WO2022210417A1 - 熱可塑性樹脂組成物、成形品 - Google Patents
熱可塑性樹脂組成物、成形品 Download PDFInfo
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- WO2022210417A1 WO2022210417A1 PCT/JP2022/014645 JP2022014645W WO2022210417A1 WO 2022210417 A1 WO2022210417 A1 WO 2022210417A1 JP 2022014645 W JP2022014645 W JP 2022014645W WO 2022210417 A1 WO2022210417 A1 WO 2022210417A1
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- vinyl
- thermoplastic resin
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 1
- UYNIHQFSTRDMAY-UHFFFAOYSA-L dipotassium 4-heptadec-1-enoxy-4-oxobutanoate Chemical compound C(CCC(=O)[O-])(=O)OC=CCCCCCCCCCCCCCCC.[K+].[K+].C(=CCCCCCCCCCCCCCCC)OC(CCC(=O)[O-])=O UYNIHQFSTRDMAY-UHFFFAOYSA-L 0.000 description 1
- DUTQNAMBWKUFQN-UHFFFAOYSA-L dipotassium 4-hexadec-1-enoxy-4-oxobutanoate Chemical compound C(CCC(=O)[O-])(=O)OC=CCCCCCCCCCCCCCC.[K+].[K+].C(=CCCCCCCCCCCCCCC)OC(CCC(=O)[O-])=O DUTQNAMBWKUFQN-UHFFFAOYSA-L 0.000 description 1
- PWZPZEQVSQVWMM-UHFFFAOYSA-L dipotassium 4-octadec-1-enoxy-4-oxobutanoate Chemical compound C(CCC(=O)[O-])(=O)OC=CCCCCCCCCCCCCCCCC.[K+].[K+].C(=CCCCCCCCCCCCCCCCC)OC(CCC(=O)[O-])=O PWZPZEQVSQVWMM-UHFFFAOYSA-L 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- GOAJGXULHASQGJ-UHFFFAOYSA-N ethene;prop-2-enenitrile Chemical group C=C.C=CC#N GOAJGXULHASQGJ-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 229940048098 sodium sarcosinate Drugs 0.000 description 1
- ZUFONQSOSYEWCN-UHFFFAOYSA-M sodium;2-(methylamino)acetate Chemical compound [Na+].CNCC([O-])=O ZUFONQSOSYEWCN-UHFFFAOYSA-M 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/105—Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
-
- 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
- C08L51/08—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 otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L51/085—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 otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0818—Alkali metal
- C08K2003/0825—Potassium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/324—Alkali metal phosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/30—Applications used for thermoforming
Definitions
- the present invention relates to thermoplastic resin compositions and molded articles thereof.
- This application claims priority based on Japanese Patent Application No. 2021-059491 filed in Japan on March 31, 2021, the content of which is incorporated herein.
- the method of using a resin material in which a rubbery polymer and a hard resin are combined to maintain the characteristics derived from the hard resin while enhancing the impact resistance of the molded product has already been industrialized.
- resin materials include acrylonitrile-styrene-acrylic acid ester (ASA) resins, acrylonitrile-ethylene/ ⁇ -olefin-styrene (AES) resins, and thermoplastic resin compositions obtained by further adding these to hard resins. mentioned.
- thermoplastic resin composition capable of obtaining a molded article excellent in weather resistance, impact resistance and molded appearance
- a thermoplastic resin composition containing a graft copolymer (A1) obtained by polymerizing an aromatic alkenyl compound and a vinyl cyanide compound on a polyalkyl acrylate rubber, and a polymethyl methacrylate resin (B) (see, for example, Patent Document 1) .
- thermoplastic resin of Patent Document 1 heat discoloration, which causes differences in the color of the resulting molded product, sometimes occurs due to differences in molding temperatures.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a thermoplastic resin composition having excellent resistance to heat discoloration (hereinafter referred to as "heat discoloration resistance”) and a molded article thereof. do.
