Classifications

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  • 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
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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  • 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
  • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F212/02—Monomers containing only one unsaturated aliphatic radical
  • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F212/06—Hydrocarbons
  • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/36—Amides or imides
  • C08F222/40—Imides, e.g. cyclic imides
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  • 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
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  • 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
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
• • 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
  • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
• • 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
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
  • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
• • 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
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/48—Isomerisation; Cyclisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
  • C08L33/12—Homopolymers or copolymers of methyl methacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/24—Homopolymers or copolymers of amides or imides
• • 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
  • C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • 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
  • C08L51/04—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 rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
  • C08J2333/12—Homopolymers or copolymers of methyl methacrylate

Definitions

• the present invention relates to an acrylic resin composition and a molded product.
• Methacrylic resin has excellent transparency, weather resistance, surface hardness, etc.
• various members used for display members, electronic / electrical members, transportation parts, and the like can be obtained.
• there has been a demand for higher performance of various members and in particular, there is a strong demand for improvement in heat resistance.
• Patent Document 1 has at least one ring structure selected from the group consisting of a structural unit derived from methyl methacrylate and the like, a lactone ring unit, a glutaric anhydride unit, and an N-substituted or unsubstituted glutarimide unit as the main chain.
• the modified methacrylic resin containing the structural unit having the above is disclosed.
• Patent Document 2 discloses a copolymer composed of a (meth) acrylic acid ester monomer unit, an unsaturated dicarboxylic acid anhydride monomer unit, and an unsaturated aromatic vinyl monomer unit.
• Patent Document 3 discloses a technique in which an acrylic resin containing a glutaric anhydride unit contains a crosslinked elastic body having a multilayer structure as an elastomer.
• Patent Document 4 discloses a technique of adding acrylic rubber as an elastomer to an acrylic resin containing a maleic anhydride unit.
• Patent Document 5 at least one ring structure selected from the group consisting of a lactone ring unit, a maleic anhydride unit, a glutaric anhydride unit, a glutarimide unit, an N-substituted maleimide unit, and a tetrahydropyran ring structure unit is mainly used.
• a technique for adding a block copolymer containing a methacrylic anhydride polymer block and an acrylic acid ester polymer block as an elastomer to an acrylic resin containing a structural unit having a chain is disclosed.
• Patent Document 6 discloses a technique for adding a graft copolymer as an elastomer to an acrylic resin having a glass transition temperature of 120 ° C. or higher and a refractive index of 1.50 or higher, and methacrylic as the acrylic resin. Imidized resins of methyl-styrene copolymers are described in the Examples.
• the problem to be solved by the present invention is to provide an acrylic resin composition and a molded product which maintain heat resistance and mechanical strength (toughness) and have excellent surface hardness and dimensional stability. be.
• An acrylic resin composition containing 51 to 99% by mass of (A) and 1 to 49% by mass of an elastomer (B).
• R 1 is an independent hydrogen atom or methyl group
• R 2 contains an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic ring. It is an organic group having 6 to 15 carbon atoms.
• At least another vinyl-based monomer unit (C) copolymerizable with the methyl methacrylate unit is selected from the group consisting of an acrylic acid ester monomer, an aromatic vinyl monomer, and a vinyl cyanide monomer.
• the other vinyl-based monomeric unit (C) copolymerizable with the methyl methacrylate unit is formed by at least one selected from the group consisting of methyl acrylate, ethyl acrylate, styrene, and acrylonitrile [1]. ] To [3].
• the acrylic resin composition of the present invention contains an acrylic copolymer (A) and an elastomer (B).
• the content of the acrylic copolymer (A) in the acrylic resin composition is 51 to 99% by mass, preferably 55 to 95% by mass, and more preferably in the range of 60 to 90% by mass. preferable.
• the acrylic resin composition of the present invention has excellent heat resistance and surface hardness when the content of the acrylic copolymer (A) is 51% by mass or more, and is brittle when it is 99% by mass or less. It will be improved.
• the acrylic copolymer (A) contains a methyl methacrylate unit, an ⁇ -methylstyrene unit, and a structural unit (R).
• the acrylic copolymer according to the present invention may further contain another vinyl-based monomer unit (C) copolymerizable with methyl methacrylate.
• Other vinyl-based monomer units (C) copolymerizable with methyl methacrylate are methacrylic acid amide units represented by the following formula (A) and 2- (hydroxyalkyl) represented by the following formula (B). It may be a methyl acrylate unit.
• R 3 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an organic group having 6 to 15 carbon atoms including an aromatic ring, preferably a hydrogen atom. It is a methyl group, an n-butyl group, a cyclohexyl group or a benzyl group, more preferably a methyl group, an n-butyl group or a cyclohexyl group.
• R 4 and R 5 are independently hydrogen atoms or 1 to 20 carbon atoms, respectively.
• the organic group is preferably a hydrogen atom or an organic group having 1 to 10 carbon atoms, more preferably an organic group having a hydrogen atom or 1 to 5 carbon atoms.
• the organic group is not particularly limited, and examples thereof include a linear or branched alkyl group, a linear or branched aryl group, -OCOCH 3 group, -CN group, and the like.
• the organic group contains a hetero atom such as an oxygen atom.
• R 4 is preferably a methyl group and R 5 is preferably a hydrogen atom.
• the proportion of methyl methacrylate units is 30 to 87% by mass, preferably 40 to 85% by mass, and more preferably 55 to 80% by mass with respect to the total structural units. %. If the proportion of methyl methacrylate units is less than this range, the total light transmittance of the obtained acrylic copolymer deteriorates, and if the proportion of methyl methacrylate units is higher than this range, the obtained acrylic copolymer weight The heat resistance of the coalescence is low.
• the proportion of ⁇ -methylstyrene units is 7 to 30% by mass, preferably 8 to 27% by mass, more preferably 11 to 25, based on the total structural units. It is mass%.
• the ratio of ⁇ -methylstyrene units is less than this range, the saturated water absorption rate of the obtained acrylic copolymer becomes high.
• an acrylic copolymer having an ⁇ -methylstyrene unit ratio of more than 30% by mass has low polymerizability and lower productivity.
• the structural unit (R) is a structural unit having at least one ring structure selected from the group consisting of a glutaric anhydride unit and an N-substituted or unsubstituted glutarimide unit in the main chain.
• the acrylic copolymer according to the present invention mainly contains a methacrylic acid amide unit represented by the above formula (A) and / or a 2- (hydroxyalkyl) acrylic acid ester unit represented by the above formula (B). It may be included in the chain.
• the glutaric anhydride unit is a unit having a 2,6-dioxodihydropyrandiyl structure.
• Examples of the unit having a 2,6-dioxodihydropyrandiyl structure include a structural unit represented by the formula (II).
• R 6 is an independent hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and both R 6 are methyl groups.
• the unit having a 2,6-dioxodihydropyranjiyl structure is derived from the methods described in JP-A-2007-197703, JP-A-2010-96919, etc., for example, two adjacent (meth) acrylic acids. It can be contained in an acrylic copolymer by intramolecular cyclization of structural units, intramolecular cyclization of structural units derived from (meth) acrylic acid and structural units derived from methyl (meth) acrylate, and the like. .. JP-A-2007-197703 and JP-A-2010-96919 are incorporated herein by reference in their entirety.
• An N-substituted or unsubstituted glutarimide unit is a unit having an N-substituted or unsubstituted 2,6-dioxopiperidinediyl structure.
• Examples of the unit having an N-substituted or unsubstituted 2,6-dioxopiperidinediyl structure include a structural unit represented by the formula (I).
• R 1 is an independent hydrogen atom or a methyl group, and both R 1 are methyl groups.
• R 2 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an organic group having 6 to 15 carbon atoms containing a cycloalkyl group or an aromatic ring, having 3 to 12 carbon atoms, preferably methyl because it can lower the water absorption It is a group, an n-butyl group, a cyclohexyl group or a benzyl group, more preferably a methyl group, an n-butyl group, or a cyclohexyl group, and most preferably a methyl group.
• the structural unit represented by the formula (I) may be produced, for example, by the reaction of the corresponding acid anhydride (IIa) and the imidizing agent represented by R 2 NH 2 as shown in the scheme (i). , May be produced by an intramolecular cyclization reaction of a copolymer having a partial structure of the formula (III). It is preferable to heat the structural unit represented by the formula (III) to be converted into the structural unit represented by the formula (I) by an intramolecular cyclization reaction.
• the N-substituted or unsubstituted glutarimide unit is a method described in WO2005 / 10838A1, JP-A-2010-254742, JP-A-2008-273140, JP-A-2008-274187, and the like, specifically, adjacent to each other.
• Structural units or glutaric anhydride units derived from two matching methyl methacrylates, such as ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, n-hexylamine, etc.
• Arophilic hydrocarbon group-containing amines such as aliphatic hydrocarbon group-containing amines, aniline, toluidine, and trichloroaniline
• alicyclic hydrocarbon group-containing amines such as cyclohexylamine, urea, 1,3-dimethylurea, 1,3 -It can be obtained by reacting an imidizing agent such as diethyl urea or 1,3-dipropyl urea. Of these, methylamine is preferred.
• WO2005 / 10838A1 Japanese Patent Application Laid-Open No. 2010-254742, Japanese Patent Application Laid-Open No. 2008-273140, and Japanese Patent Application Laid-Open No.
