mixed solvent consisting of 92% methylene chloride and 8% ethanol was used as the dispersion medium for measuring the particle size distribution. A resin dope having a solid content concentration of 10% as a measurement sample was prepared from the powder and the mixed solvent immediately before the measurement. The resin dope was dropped while circulating the dispersion medium in the apparatus, and the measurement was performed so that the laser scattering intensity was 0.5 to 2.0%. The graft copolymer powder was stored under the conditions of 50 ° C. and 95% RH, and the above measurement was performed for each of the powders at the start of storage 0, 3, or 14 days. Table 2 shows the volume% occupied by particles having a diameter of 1 ⁇ m or more with respect to the total particles.
• the storage stability of the resin dope containing the graft copolymer was evaluated in the same manner as the storage stability of the graft copolymer powder described above.
• As the mixed solvent for preparing the resin dope a mixed solvent consisting of 82% methylene chloride and 18% methanol or a mixed solvent consisting of 92% methylene chloride and 8% ethanol was used.
• the resin dope prepared at a solid content concentration of 10% was stored at room temperature, and measurement was performed for each of the resin dops on the 0th, 3rd, or 14th days of storage using a mixed solvent having the same composition as the resin dope as a dispersion medium. rice field.
• Table 2 shows the volume% occupied by particles having a diameter of 1 ⁇ m or more with respect to the total particles.
• the weight average molecular weight of the non-crosslinked methacrylic polymer component is set as low as less than 250,000, and the graft co-weight containing the crosslinked (meth) acrylic polymer particles that do not use styrene and the non-crosslinked methacrylic polymer component.
• the produced resin film had a low glass transition temperature and low heat resistance, and also had a small phase difference.
• Comparative Example 2 in which a resin film was produced by blending a core-shell type graft copolymer with a methacrylic resin as in the prior art, the haze of the resin film was large, the phase difference was small, and the core-shell type graft copolymer powder and In both core-shell type graft copolymer-containing dope, the content of coarse particles increased with time, and the storage stability was poor.
• the resin film of Comparative Example 3 produced only from a general methacrylic resin had insufficient bending resistance and trimming resistance, and had a small phase difference. Further, as shown in Comparative Example 4, a resin film could not be produced only from the conventional core-shell type graft copolymer.

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