- the present invention has the following aspects.
- the following graft copolymer (A), the following vinyl copolymer (B), and the following metal component (C) are included, and the content of the following metal component (C) is the thermoplastic resin composition A thermoplastic resin composition that is 60 ppm or more based on the total mass of the product.
- Graft polymer obtained by polymerizing B): Vinyl-based copolymer (C) obtained by polymerizing vinyl-based monomer mixture (m2) containing alkyl (meth)acrylate-based monomer: Alkali metal Metal component [2]
- thermoplastic resin composition according to [1] or [2], wherein the metal component (C) contains potassium.
- the content of the graft polymer (A) is 20 parts by mass to 80 parts by mass with respect to the total mass of the thermoplastic resin composition.
- the thermoplastic resin composition of. [5] The content of the graft copolymer (A) is preferably 20 parts by mass to 80 parts by mass, more preferably 30 parts by mass to 70 parts by mass, relative to the total mass of the thermoplastic resin composition.
- the content of the metal component (C) is 60 ppm or more, preferably 100 ppm or more, more preferably 100 ppm to 700 ppm, and further preferably 100 ppm to 400 ppm, relative to the total mass of the thermoplastic resin composition.
- the thermoplastic resin composition according to any one of [5].
- the polyorganosiloxane is preferably a vinyl-polymerizable functional group-containing polyorganosiloxane (vinyl-polymerizable functional group-containing polyorganosiloxane); has a vinyl-polymerizable functional group-containing siloxane unit and a dimethylsiloxane unit Polyorganosiloxane is more preferred; polyorganosiloxane having vinyl-polymerizable functional group-containing siloxane units and dimethylsiloxane units, wherein the vinyl-polymerizable functional group-containing siloxane units are bonded to the dimethylsiloxane units via siloxane bonds
- the thermoplastic resin composition according to any one of [1] to [6], which is more preferably organosiloxane.
- the rubber-like polymer (a) is preferably a composite rubber in which the polyorganosiloxane and the alkyl (meth)acrylate polymer are combined; , and a structure derived from an alkyl (meth)acrylate polymer as the branch polymer.
- the rubber-like polymer (a) according to any one of [1] to [8], wherein the side chains of the alkyl (meth)acrylate polymer are preferably crosslinked.
- a thermoplastic resin composition is preferably a composite rubber in which the polyorganosiloxane and the alkyl (meth)acrylate polymer are combined; , and a structure derived from an alkyl (meth)acrylate polymer as the branch polymer.
- the ratio of polyorganosiloxane to the total weight (100% by weight) of the polyorganosiloxane and the alkyl (meth)acrylate polymer is 3% by weight or more and 24% by weight. %, more preferably 5% by mass or more and 20% by mass or less, even more preferably 7% by mass or more and 15% by mass or less, any one of [1] to [9]
- the vinyl-based monomer mixture (m1) contains an aromatic vinyl compound, and the content of the aromatic vinyl compound is the total mass (100% by mass) of the vinyl-based monomer mixture (m1).
- the vinyl monomer mixture (m1) contains a vinyl cyanide compound, and the content of the vinyl cyanide compound is the total mass (100% by mass) of the vinyl monomer mixture (m1). On the other hand, 18% by mass to 35% by mass is preferable, 20% by mass to 27% by mass is more preferable, and 20% by mass to 25% by mass is even more preferable.
- the metal component (C) preferably contains an alkali metal: preferably contains at least one selected from the group consisting of sodium and potassium, any one of [1] to [12]
- the index ⁇ b* of thermal discoloration specified by the method described in Examples below is preferably 1.0 or less, more preferably 0.8 or less, and 0.7 or less.
- the thermoplastic resin composition contains a resin, and the resin consists essentially of a graft copolymer (A) and the following vinyl copolymer (B), [1] to [14] The thermoplastic resin composition according to any one of .