• methyl methacrylate unit may be hydrolyzed to a carboxyl group, and this carboxyl group is converted to the original methyl methacrylate unit in the esterification reaction treated with an esterifying agent. It is preferable to put it back.
• the esterifying agent is not particularly limited as long as the effects of the present application can be exhibited, but dimethyl carbonate and trimethylacetate can be preferably used.
• a tertiary amine such as trimethylamine, triethylamine, or tributylamine can be used in combination as a catalyst.
• the ratio of the structural unit (R) is 6 to 40% by mass, preferably 7.5 to 35% by mass, more preferably 8 with respect to the total structural units. ⁇ 30% by mass.
• the other vinyl-based monomer unit (C) (hereinafter, may be referred to as (C) monomer unit) copolymerizable with the methyl methacrylate unit is an acrylic acid ester monomer unit (C-). 1), aromatic vinyl monomer unit (C-2), vinyl cyanide monomer unit (C-3), and other monomer units (C-4) can be mentioned.
• As the other vinyl-based monomer unit (C) copolymerizable with the methyl methacrylate unit only one type may be used alone, or two or more types may be combined.
• the material of the (C) monomer unit can be appropriately selected according to the properties required for the acrylic copolymer according to the present invention, but it has thermal stability, fluidity, chemical resistance, and optical property. , At least one selected from the group consisting of an acrylic acid ester monomer unit, an aromatic vinyl monomer unit, and a vinyl cyanide monomer unit is preferable when properties such as compatibility with other resins are particularly required. Is.
• the acrylic acid ester monomer unit (C-1) constituting the acrylic copolymer according to the present invention is not particularly limited, but from the viewpoints of heat resistance, fluidity, heat stability, productivity and the like. Therefore, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, cyclohexyl acrylate, phenyl acrylate and the like are preferable.
• Methyl acrylate, ethyl acrylate, and n-butyl acrylate are preferable, and methyl acrylate and ethyl acrylate are more preferable from the viewpoint of productivity.
• the acrylic acid ester monomer unit (C-1) only one type may be used alone, or two or more types may be used in combination.
• the content is preferably 20% by mass or less, more preferably 20% by mass or less, based on the total structural units, from the viewpoint of heat resistance and thermal stability. It is 10% by mass or less.
• the aromatic vinyl monomer unit (C-2) constituting the acrylic copolymer according to the present invention is not particularly limited, but from the viewpoints of heat resistance, fluidity, heat stability, productivity and the like.
• Styrene (St) o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-Ethylstyrene, m-ethylstyrene, o-ethylstyrene, p-tert-butylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 1,1-diphenylethylene, isopropenyltoluene, isopropenylethylbenzene, isopropenylpropyl Benz
• the content is preferably 3% by mass or more and 20% by mass or less with respect to all the structural units from the viewpoint of heat resistance and thermal stability. , More preferably 4% by mass or more and 15% by mass or less.
• the vinyl cyanide monomer unit (C-3) constituting the acrylic copolymer according to the present invention is not particularly limited, but has heat resistance, fluidity, heat stability, chemical resistance, and production. From the viewpoint of properties and the like, acrylonitrile (AN), methacrylonitrile, vinylidene cyanide and the like are preferable, and among them, acrylonitrile is preferable from the viewpoint of easy availability and imparting chemical resistance. As the vinyl cyanide monomer unit (C-3), only one type may be used alone, or two or more types may be used in combination.
• the content is preferably 20% by mass or less, more preferably 20% by mass or less, based on the total structural units, from the viewpoint of heat resistance and thermal stability. It is 10% by mass or less.
• the monomer forming the monomer unit (C-4) other than (C-1) to (C-3) constituting the acrylic copolymer according to the present invention is not particularly limited.
• the monomer corresponding to the methacrylic acid amide unit represented by the formula (A), and the monomer corresponding to the 2- (hydroxyalkyl) acrylic acid ester unit represented by the formula (B) may be used, for example, acrylamide.
• Amidos such as methacrylamide; ethylene glycols such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, or both ends of the oligomer.
• the hydroxyl groups are esterified with acrylic acid or methacrylic acid; the hydroxyl groups of two alcohols such as neopentyl glycol di (meth) acrylate and di (meth) acrylate are esterified with acrylic acid or methacrylic acid; and trimerol propane. , Pentaerythritol and other polyhydric alcohol derivatives esterified with acrylic acid or methacrylic acid and the like.
• the monomers constituting the above-mentioned (C) monomer unit at least one selected from the group consisting of methyl acrylate (MA), ethyl acrylate, styrene, and acrylonitrile is easy to obtain. Therefore, styrene is more preferable from the viewpoint of moisture resistance.
• MA methyl acrylate
• ethyl acrylate ethyl acrylate
• styrene acrylonitrile
• the ratio of the other vinyl-based monomer unit (C) copolymerizable with the methyl methacrylate unit is preferably 0 to 20% by mass with respect to the total structural units. It is more preferably 0 to 15% by mass, still more preferably 0 to 10% by mass.
• An acrylic copolymer in which the proportion of the other vinyl-based monomer unit (C) copolymerizable with the methyl methacrylate unit exceeds 20% by mass has reduced heat resistance and rigidity.
• the ratio of the methyl methacrylate unit, the ⁇ -methylstyrene unit, the structural unit (R), and the monomer unit (C) can be measured by 1 H-NMR, 13 C-NMR, or the like.
• the acrylic copolymer (A) according to the present invention has a weight average molecular weight (Mw) of preferably 40,000 to 200,000, more preferably 50,000 to 1,800,000, and even more preferably 55,000 to 1,600,000.
• Mw weight average molecular weight
• Mw is 40,000 or more
• the strength and toughness of the molded product of the present invention are improved.
• Mw is 200,000 or less, the fluidity of the acrylic copolymer is improved and the molding processability is improved.
• the weight average molecular weight (Mw) is a value calculated by converting a chromatogram measured by gel permeation chromatography into the molecular weight of standard polystyrene.
• the acrylic copolymer (A) according to the present invention has an acid value of preferably 0.01 to 0.30 mmol / g, more preferably 0.05 to 0.28 mmol / g.
• the acid value is a value proportional to the content of the carboxylic acid unit and the carboxylic acid anhydride unit in the acrylic copolymer.
• the acid value can be calculated, for example, by the method described in JP-A-2005-23272. When the acid value is within the above range, the balance between heat resistance, mechanical properties, and molding processability is excellent.
• the acrylic copolymer (A) according to the present invention has a glass transition temperature of preferably 130 ° C., more preferably 131 ° C., still more preferably 132 ° C. as a lower limit, and the upper limit is not particularly limited, but is preferable. Is 160 ° C.
• the "glass transition temperature (Tg)" is measured according to JIS K7121. Specifically, the DSC curve is measured under the condition that the temperature is raised to 230 ° C., then cooled to room temperature, and then the temperature is raised from room temperature to 230 ° C. at 10 ° C./min. The intermediate point obtained from the DSC curve measured at the time of the second temperature rise is obtained as the "glass transition temperature (Tg)".
• the saturated water absorption rate of the acrylic copolymer (A) according to the present invention is measured under the following conditions.
• the acrylic copolymer is press-molded into a sheet having a thickness of 1.0 mm.
• a 50 mm ⁇ 50 mm test piece is cut out from the central portion of the obtained press-molded sheet, and dried in a dryer at 80 ° C. for 16 hours or more.
• the weight is measured to 0.1 mg, and the weight is defined as the initial weight Wo.
• the test piece Within 1 minute of removal from water, weigh the test piece up to 0.1 mg again. The test piece is dipped again and after 24 hours weigh again in the same manner as above. The weight when the weight change rate of the test piece is within 0.02% of Wo is defined as the saturated weight Ws. The saturated water absorption rate is calculated from the formula (2).
• the saturated water absorption rate is preferably 2.5% or less, more preferably 2.1% or less, still more preferably 2.0% or less.
• the 1% thermogravimetric reduction temperature of the acrylic copolymer (A) according to the present invention under a nitrogen atmosphere is preferably 265 ° C. or higher, more preferably 270 ° C. or higher.
• the acrylic copolymer (A) according to the present invention is a copolymer of methyl methacrylate, ⁇ -methylstyrene, and other vinyl-based monomer units (C) that can be copolymerized with methyl methacrylate, if necessary.
• a precursor polymer can be obtained by a method including a ring structure forming reaction. That is, the production method is radical polymerization with a monomer mixture containing 60 to 93% by mass of methyl methacrylate, 30 to 7% by mass of ⁇ -methylstyrene, and 0 to 20% by mass of a copolymerizable monomer (C).
• Each step can be carried out by a known technique, including a step of causing the obtained precursor polymer to undergo a ring structure forming reaction.
• the precursor polymer is produced by polymerizing from a reaction raw material containing a monomer mixture, a radical polymerization initiator and, if necessary, a chain transfer agent, and the monomer mixture contains methyl methacrylate as a monomer.
• the mixture contains 51 to 90% by mass, preferably 65 to 85% by mass.
• the monomer mixture contains 49 to 10% by mass, preferably 35 to 15% by mass of ⁇ -methylstyrene. Further, the monomer mixture contains 0 to 20% by mass, preferably 0 to 15% by mass of the copolymerizable monomer (C).
• the monomer mixture preferably has b * of -1 to 2, more preferably -0.5 to 1.5.
• b * is in this range, it is advantageous to obtain a molded product with almost no coloring when the obtained acrylic copolymer composition is molded with high production efficiency.