- thermoplastic resin composition contains a resin, and the resin consists of the graft copolymer (A) and the vinyl copolymer (B). 1.
- the amount of the emulsifier used is preferably 0.05 parts by mass to 5 parts by mass, more preferably 0.1 parts by mass to 3 parts by mass, and 0.3 parts by mass to 2 parts by mass with respect to 100 parts by mass of the siloxane mixture.
- the metal component (C) preferably contains an alkali metal: preferably contains at least one selected from the group consisting of sodium and potassium, any one of [17] to [19]
- a vinyl-based monomer mixture is A method for producing a graft copolymer (A), comprising a step of polymerizing (m1) to obtain a graft copolymer (A).
- thermoplastic resin composition having excellent resistance to heat discoloration and a molded article thereof.
- (Meth)acrylate means acrylate or methacrylate.
- a "molded article” means an article obtained by molding a thermoplastic resin composition.
- "-" indicating a numerical range means that the numerical values before and after it are included as lower and upper limits.
- thermoplastic resin composition A thermoplastic resin composition according to one embodiment of the present invention comprises a graft copolymer (A), a vinyl copolymer (B), and a metal component (C).
- the thermoplastic resin composition of the present embodiment may optionally contain other thermoplastic resins and various additives within a range that does not impair the effects of the present invention.
- the graft copolymer (A) comprises one or more vinyl monomers in the presence of 20% to 80% by mass of a rubber-like polymer (a) containing polyorganosiloxane and an alkyl (meth)acrylate polymer. It is obtained by polymerizing 80% by mass to 20% by mass of a vinyl monomer mixture (m1) containing.
- the vinyl-based copolymer (B) is obtained by polymerizing a vinyl-based monomer mixture (m2) containing an alkyl (meth)acrylate-based monomer.
- Metal component (C) is an alkali metal. Each component ((A) to (C), (m1), (m2), etc.) will be described below.
- Polyorganosiloxane The polyorganosiloxane is not particularly limited, but is preferably polyorganosiloxane containing a vinyl polymerizable functional group (vinyl polymerizable functional group-containing polyorganosiloxane), and vinyl polymerizable functional group-containing siloxane units and dimethylsiloxane units. is more preferred.
- vinyl-polymerizable functional groups examples include methacryloyloxyalkyl groups, acryloyloxyalkyl groups, vinyl groups, and vinyl-substituted phenyl groups.
- the number of carbon atoms in the alkyl group in the methacryloyloxyalkyl group and acryloyloxyalkyl group may be, for example, 1-20.
- the vinyl-polymerizable functional group-containing siloxane unit may have another organic group other than the vinyl-polymerizable functional group.
- Other organic groups include, for example, an alkyl group such as a methyl group, a phenyl group, and the like.
- the content of vinyl-polymerizable functional group-containing siloxane units is preferably 0.3 mol % to 3 mol % with respect to the total number of moles (100 mol %) of all units constituting the polyorganosiloxane.
- the content of the vinyl-polymerizable functional group-containing siloxane unit is within the above range, the polyorganosiloxane and the alkyl (meth)acrylate polymer are sufficiently combined, and the polyorganosiloxane bleeds out on the surface of the molded article. become difficult. Therefore, the color developability is further improved, and the impact resistance of the molded product is further improved.
- the content of silicon atoms having 3 or more siloxane bonds is based on the total number of moles (100 mol%) of all silicon atoms in the polyorganosiloxane. , 0 mol % to 1 mol %.
- polyorganosiloxane As a preferred embodiment of the polyorganosiloxane, 0.3 mol % to 3 mol % of vinyl polymerizable functional group-containing siloxane units and 99.7 mol % to 97 mol % of dimethylsiloxane units (however, vinyl polymerizable functional group-containing siloxane The total number of units and dimethylsiloxane units is 100 mol%. Organosiloxanes may be mentioned.