• b * is a value measured in accordance with the International Commission on Illumination (CIE) standard (1976) or JIS Z8722.
• the polymerization initiator used is not particularly limited as long as it generates reactive radicals.
• examples thereof include peroxide-based initiators such as diisopropylbenzene hydroperoxide and t-butyl hydroperoxide, and azo-based initiators such as 2,2'-azobis (2-methylpropionitrile).
• the polymerization initiator used has an uncracked average initiator concentration in the range of 5.1 ⁇ 10-5 to 2.4 ⁇ 10 -4 (mol / L) at the polymerization temperature in the tank reactor described later. Is desirable.
• the amount of the polymerization initiator used is adjusted to the polymerization temperature and added to the monomer mixture so as to have the above-mentioned initiator concentration.
• chain transfer agent used monofunctional alkyl mercaptans such as n-octyl mercaptan and n-dodecyl mercaptan are preferable. These chain transfer agents can be used alone or in combination of two or more.
• the amount of the chain transfer agent used is preferably 0 to 1 part by mass, more preferably 0.01 to 0.8 parts by mass, and further preferably 0.02 to 0.6 parts by mass with respect to 100 parts by mass of the monomer mixture. It is a mass part.
• the temperature in the tank reactor that is, the temperature of the liquid in the reaction tank is preferably 110 to 140 ° C, more preferably 114 to 135 ° C. If the temperature is higher than this range, it is difficult to form a high molecular weight substance containing ⁇ -methylstyrene, which causes a decrease in heat resistance.
• bulk polymerization is preferably carried out until the polymerization conversion rate is 30 to 65% by mass, preferably 35 to 60% by mass.
• the average residence time ( ⁇ ) of the reaction raw material in the tank reactor is preferably 1.5 to 5 hours, more preferably 2 to 4.5 hours, and even more preferably 2.5 to 4 hours. If the average residence time is too short, the required amount of polymerization initiator will increase. Further, increasing the amount of the polymerization initiator makes it difficult to control the polymerization reaction and tends to make it difficult to control the molecular weight. On the other hand, if the average residence time is too long, it takes time for the reaction to reach a steady state, and the productivity tends to decrease.
• the average residence time can be adjusted by the capacity of the tank reactor and the supply amount of the reaction raw material.
• Bulk polymerization is preferably carried out in an atmosphere of an inert gas such as nitrogen gas.
• the production method according to the present invention includes a step of removing the monomer mixture in the reaction product.
• the removal method is not particularly limited, but a thermal devolatile method is preferable.
• the acrylic resin composition can be pelletized or powdered according to a known method in order to facilitate handling as a molding material.
• the content of the monomer mixture in the obtained acrylic resin composition is preferably 1% by mass or less, and more preferably 0.5% by mass or less.
• the precursor polymer has a glass transition temperature of preferably 115 ° C. as a lower limit, more preferably 120 ° C., still more preferably 125 ° C., and preferably 150 ° C. as an upper limit.
• the glass transition temperature can be changed by adjusting the molecular weight, the amount of ⁇ -methylstyrene copolymerization, and the like. The higher the glass transition temperature of the precursor polymer, the better the heat resistance. Since the acrylic copolymer obtained by using the precursor polymer having a high glass transition temperature has high heat resistance even if the amount of the structural unit (R) is small, it is unlikely to cause deterioration of the saturated water absorption rate.
• the precursor polymer has a total content of structural units derived from methyl methacrylate of 60 to 93% by mass, a total content of structural units derived from ⁇ -methylstyrene of 30 to 7% by mass, and a copolymerizable single amount.
• the structural unit derived from the body (C) is not particularly limited as long as it is 0 to 20% by mass. From the viewpoint of polymerizable property, transparency, etc., the total content of structural units derived from methyl methacrylate of the precursor polymer is preferably 65% by mass or more and 93% by mass or less, and more preferably 70% by mass or more and 92% by mass or less. Most preferably, it is 75% by mass or more and 92% by mass or less.
• the total content of structural units derived from ⁇ -methylstyrene of the precursor polymer is preferably 7% by mass or more and 30% by mass or less, more preferably 8% by mass or more. It is 27% by mass or less, more preferably 11 to 25% by mass. If the number of structural units derived from ⁇ -methylstyrene is less than this range, sufficient heat resistance cannot be obtained, and if it is more than this range, the polymerizable property is significantly lowered.
• the total content of the structural units derived from the copolymerizable monomer (C) of the precursor polymer is 0 to 20% by mass, preferably 0 to 15% by mass.
• the precursor polymer has a polystyrene-equivalent weight average molecular weight Mw of preferably 30,000 or more and 200,000 or less, more preferably 40,000 or more and 180,000 or less, and further preferably 50,000 or more and 160000 or less in a chromatogram obtained by gel permeation chromatography. .. If the weight average molecular weight Mw is smaller than this range, the obtained molded product becomes brittle, and if it is higher than this range, the productivity deteriorates. Mw can be controlled by adjusting the type, amount, addition timing, etc. of the polymerization initiator and chain transfer agent (arbitrary component) used in the production of the precursor polymer.
• the ring structure formation reaction can be carried out using, for example, an extruder.
• the extruder include a single-screw extruder, a twin-screw extruder, and a multi-screw extruder.
• a twin-screw extruder is preferable from the viewpoint of mixing performance.
• the twin-screw extruder includes a non-meshing type omnidirectional rotation type, a meshing type unidirectional rotation type, a non-meshing type different direction rotation type, and a meshing type different direction rotation type.
• the meshing type co-rotation type is preferable because it can rotate at high speed and can efficiently promote mixing. These extruders may be used alone or in series.
• a precursor polymer as a raw material is charged from the raw material input section of the extruder, the precursor polymer is melted, filled in a cylinder, and then an addition pump is used.
• an imidizing agent arbitrary component or the like
• the ring structure forming reaction can proceed in the extruder.
• the structural unit (R) may contain an N-substituted or unsubstituted glutarimide unit, and may optionally contain a lactone ring unit and / or a glutaric anhydride unit.
• Preferred imidizing agent is represented by R 2 -NH 2 (R 2 is as defined above).
• the imidizing agent is preferably used in an amount of 1.6 to 12 parts by mass with respect to 100 parts by mass of the acrylic copolymer.
• amount of the imidizing agent used is within the above range, by-production of the methacrylic acid amide unit can be suppressed.
• the resin temperature of the reaction zone in the extruder is preferably in the range of 180 to 280 ° C, more preferably in the range of 200 to 280 ° C. If the resin temperature in the reaction zone is less than 180 ° C., the heat resistance of the acrylic copolymer tends to decrease due to a decrease in the reaction efficiency of the ring structure forming reaction, a by-product of the methacrylic acid amide unit, and the like. When the resin temperature in the reaction zone exceeds 280 ° C., the resin is significantly decomposed, and the mechanical strength such as the tensile breaking strength of the molded product and the film made of the acrylic copolymer tends to decrease.
• the reaction zone in the extruder means a region in the cylinder of the extruder from the injection position of the imidizing agent or the like to the resin discharge port (die portion).
• the ring structure formation reaction can be further advanced.
• the reaction time in the reaction zone of the extruder is preferably longer than 10 seconds, more preferably longer than 30 seconds. If the reaction time is 10 seconds or less, the ring structure formation reaction may hardly proceed.
• the resin pressure in the extruder is preferably in the range of atmospheric pressure to 50 MPa, and more preferably in the range of 1 to 30 MPa. If it is 50 MPa or more, it exceeds the limit of the mechanical pressure resistance of a normal extruder, and a special device is required, which is not preferable in terms of cost.
• an extruder having a vent hole that can reduce the pressure below atmospheric pressure. According to such a configuration, unreacted substances, by-products such as methanol and monomers can be removed, and the breaking strength of the molded product containing the acrylic resin composition of the present invention tends to be improved.
• a horizontal twin-screw reactor such as Vivolac manufactured by Sumitomo Heavy Industries, Ltd. or a vertical twin-screw tank such as Super Blend can be used for high viscosity.
• the reactor of the above can also be preferably used.
• a carboxy group may be produced as a by-product in the acrylic copolymer during the ring structure formation reaction.
• This carboxy group may be converted into an ester group by an esterifying agent, a catalyst or the like, if necessary.
• an ester group contains a methyl methacrylate unit from the viewpoint of reducing the melt viscosity of the resin during melt molding, the reactivity of esterification, and the heat resistance of the resin after esterification, although it depends on the esterifying agent and the catalyst used. It is preferable, and it is more preferable to contain both the methyl methacrylate unit and the ethyl methacrylate unit.
• the esterifying agent dimethyl carbonate is preferable from the viewpoint of cost, reactivity and the like.
• the content of the elastomer (B) in the acrylic resin composition of the present invention is 1 to 49% by mass, preferably 5 to 45% by mass, and more preferably 10 to 40% by mass. ..
• the brittleness of the acrylic resin composition of the present invention is improved when the content of the elastomer (B) is in the range of 1 to 49% by mass.
• the elastomer (B) used in the present invention is not particularly limited as long as the resin composition can be obtained by kneading with the acrylic copolymer (A).
• the elastomer (B) preferably forms a dispersed phase in the resin composition.
• the form of the dispersed phase is not particularly limited, and examples thereof include a spherical shape, an ellipsoidal shape, a rod shape, a flat body shape, and a string shape.
• the elastomer (B) preferably has an acrylic acid ester unit.
• Acrylic acid esters include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate and butyl acrylate; acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; acrylics such as cyclohexyl acrylate and norbornenyl acrylate. Acid cycloalkyl ester; is preferable, acrylic acid alkyl ester is preferable, and butyl acrylate is most preferable.
• the amount of the acrylic acid ester unit contained in the elastomer (B) is preferably 30% by mass or more, more preferably 35% by mass or more and 90% by mass or less, and further preferably 40% by mass or more and 80% by mass or less.
• the elastomer (B) may have, in addition to the acrylic acid ester unit, a vinyl-based monomer unit having only one polymerizable carbon-carbon double bond in one molecule.
• the vinyl-based monomer include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate; and aryl methacrylate esters such as phenyl methacrylate; Cycloalkyl methacrylate esters such as cyclohexyl methacrylate and norbornenyl methacrylate; aromatic vinyl compounds such as styrene and ⁇ -methylstyrene; acrylamide; methacrylicamide; acrylonitrile; methacrylonitrile; and the like.
• the elastomer (B) may have, in addition to the acrylic acid ester unit, a vinyl-based monomer unit having only one polymerizable carbon-carbon double bond in one molecule.
• the vinyl-based monomer include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate; and aryl methacrylate esters such as phenyl methacrylate; Cycloalkyl methacrylate esters such as cyclohexyl methacrylate and norbornenyl methacrylate; aromatic vinyl compounds such as styrene and ⁇ -methylstyrene; acrylamide; methacrylicamide; acrylonitrile; methacrylonitrile; and the like.
• the elastomer (B) may also have a conjugated diene monomer unit.
• the conjugated diene monomer unit include those containing 1,3-butadiene, isoprene, or both of these units.
• the elastomer (B) is not particularly limited depending on its molecular form, and examples thereof include a linear polymer elastomer, a branched chain polymer elastomer, a multilayer copolymer elastomer, and a block copolymer elastomer.
• the elastomer (B) contains a multilayer copolymer elastomer having a methacrylic acid ester unit and an acrylic acid ester unit, or a polymer block (b1) having a methacrylic acid ester unit and an acrylic acid ester.
• Those containing a block copolymer elastomer composed of a polymer block (b2) having a unit are preferable.
• the elastomer (B) may contain a block copolymer elastomer and a multilayer copolymer elastomer in combination.
• Examples of the multilayer copolymer elastomer include those composed of an outermost layer made of a thermoplastic polymer (P) and an inner layer made of a crosslinked polymer in contact with and covered with the outermost layer, and the inner layer and the outermost layer can be mentioned. Preferably forms a core and a shell.
• the multilayer copolymer elastomer is, for example, a two-layer polymer elastomer in which the core (inner layer) is a crosslinked rubber polymer (Q) -the outer shell (outermost layer) is a thermoplastic polymer (P), and the core (inner layer) is a crosslinked weight.
• Combined (R) -inner shell (inner layer) is a crosslinked rubber polymer (Q) -outer shell (outermost layer) is a thermoplastic polymer (P) three-layer polymer elastomer, and core (inner layer) is a crosslinked rubber polymer (inner layer) Q) -The first inner shell (inner layer) is a crosslinked polymer (R) -The second inner shell (inner layer) is a crosslinked rubber polymer (Q) -The outer shell (outermost layer) is a thermoplastic polymer (P) 4 Layer polymer elastomer and the like can be mentioned.
• the polymer contained in each layer so that the difference in refractive index between adjacent layers is preferably less than 0.005, more preferably less than 0.004, and even more preferably less than 0.003. It is preferable to select.
• the mass ratio of the inner layer to the outermost layer in the multilayer copolymer elastomer is preferably 60/40 to 95/5, more preferably 70/30 to 90/10.
• the ratio of the layer containing the crosslinked rubber polymer (Q) is preferably 20 to 70% by mass, more preferably 30 to 50% by mass.
• the multi-layer copolymer elastomer has an average particle size of preferably 0.05 to 3 ⁇ m, more preferably 0.1 to 2 ⁇ m, and even more preferably 0.2 to 1 ⁇ m.
• an average particle size within such a range, particularly an average particle size of 0.2 to 1 ⁇ m, is used, toughness can be exhibited with a small amount of compounding, and therefore rigidity and surface hardness can be exhibited. Does not spoil.
• the average particle size in the present specification is an average value in a volume-based particle size distribution measured by the light scattered light method.
• thermoplastic polymer (P) is a polymer composed of a methacrylic acid alkyl ester unit having an alkyl group having 1 to 8 carbon atoms and, if necessary, a monofunctional monomer unit other than the methacrylic acid alkyl ester.
• the thermoplastic polymer (P) preferably does not contain a polyfunctional monomer unit.
• the amount of the methacrylic acid alkyl ester unit having an alkyl group having 1 to 8 carbon atoms constituting the thermoplastic polymer (P) is preferably 80 to 100% by mass with respect to the mass of the thermoplastic polymer (P). More preferably, it is 85 to 95% by mass.
• methacrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms (hereinafter, may be referred to as methacrylic acid C1-8 alkyl ester), for example, methyl methacrylate is preferable.
• the amount of the monofunctional monomer unit other than the methacrylic acid C1-8 alkyl ester constituting the thermoplastic polymer (P) is preferably 0 to 20% by mass with respect to the mass of the thermoplastic polymer (P). More preferably, it is 5 to 15% by mass.
• monofunctional monomers other than methacrylic acid C1-8 alkyl ester include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and prol acrylate; aromatic vinyl such as styrene. Compounds can be mentioned.
• the outermost layer may be a single layer made of one type of thermoplastic polymer (P), or may be a multi-layer made of two or more types of thermoplastic polymer (P).
• the amount of the thermoplastic polymer (P) is preferably 40 to 75% by mass, more preferably 45 to 70% by mass, and further preferably 50 to 65% by mass with respect to the amount of the multilayer copolymer elastomer.
• the crosslinked elastic layer which is an inner layer, has an intermediate layer made of a crosslinked rubber polymer (Q) and an inner layer made of a crosslinked polymer (R) and covered in contact with the intermediate layer.
• the crosslinked polymer (R) is composed of a methyl methacrylate unit, a monofunctional monomer unit other than methyl methacrylate, and a polyfunctional monomer unit.
• the amount of the methyl methacrylate unit constituting the crosslinked polymer (R) is preferably 40 to 98.5% by mass, more preferably 45 to 95% by mass, based on the mass of the crosslinked polymer (R).
• the amount of the monofunctional monomer unit other than methyl methacrylate constituting the crosslinked polymer (R) is 1 to 59.5% by mass, preferably 5 to 55% by mass, based on the mass of the crosslinked polymer (R). %.
• the monofunctional monomer other than methyl methacrylate include acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and propyl acrylate; and aromatic vinyl compounds such as styrene. Can be done.
• the amount of the polyfunctional monomer unit constituting the crosslinked polymer (R) is preferably 0.05 to 0.4% by mass, more preferably 0.1 to 0.1, based on the mass of the crosslinked polymer (R). It is 0.3% by mass.
• the polyfunctional monomer include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, triethylene glycol dimethacrylate, hexanediol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, triethylene glycol diacrylate, allyl methacrylate, and triallyl. Isocyanurate and the like can be mentioned.
• the amount of the crosslinked polymer (R) is preferably 5 to 40% by mass, more preferably 7 to 35% by mass, and further preferably 10 to 30% by mass with respect to the amount of the multilayer copolymer elastomer.
• the crosslinked rubber polymer (Q) is composed of an acrylic acid alkyl ester unit having an alkyl group having 1 to 8 carbon atoms and / or a conjugated diene unit, and a polyfunctional monomer unit.
• the amount of the acrylic acid alkyl ester unit and / or the conjugated diene unit having an alkyl group having 1 to 8 carbon atoms constituting the crosslinked rubber polymer (Q) is preferable with respect to the mass of the crosslinked rubber polymer (Q). It is 85 to 99% by mass, more preferably 95 to 98% by mass.
• acrylic acid alkyl ester having an alkyl group having 1 to 8 carbon atoms examples include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and propyl acrylate.
• conjugated diene examples include 1,3-butadiene, isoprene and the like.
• Examples of the crosslinked rubber polymer (Q) containing 1,3-butadiene as a monomer include a 1,3-polybutadiene homopolymer or a copolymer composed of 50% by weight or more of 1,3-polybutadiene units. be able to.
• Examples of the copolymer include, for example, a butadiene-aromatic vinyl compound copolymer such as a butadiene-styrene copolymer, a butadiene-vinyltoluene copolymer, etc., and further, a 1,3-butadiene unit of 50 weights by weight. Also includes ternary copolymers composed of% or more. These can usually be easily produced by known emulsion polymerization.
• the amount of the polyfunctional monomer unit constituting the crosslinked rubber polymer (Q) is preferably 1 to 1.7% by mass, more preferably 1.2 to 1% by mass, based on the mass of the crosslinked rubber polymer (Q). It is 1.6% by mass, more preferably 1.3 to 1.5% by mass.
• Examples of the polyfunctional monomer include those mentioned in the crosslinked polymer (R).
• the ratio of the mass of the polyfunctional monomer unit in the crosslinked rubber polymer (Q) to the mass of the polyfunctional monomer unit in the crosslinked polymer (R) is preferable. It is 0.05 to 0.25, more preferably 0.1 to 0.2.
• the glass transition temperature of the crosslinked rubber polymer (Q) is preferably lower than the glass transition temperature of the crosslinked polymer (R).
• the amount of the crosslinked rubber polymer (Q) is preferably 20 to 55% by mass, more preferably 25 to 45% by mass, and further preferably 30 to 40% by mass with respect to the amount of the multilayer copolymer elastomer.
• the average diameter (d) of the crosslinked elastic layer is preferably 60 to 110 nm, more preferably 65 to 105 nm, and further preferably 70 to 100 nm.
• the average diameter d (nm) of the layer of the crosslinked elastic body can be measured as follows. Using a hydraulic press molding machine, the resin composition containing the multilayer copolymer elastomer is cooled in a mold size of 50 mm ⁇ 120 mm, press temperature of 250 ° C., preheating time of 3 minutes, press pressure of 50 kg / cm 2 , press time of 30 seconds, and cooling.
• the obtained flat plate is cut at ⁇ 100 ° C. in a direction parallel to the long side to obtain a slice having a thickness of 40 nm, and the slice is dyed with ruthenium.
• the dyed flakes are observed with a scanning transmission electron microscope (JSM7600F manufactured by JEOL Ltd.) at an acceleration voltage of 25 kV and a photograph is taken.
• the multilayer copolymer elastomer is not particularly limited depending on the production method thereof.
• emulsion polymerization and the like can be mentioned.
• the monomer (r) for forming the crosslinked polymer (R) is emulsified and polymerized to obtain a latex containing the crosslinked polymer (R), and the crosslinked rubber polymer (R) is obtained.
• a monomer (q) for constituting Q) is added, and the monomer (q) is seed-emulsified and polymerized to obtain a latex containing a crosslinked polymer (R) and a crosslinked rubber polymer (q).
• the monomer (p) for forming the thermoplastic polymer (P) can be added thereto, and the monomer (p) can be seed-emulsified and polymerized to obtain a latex containing a multilayer copolymer elastomer.
• Emulsion polymerization is a known method used to obtain a latex containing a polymer.
• Seed emulsion polymerization is a method in which a monomer polymerization reaction is carried out on the surface of seed particles. Seed emulsion polymerization is preferably used to obtain core-shell structural polymer particles.
• the block copolymer elastomer is preferably composed of a polymer block (b1) having a methacrylic acid ester unit and a polymer block (b2) having an acrylic acid ester unit.
• the block copolymer elastomer may have only one polymer block (b1) in one molecule, or may have a plurality of block copolymer elastomers. Further, the block copolymer elastomer may have only one polymer block (b2) in one molecule, or may have a plurality of block copolymer elastomers.
• the amount of the methacrylic acid ester unit contained in the polymer block (b1) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more. ..
• the methacrylic acid ester for example, methyl methacrylate is preferable.
• the methacrylic acid ester can be used alone or in combination of two or more in the polymer block (b1).
• the amount of the polymer block (b1) contained in the block copolymer elastomer is preferably from the viewpoints of transparency, flexibility, bending resistance, impact resistance, flexibility, molding processability, surface smoothness and the like. It is 40% by mass or more and 90% by mass or less, more preferably 45% by mass or more and 80% by mass or less.
• the glass transition temperature of the polymer block (b2) is preferably 20 ° C. or lower, more preferably ⁇ 20 ° C. or lower.
• the amount of the acrylic acid ester unit contained in the polymer block (b2) is preferably 90% by mass or more.
• the acrylic acid ester include n-butyl acrylate and benzyl acrylate. These acrylic acid esters can be used alone or in combination of two or more for the polymer block (b2).
• the polymer block (b2) may contain a monomer unit other than the acrylic acid ester as long as it does not interfere with the object and effect of the present invention.
• the polymer block (b2) is preferably composed of an acrylic acid alkyl ester unit and a (meth) acrylic acid aromatic ester unit from the viewpoint of transparency and the like.
• the mass ratio of the acrylic acid alkyl ester unit / (meth) acrylic acid aromatic ester is preferably 50/50 to 90/10, more preferably 60/40 to 80/20.
• the bond form between the polymer block (b1) and the polymer block (b2) contained in the block copolymer elastomer is not particularly limited.
• one end of the polymer block (b1) is connected to one end of the polymer block (b2) (b1-b2 diblock copolymer); a polymer is attached to both ends of the polymer block (b2).
• a block (b1) in which one end is connected is preferable.
• the block copolymer elastomer has a weight average molecular weight of preferably 52,000 or more and 400,000 or less, and more preferably 60,000 or more and 300,000 or less.
• the ratio of the weight average molecular weight to the number average molecular weight of the block copolymer elastomer is preferably 1.01 or more and 2.00 or less, and more preferably 1.05 or more and 1.60 or less.
• the weight average molecular weight and the number average molecular weight of the block copolymer elastomer can be appropriately set from the viewpoints of moldability, tensile strength, appearance and the like.
• the weight average molecular weight and the number average molecular weight are standard polystyrene-equivalent values measured by GPC (gel permeation chromatography).
• the block copolymer elastomer is not particularly limited depending on the production method thereof, and can be obtained by a known method. For example, a method including living polymerization of the monomers constituting each polymer block is generally used. As a living polymerization method, a high-purity block copolymer elastomer can be obtained, the molecular weight and composition ratio can be easily controlled, and the cost is low. Therefore, in the presence of an organoalkali metal compound and an organoaluminum compound. A method involving anionic polymerization is preferred.
• the mass ratio of the acrylic copolymer (A) / elastomer (B) is 99/1 to 51/49 from the viewpoint of impact resistance and surface hardness, which is 95/5. It is preferably ⁇ 55/45, and more preferably 90/10 to 60/40.
• the acrylic resin composition of the present invention has a melt flow rate of preferably 1 g / 10 minutes or more, more preferably 1.5 to 35 g / 10 minutes, still more preferably 2 to 2 to 10 minutes or more under the conditions of 230 ° C. and a load of 3.8 kg. 20 g / 10 minutes.
• the melt flow rate is a value of the melt mass flow rate measured in accordance with JIS K7210.
• the acrylic resin composition of the present invention has a glass transition temperature of preferably 100 to 160 ° C, more preferably 105 to 155 ° C, and even more preferably 110 to 150 ° C.
• the glass transition temperature is 100 ° C. or lower, the heat resistance tends to decrease, and when the glass transition temperature is 160 ° C. or higher, the moldability tends to decrease.
• the softening temperature of the molded product measured by the method specified by the B50 method of JIS K7206 is preferably 110 ° C. or higher, more preferably 115 ° C. or higher, still more preferably 120 ° C. or higher. be.
• the softening temperature is 110 ° C. or higher, the molded product has excellent heat resistance and excellent dimensional stability at high temperatures.
• the acrylic resin composition of the present invention has a saturated water absorption rate of 2.5% or less, more preferably 2.1% or less, which is measured under the same conditions as the measurement of the saturated water absorption rate of the acrylic copolymer (A). It is preferably 2.0% or less. Since the saturated water absorption rate is 2.5% or less, the dimensional stability at high humidity is excellent.
• the acrylic resin composition of the present invention may contain a filler, if necessary, as long as the effects of the present invention are not impaired.
• the filler include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, magnesium carbonate and the like.
• the amount of the filler that can be contained in the resin composition of the present invention is preferably 3% by mass or less, more preferably 1.5% by mass or less.
• the acrylic resin composition of the present invention may contain other polymers as long as the effects of the present invention are not impaired.
• Other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, polynorbornene; ethylene-based ionomers; polystyrene, styrene-maleic anhydride copolymers, high-impact polystyrene, etc.
• Sterite resins such as AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; methyl methacrylate-based polymers other than acrylic copolymer (A), methyl methacrylate-styrene copolymer; polyethylene terephthalate, Polyester resin such as polybutylene terephthalate; polyamide such as nylon 6, nylon 66, polyamide elastomer; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, vinylidene fluoride, polyurethane, phenoxy resin, Modified polyphenylene ethers, polyphenylene sulfides, silicone-modified resins; silicone rubbers; styrene-based thermoplastic polymers such as SEPS, SEBS, and SIS; olefin-based rubbers such as IR, EPR, and EPDM can be mentioned.
• the acrylic resin composition of the present invention includes antioxidants, heat deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, as long as the effects of the present invention are not impaired. It may contain additives such as antistatic agents, flame retardants, dyes and pigments, light diffusing agents, organic dyes, matting agents and phosphors.
• the antioxidant is effective in preventing oxidative deterioration of the resin by itself in the presence of oxygen.
• phosphorus-based antioxidants hindered phenol-based antioxidants, thioether-based antioxidants, and the like can be mentioned. These antioxidants can be used alone or in combination of two or more. Of these, phosphorus-based antioxidants and hindered phenol-based antioxidants are preferable from the viewpoint of the effect of preventing deterioration of optical properties due to coloring, and the combined use of phosphorus-based antioxidants and hindered phenol-based antioxidants is more preferable. preferable.
• the ratio is not particularly limited, but the mass ratio of the phosphorus-based antioxidant / hindered phenol-based antioxidant is preferably 1/5. It is ⁇ 2/1, more preferably 1/2 ⁇ 1/1.
• Phosphorus antioxidants include 2,2-methylenebis (4,6-dit-butylphenyl) octylphosphite (manufactured by ADEKA; trade name: ADEKA STAB HP-10), tris (2,4-dit-). Butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals; trade name: IRUGAFOS168), 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10- Examples thereof include tetraoxa-3,9-diphosphaspiro [5.5] undecane (manufactured by ADEKA; trade name: ADEKA STUB PEP-36).
• pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals; trade name IRGANOX1010)
• examples thereof include octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by Ciba Specialty Chemicals Co., Ltd .; trade name IRGANOX1076).
• the thermal deterioration inhibitor is a compound capable of preventing thermal deterioration of a resin by capturing polymer radicals generated when exposed to high heat under a substantially oxygen-free state, and is, for example, 2-t-butyl-6-. (3'-t-butyl-5'-methyl-hydroxybenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name: Sumilyzer GM), 2,4-di-t-amyl-6- (3', Examples thereof include 5'-di-t-amyl-2'-hydroxy- ⁇ -methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name: Sumilyzer GS).
• An ultraviolet absorber is a compound having an ability to absorb ultraviolet rays.
• the ultraviolet absorber is a compound that is said to have a function of mainly converting light energy into heat energy.
• Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic acid esters, formamidines and the like. These may be used alone or in combination of two or more.
• benzotriazoles, triazines, and ultraviolet absorbers having a maximum molar extinction coefficient ⁇ max at a wavelength of 380 to 450 nm of 1200 dm 3 mol -1 cm -1 or less are preferable.
• benzotriazoles examples include 2- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by BASF; trade name TINUVIN329), 2- (2H-).
• Benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF; trade name TINUVIN234), 2,2'-methylenebis [6- (2H-benzotriazole-2) -Il) -4-tert-octylphenol] (manufactured by ADEKA; trade name LA-31), 2- (5-octylthio-2H-benzotriazole-2-yl) -6-tert-butyl-4-methylphenol, etc. Is preferable.
• a triazine-type ultraviolet absorber is preferably used.
• examples of such an ultraviolet absorber include 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (manufactured by ADEKA; trade name LA-F70). And its relatives, hydroxyphenyltriazine-based ultraviolet absorbers (manufactured by BASF; trade names TINUVIN477, TINUVIN460 and TINUVIN479), 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1, Examples include 3,5-triazine.
• the light stabilizer is a compound that is said to have a function of capturing radicals mainly generated by oxidation by light, and examples thereof include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton. Be done.
• lubricant examples include stearic acid, behenic acid, stearoamic acid, methylene bisstearoamide, hydroxystearic acid triglyceride, paraffin wax, ketone wax, octyl alcohol, and hydrogenated oil.
• the mold release agent is a compound having a function of facilitating the mold release of a molded product from a mold, and is, for example, higher alcohols such as cetyl alcohol and stearyl alcohol; and glycerin higher fatty acids such as stearic acid monoglyceride and stearic acid diglyceride. Esther and the like can be mentioned. Since the use of glycerin higher fatty acid ester may cause gel-like foreign substances, it is preferable to use higher alcohols.
• the polymer processing aid is a compound that exerts an effect on thickness accuracy and thinning when molding an acrylic resin composition.
• the polymer processing aid can usually be produced by an emulsification polymerization method.
• the polymer processing aid is preferably polymer particles having a particle size of 0.05 to 0.5 ⁇ m.
• the polymer particles may be single-layer particles composed of a polymer having a single composition ratio and a single extreme viscosity, or may be multilayer particles composed of two or more kinds of polymers having different composition ratios or ultimate viscosities. You may.
• particles having a two-layer structure having a polymer layer having a low ultimate viscosity in the inner layer and a polymer layer having a high ultimate viscosity of 5 dl / g or more in the outer layer are preferable.
• the polymer processing aid preferably has an ultimate viscosity of 3 to 6 dl / g. If the ultimate viscosity is too small, the effect of improving moldability is low. If the ultimate viscosity is too large, the melt fluidity of the acrylic resin composition tends to decrease.
• Antistatic agents include sodium heptyl sulfonate, sodium octyl sulfonate, sodium nonyl sulfonate, sodium decyl sulfonate, sodium dodecyl sulfonate, sodium cetyl sulfonate, sodium octadecyl sulfonate, sodium diheptyl sulfonate, heptyl sulfonic acid.
• potassium octyl sulfonate potassium nonyl sulfonate, potassium decyl sulfonate, potassium dodecyl sulfonate, potassium cetyl sulfonate, potassium octadecyl sulfonate, potassium diheptyl sulfonate, lithium heptyl sulfonate, lithium octyl sulfonate, nonyl sulfonate
• alkyl sulfonates such as lithium acid, lithium decyl sulfonate, lithium dodecyl sulfonate, lithium cetyl sulfonate, lithium octadecyl sulfonate, and lithium diheptyl sulfonate.
• Examples of the flame retardant include metal hydrates having a hydroxyl group or crystalline water such as magnesium hydroxide, aluminum hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, and hydrotalcite, and phosphoric acid such as polyphosphate amine and phosphoric acid ester.
• Examples include compounds and silicon compounds, including trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, and dimethyl ethyl.
• Phosphate-based flame retardants such as phosphate, methyldibutyl phosphate, ethyldipropyl phosphate, and hydroxyphenyldiphenyl phosphate are preferred.
• Dyes / pigments include red organic pigments such as parared, fire red, pyrazolone red, thioindico red, and perylene red, blue organic pigments such as cyanine blue and indanslen blue, and green organic pigments such as cyanine green and naphthol green. Pigments are mentioned, and one or more of these can be used.
• the organic dye a compound having a function of converting ultraviolet rays into visible light is preferably used.
• the light diffusing agent and the matting agent include glass fine particles, polysiloxane-based crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, barium sulfate and the like.
• the phosphor include a fluorescent pigment, a fluorescent dye, a fluorescent white dye, a fluorescent whitening agent, and a fluorescent bleaching agent.
• additives may be used alone or in combination of two or more. Further, these additives may be added to the polymerization reaction solution for producing the acrylic copolymer (A) and the elastomer (B), or the produced acrylic copolymer (A) or crosslinks may be added. It may be added to the rubber (B), or may be added when preparing the acrylic resin composition of the present invention.
• the total amount of the additives contained in the acrylic resin composition of the present invention is preferably 7% by mass or less, more preferably 5 with respect to the acrylic resin composition, from the viewpoint of suppressing poor appearance of the molded product. It is mass% or less, more preferably 4 mass% or less.
• the method for preparing the acrylic resin composition of the present invention is not particularly limited. For example, a method of polymerizing a monomer mixture containing methyl methacrylate or the like in the presence of an elastomer (B) to produce an acrylic copolymer (A), or an acrylic copolymer (A) and an elastomer (B). ) Can be melt-kneaded. At the time of melt-kneading, other polymers and additives may be mixed as needed, or the acrylic copolymer (A) is mixed with other polymers and additives and then with the elastomer (B).
• the elastomer (B) may be mixed with another polymer and an additive, and then mixed with the acrylic copolymer (A), or another method may be used. Kneading can be performed using, for example, a known mixing device or kneading device such as a kneader ruder, an extruder, a mixing roll, a Banbury mixer. Of these, a twin-screw extruder is preferable.
• the acrylic resin composition of the present invention can be in the form of pellets or the like in order to enhance convenience during storage, transportation, or molding.
• the molded product of the present invention comprises the acrylic resin composition of the present invention.
• the method for producing the molded product of the present invention is not particularly limited.
• T-die method laminate method, coextrusion method, etc.
• inflation method coextrusion method, etc.
• compression molding method blow molding method
• calendar molding method vacuum molding method
• injection molding method insert method, two-color method, etc.
• a melt molding method such as a pressing method, a core back method, a sandwich method, etc., and a solution casting method can be mentioned.
• the T-die method, the inflation method, or the injection molding method is preferable from the viewpoint of high productivity, cost, and the like.
• the type of the molded body is not limited, but a film (a flat molded body having a thickness of 5 ⁇ m or more and 250 ⁇ m or less) or a sheet (a flat molded body having a thickness of 5 ⁇ m or more and 250 ⁇ m or less) is mentioned as preferable, and a film is particularly preferable.
• the film which is a form of the molded product of the present invention, can be produced by a solution casting method, a melt casting method, an extrusion molding method, an inflation molding method, a blow molding method, or the like.
• the extrusion molding method is preferable from the viewpoint of being able to obtain a film having excellent transparency, improved toughness, excellent handleability, and an excellent balance between toughness, surface hardness, and rigidity.
• the temperature of the molten resin discharged from the extruder is preferably set to 160 to 270 ° C, more preferably 220 to 260 ° C.
• the T-die method is preferable from the viewpoint of obtaining a film having good surface smoothness, good mirror gloss, and low haze.
• this T-die method it is preferable that the molten resin discharged from the T-die via an extruder, a gear pump, a polymer filter, and a mixer is sandwiched between two or more mirror rolls or a mirror belt to form a film. Banks may or may not be formed when sandwiched between mirror rolls or mirror belts.
• the die has a function of automatically adjusting the lip opening degree, and the air gap is preferably 100 mm or less.
• the mirror roll or mirror belt is preferably made of metal.
• the mirror surface roll a metal rigid body roll, a metal elastic body roll, or the like can be used, and it is preferable to use a gold bullet elastic body roll and a metal rigid body roll in combination.
• the surface temperature of the mirror surface roll or the mirror surface belt is 130 ° C. or lower.
• the surface temperature of at least one of the pair of mirror rolls or mirror belts is 60 ° C. or higher.
• the linear pressure between the pair of rolls or belts is preferably 10 N / mm or more, more preferably 30 N / mm or more.
• the thickness of the unstretched film obtained by extrusion molding is preferably 10 to 300 ⁇ m.
• the haze of the film is preferably 0.57% or less, more preferably 0.35% or less, still more preferably 0.3% or less at a thickness of 100 ⁇ m.
• the unstretched film obtained as described above may be stretched.
• the stretching method is not particularly limited, and examples thereof include a simultaneous biaxial stretching method, a sequential biaxial stretching method, and a tuber stretching method.
• the lower limit of the temperature at the time of stretching is a temperature 10 ° C. higher than the glass transition temperature of the acrylic copolymer or the acrylic resin composition, which is the temperature at the time of stretching.
• the upper limit is a temperature 40 ° C. higher than the glass transition temperature of the acrylic copolymer or acrylic resin composition.
• Stretching is usually performed at 100-5000% / min. By performing heat fixation after stretching, a film having less heat shrinkage can be obtained.
• the thickness of the film after stretching is preferably 10 to 200 ⁇ m.
• a functional layer may be provided on the surface of a film which is a form of a molded product of the present invention.
• the functional layer include a hard coat layer, an anti-glare layer, an anti-reflection layer, an anti-sticking layer, a diffusion layer, an anti-glare layer, an anti-static layer, an anti-fouling layer, and an easy-to-slip layer such as fine particles.
• the acrylic resin composition of the present invention is suitable as a molding material.
• the molded product of the present invention can be used as a member for various purposes. Specific applications include, for example, signboard parts such as advertising towers, stand signs, sleeve signs, column signs, roof signs, and marking films; display parts such as showcases, dividers, and store displays; fluorescent lamp covers, mood lighting. Lighting parts such as covers, lamp shades, light ceilings, light walls, chandeliers; interior parts such as furniture, pendants, mirrors; doors, dome, safety window glass, partitions, staircase wainscots, balcony wainscots, roofs of leisure buildings, etc.
• Related parts Nameplates for audiovisual images, stereo covers, TV protective masks, vending machines, mobile phones, personal computers and other electronic equipment parts; incubators, roentgen parts and other medical equipment parts; machine covers, instrument covers, experimental equipment, rulers , Dials, observation windows and other equipment-related parts; LCD protective plates, light guide plates, light guide films, Frenel lenses, lenticular lenses, front plates of various displays, diffuser plates and other optical parts; Road signs, guide plates, curves Transportation-related parts such as mirrors and soundproof walls; Others, greenhouses, large water tanks, box water tanks, bathroom parts, clock panels, bathtubs, sanitary, desk mats, game parts, toys, musical instruments, face protection masks during welding, solar cells Backsheets, frontsheets for flexible solar cells, decorative films; surface materials used
• a laminated body can be obtained by laminating a layer containing the acrylic resin composition of the present invention and another material (for example, a layer containing another thermoplastic copolymer).
• other materials used for the laminate include steel, plastic (for example, thermoplastic resin), wood, glass and the like.
• the laminate obtained by the present invention is suitably used for wallpaper; automobile interior member surface; automobile exterior member surface such as bumper; mobile phone surface; furniture surface; personal computer surface; vending machine surface; bathroom member surface such as bathtub. be able to.
• the film which is a form of the molded product of the present invention, has high transparency and heat resistance, and is therefore suitable for optical applications. It is particularly suitable for display window protective films, light guide films, transparent conductive films coated with silver nanowires and carbon nanotubes on the surface, and front panel applications of various displays. Since the film of the present invention has high transparency and heat resistance, it can be used for applications other than optical applications such as infrared cut film, security film, shatterproof film, decorative film, metal decorative film, shrink film, and in-mold label film. Can be used for.
• the film which is one form of the molded product of the present invention is used as a polarizer protective film or a retardation film, it may be laminated on only one side of the polarizer film or on both sides. When laminated with the polarizer film, it can be laminated via an adhesive layer or an adhesive layer.
• a stretched film made of a polyvinyl alcohol-based resin and iodine can be used, and the film thickness is preferably 1 to 100 ⁇ m.
• the weight average molecular weight (Mw) of the resin obtained in the production example was determined by the GPC method (gas chromatography method).
• a sample solution was prepared by dissolving 4 mg of the resin to be measured in 5 ml of tetrahydrofuran.
• the temperature of the column oven was set to 40 ° C., the eluent flow rate was 0.35 ml / min, 20 ⁇ l of the sample solution was injected into the apparatus, and the chromatogram was measured.
• Ten standard polystyrenes having a molecular weight in the range of 400 to 5,000,000 were GPC-measured to prepare a calibration curve showing the relationship between the retention time and the molecular weight.
• the Mw of the resin to be measured was determined based on this calibration curve. From the chromatogram measured by GPC (gel permeation chromatography), the value corresponding to the molecular weight of standard polystyrene was taken as the molecular weight of the copolymer.
• Equipment Tosoh GPC equipment
• Eluent tetrahydrofuran
• Eluent flow rate 0.35 ml / min
• Column temperature 40 ° C.
• Detection method Differential refractometer (RI)
• composition of each unit in the copolymer 13
• the carbon ratio of the phenyl group of ⁇ -methylstyrene unit, the carbonyl group of methyl methacrylate unit and the phenyl group of styrene unit was determined by C-NMR, and the composition of each unit was calculated by this.
• Glass transition temperature Tg Glass transition temperature Tg
• the resin obtained in the production example is once heated to 250 ° C. and then cooled to room temperature using a differential scanning calorimetry device (manufactured by Shimadzu Corporation, DSC-50 (product number)) in accordance with JIS K7121. After that, the DSC curve was measured under the condition that the temperature was raised from room temperature to 200 ° C. at 10 ° C./min.
• the midpoint glass transition temperature obtained from the DSC curve measured at the time of the second temperature rise was defined as the glass transition temperature in the present invention.
• composition of each unit of acrylic copolymer The ⁇ -methylstyrene unit and the styrene unit had the same composition as each unit composition of the precursor polymer. Using 1 H-NMR (manufactured by Bruker; trade name ULTRA SHIELD 400 PLUS), 1 H-NMR measurement of the acrylic copolymer was performed, and glutarialimide units and methyl methacrylate units in the acrylic copolymer were measured. Obtain the content (mol%) of each monomer unit such as aromatic vinyl ( ⁇ -methylstyrene and styrene) unit, and use the molecular weight of each monomer unit to determine the content (mol%). Converted to content (% by weight).
• thermogravimetric reduction temperature The acrylic copolymer obtained in the production example and the acrylic resin composition obtained in the examples and comparative examples were subjected to thermogravimetric analysis (manufactured by Shimadzu Corporation, TGA-50) at 10 ° C. in a nitrogen atmosphere. The temperature at the time when the temperature was raised at / min and the weight was reduced by 1% was defined as the 1% thermogravimetric reduction temperature.
• Vicat softening temperature Acrylic resins obtained in Examples and Comparative Examples using an injection molding machine (M-100C, manufactured by Meiki Co., Ltd.) under the conditions of a cylinder temperature of 260 ° C., a mold temperature of 50 ° C., and an injection speed of 50 mm / sec. The composition was injection molded to obtain a rectangular test piece having a thickness of 4 mm, a long piece of 80 mm, and a short side of 10 mm. The Vicat softening temperature (VST) of each test piece was measured using an HDT test device 3M-2 manufactured by Toyo Seiki Seisakusho Co., Ltd. in accordance with the method described in the B50 method of JIS K7206.
• the test piece was then immersed in distilled water at 23 ° C. The test piece was taken out of water, the water adhering to the surface was wiped off, and the mass was measured. Immersion in distilled water and mass measurement were repeated until there was no change in mass.
• the acrylic resin compositions obtained in Examples and Comparative Examples were extruded from a T-die having a width of 150 mm at a resin temperature of 260 ° C., and the width was 100 mm and the thickness was 80 ⁇ m.
• Single layer film was obtained.
• the appearance of the flat plate was visually observed.
• the quality of moldability was judged based on the presence or absence of molding defects such as sink marks and silver.
• the appearance of the film was visually observed.
• the quality of moldability was judged based on the presence or absence of foaming and gel lumps.
• ⁇ No sink mark on the molded product, no silver generation, no foaming of the film, no gel lumps
• the flat plate was taken out from the incubator and the dimensions in the length direction were measured.
• the dimensional change rate from the dimension in the length direction before putting it in the incubator was calculated.
• " ⁇ " indicates that the dimensional change rate is 0.3% or less under both conditions (1) and (2).
• " ⁇ ” indicates that the dimensional change rate is 0.3% or less under either of (1) and (2) conditions. Those having a dimensional change rate greater than 0.3% under both the conditions (1) and (2) were designated as "x".
• Acrylic resins obtained in Examples and Comparative Examples using an injection molding machine (M-100C, manufactured by Meiki Co., Ltd.) under the conditions of a cylinder temperature of 260 ° C., a mold temperature of 50 ° C., and an injection speed of 50 mm / sec. The composition was injection molded to obtain a square test piece having a thickness of 3 mm and a side of 50 mm. Further, using a single-screw extruder having a shaft diameter of 20 m, the acrylic resin compositions obtained in Examples and Comparative Examples were extruded from a T-die having a width of 150 mm at a resin temperature of 260 ° C., and the width was 100 mm and the thickness was 80 ⁇ m.
• M-100C manufactured by Meiki Co., Ltd.
• Precursor polymer The precursor polymers Aa to Af and Ah according to this production example were produced by the following methods. Precursor polymers Aa-Af, and Ah Purified methyl methacrylate (MMA), ⁇ -methylstyrene ( ⁇ MSt), styrene (St), 2,2'-azobis (2-methylpropionitrile) (AIBN) and n-octyl in an autoclave with a stirrer. Mercaptan (n-OM) was charged at the ratio shown in Table 1 and uniformly dissolved to obtain a polymerization raw material. Nitrogen gas was blown into the reaction raw material to remove up to 3 ppm of dissolved oxygen.
• MMA methyl methacrylate
• ⁇ MSt ⁇ -methylstyrene
• St styrene
• AIBN 2,2'-azobis (2-methylpropionitrile
• the polymerization raw material is continuously supplied into the tank reactor at a constant flow rate so as to have the average residence time shown in Table 1, and bulk polymerization is carried out at the polymerization temperature shown in Table 1 to carry out a tank reaction.
• the liquid containing the precursor polymer was continuously discharged from the reactor.
• the pressure in the tank reactor was adjusted by a pressure regulating valve connected to the brine cooling condenser.
• the polymerization conversion rate was the value shown in Table 1.
• the liquid discharged from the reactor was heated to 230 ° C. and supplied to a twin-screw extruder controlled to 240 ° C.
• the volatile matter containing the unreacted monomer as a main component was separated and removed, and the precursor polymer was extruded as a strand.
• the strands were cut with a pelletizer to give a precursor polymer.
• the weight average molecular weight Mw of the obtained precursor polymer, the ratio of each monomer unit, and the glass transition temperature were measured. The results are shown in Table 1.
• Precursor polymer Ag MS resin (copolymer of methyl methacrylate (MMA) and styrene (St)) is produced according to the method for producing a copolymer (A) described in the section of [Example] of JP-A-2003-231785. bottom.
• MMA methyl methacrylate
• St styrene
• the amount was adjusted and injected from the additive supply port of the twin-screw extruder to react the acrylic copolymer [Aa] with monomethylamine.
• Most of the melt-kneaded portion is composed of a kneading disc, and seal elements are attached to both ends thereof.
• the devolatilization section by-products and excess monomethylamine were volatilized from the molten resin that had passed through the melt-kneading section and discharged through a plurality of vents.
• the molten resin extruded as a strand from a die provided at the end of the discharge section of the twin-screw extruder was cooled in a water tank and then cut with a pelletizer to obtain a pellet-shaped imidized resin [A-1]. ..
• the content of the structural unit derived from glutarimide in the imidized resin [A-1] was 9 wt%. Table 1 shows the composition and physical characteristics of the imidized resin [A-1].
• Production example 5 An acrylic copolymer [Ad] is used instead of the acrylic copolymer [AA], and the amount of monomethylamine added is such that the content of the structural unit derived from glutarimide is 9 wt%.
• An imidized resin [A-5] was obtained in the same manner as in Example 1 except that it was changed. Table 1 shows the composition and physical characteristics of the imidized resin [A-5].
• Production example 6 An acrylic copolymer [Ad] is used instead of the acrylic copolymer [AA], and the amount of monomethylamine added is such that the content of the structural unit derived from glutarimide is 23 wt%.
• An imidized resin [A-6] was obtained in the same manner as in Example 1 except that it was changed. Table 1 shows the composition and physical characteristics of the imidized resin [A-6].
• Production example 7 An acrylic copolymer [Ad] is used instead of the acrylic copolymer [AA], and the amount of ammonia added instead of monomethylamine is 15 wt% of the content of the structural unit derived from glutarimide.
• An imidized resin [A-7] was obtained in the same manner as in Example 1 except that the resin was changed to. Table 1 shows the composition and physical characteristics of the imidized resin [A-7].
• Production Example 8 An acrylic copolymer [Ae] is used instead of the acrylic copolymer [Aa], and the amount of monomethylamine added is such that the content of the structural unit derived from glutarimide is 19 wt%.
• An imidized resin [A-8] was obtained in the same manner as in Example 1 except that it was changed. Table 1 shows the composition and physical characteristics of the imidized resin [A-8].
• Production Example 10 An acrylic copolymer [Ab] is used instead of the acrylic copolymer [Aa], and the amount of monomethylamine added is such that the content of the structural unit derived from glutarimide is 45 wt%.
• An imidized resin [A-10] was obtained in the same manner as in Example 1 except that it was changed. Table 1 shows the composition and physical characteristics of the imidized resin [A-10].
• Example 11 An acrylic copolymer [Ag] is used instead of the acrylic copolymer [Aa], and the amount of monomethylamine added is such that the content of the structural unit derived from glutarimide is 10 wt%.
• An imidized resin [A-11] was obtained in the same manner as in Example 1 except that it was changed. Table 1 shows the composition and physical characteristics of the imidized resin [A-11].
• Production Example 12 An acrylic copolymer [Ag] is used instead of the acrylic copolymer [Aa], and the amount of monomethylamine added is adjusted so that the content of the structural unit derived from glutarimide is 44 wt%.
• An imidized resin [A-12] was obtained in the same manner as in Example 1 except that it was changed. Table 1 shows the composition and physical characteristics of the imidized resin [A-12].
• Example 13 An acrylic copolymer [Ah] is used instead of the acrylic copolymer [Aa], and the amount of monomethylamine added is adjusted so that the content of the structural unit derived from glutarimide is 24 wt%.
• An imidized resin [A-13] was obtained in the same manner as in Example 1 except that it was changed. Table 1 shows the composition and physical characteristics of the imidized resin [A-13].
• Production example 14 In the same manner as in Example 1, an acrylic copolymer [Ab] was used instead of the acrylic copolymer [Aa], and the extruder was passed through without adding an imidizing agent. An imidized resin [A-14] was obtained. Table 1 shows the composition and physical characteristics of the imidized resin [A-14].
• the latex was frozen and solidified. Then, it was washed with water and dried to obtain a multilayer copolymer elastomer (B-1).
• the average particle size of the multilayer copolymer elastomer (B-1) was 0.2 ⁇ m.
• Production example 16 In a pressure resistant autoclave, 150 parts by mass of ion-exchanged water, 85 parts by mass of 1,3-butadiene, 15 parts by mass of styrene, 0.5 parts by mass of t-dodecyl mercaptan, 0.4 parts by mass of diisopropylbenzene hydroperoxide, sodium pyrophosphate 1 .5 parts by mass, 0.02 parts by mass of ferrous sulfate, 1.0 part by mass of dextrose, and 1.0 part by mass of potassium oleate were charged and reacted at 50 ° C. for 15 hours with stirring to produce a butadiene rubber. A polymerized latex was produced.
• t-BH t-butyl hydroperoxide
• Production example 17 Dry toluene at room temperature 735 kg, hexamethyltriethylenetetramine 0.4 kg, and isobutylbis (2,6) in a glass-lined 3 m 3 reaction vessel with a degassed, nitrogen-replaced brine-coolable jacket and stirrer. -Di-t-Butyl-4-methylphenoxy) 39.4 kg of a toluene solution containing 20 mol of aluminum was added, and 1.17 mol of sec-butyllithium was further added.
• Methyl methacrylate (35.0 kg) was added thereto, and the mixture was reacted at room temperature for 1 hour to obtain a methyl methacrylate polymer having a weight average molecular weight (hereinafter referred to as Mw (b1-1)) of 40,000 (polymer block (b1). -1)) was obtained.
• a mixed solution of 24.5 kg of n-butyl acrylate and 10.5 kg of benzyl acrylate was added dropwise over 0.5 hours to obtain a polymer block (b1-1).
• a polymer block (b2) composed of a copolymer of n-butyl acrylate and benzyl acrylate was grown from one end to obtain a diblock copolymer elastomer (B-3) having a weight average molecular weight of 80,000. .. Since the weight average molecular weight of the polymer block (b1-1) was 40,000, it was determined that the weight average molecular weight (Mw (b2)) of the polymer block (b2) was 40,000.
• the diblock copolymer elastomer (B-3) has an acrylic acid ester content of 50% by mass.
• Example 1 80 parts by mass of the acrylic copolymer (A-1) and 20 parts by mass of the multilayer copolymer elastomer (B-1) are mixed and melt-kneaded at 250 ° C. in a twin-screw extruder having a shaft diameter of 20 mm. , Extruded to obtain a pellet-shaped acrylic resin composition (C-1) having a glass transition temperature of 120 ° C. The evaluation results are shown in Table 2.
• Examples 2-12 An acrylic resin composition was obtained in the same manner as in Example 1 except for the formulations shown in Table 2. The evaluation results are shown in Table 2.
• Comparative Examples 1 to 7 An acrylic resin composition was obtained in the same manner as in Example 1 except for the formulations shown in Table 2. The evaluation results are shown in Table 3.
• the acrylic resin composition of the present invention has high heat resistance even when an elastomer is added by containing an acrylic copolymer having an excellent balance of heat resistance, low water absorption, and heat decomposition resistance. It retains properties, low water absorption, and high rigidity, and has good thermal stability.
• the acrylic resin composition of the present invention can provide a molded product and a film having excellent dimensional stability, moldability, and surface hardness.

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