- the average particle size of the polyorganosiloxane is not particularly limited, but is preferably 400 nm or less, more preferably 150 nm or less, because the molded article has better color development.
- the lower limit is preferably 20 nm or more.
- the average particle size of the polyorganosiloxane is a value calculated from the particle size distribution obtained by measuring the mass-based particle size distribution using a dynamic light scattering particle size distribution analyzer (mass average particle diameter).
- Method for producing polyorganosiloxane Polyorganosiloxane can be obtained, for example, by polymerizing a siloxane mixture containing a dimethylsiloxane oligomer and vinyl-polymerizable functional group-containing siloxane.
- dimethylsiloxane oligomer a dimethylsiloxane-based cyclic body having a 3-membered ring or more is preferable, and a dimethylsiloxane-based cyclic body having a 3- to 7-membered ring is more preferable.
- Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like. These dimethylsiloxane oligomers may be used singly or in combination of two or more.
- the vinyl-polymerizable functional group-containing siloxane is not particularly limited as long as it contains a vinyl-polymerizable functional group and can bond with the dimethylsiloxane oligomer via a siloxane bond. Considering that, alkoxysilane compounds containing vinyl polymerizable functional groups are preferred.
- alkoxysilane compound containing a vinyl polymerizable functional group examples include ⁇ -methacryloyloxyethyldimethoxymethylsilane, ⁇ -methacryloyloxypropyldimethoxymethylsilane, ⁇ -methacryloyloxypropylmethoxydimethylsilane, ⁇ -methacryloyloxypropyltri Methacryloyloxysiloxanes such as methoxysilane, ⁇ -methacryloyloxypropylethoxydiethylsilane, ⁇ -methacryloyloxypropyldiethoxymethylsilane, ⁇ -methacryloyloxybutyldiethoxymethylsilane; tetramethyltetravinylcyclotetrasiloxane, p-vinylphenyldimethoxy vinyl siloxane such as methylsilane; and the like.
- Emulsion polymerization of siloxane mixtures is typically carried out using an emulsifier, water and an acid catalyst.
- An anionic emulsifier is preferred as the emulsifier.
- Specific examples include sodium alkylbenzenesulfonate, sodium laurylsulfonate, and sodium polyoxyethylene nonylphenyl ether sulfate.
- sulfonic acid-based emulsifiers such as sodium alkylbenzenesulfonate and sodium laurylsulfonate are preferred. These emulsifiers may be used singly or in combination of two or more.
- the amount of the emulsifier used is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the siloxane mixture.
- the amount of the emulsifier used is 0.05 parts by mass or more, the dispersed state of the siloxane mixture tends to be stable, and the emulsified state of fine particles can be easily maintained.
- the emulsifier is used in an amount of 5 parts by mass or less, it is possible to suppress the coloring of the molded product due to the emulsifier.
- Acid catalysts include organic acid catalysts such as sulfonic acids (e.g., aliphatic sulfonic acid, aliphatic-substituted benzenesulfonic acid, aliphatic-substituted naphthalenesulfonic acid, etc.); inorganic acids such as mineral acids (e.g., sulfuric acid, hydrochloric acid, nitric acid, etc.); A catalyst etc. are mentioned. These acid catalysts may be used alone or in combination of two or more.
- sulfonic acids e.g., aliphatic sulfonic acid, aliphatic-substituted benzenesulfonic acid, aliphatic-substituted naphthalenesulfonic acid, etc.
- inorganic acids such as mineral acids (e.g., sulfuric acid, hydrochloric acid, nitric acid, etc.); A catalyst etc. are mentioned. These acid catalysts may be used alone or
- aliphatic-substituted benzenesulfonic acid is preferred, and n-dodecylbenzenesulfonic acid is particularly preferred, in terms of its excellent stabilizing action for siloxane latex, which will be described later.
- n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used together, the influence of the color of the emulsifier used in the production of the polyorganosiloxane on the color of the molded product can be reduced.
- the amount of the acid catalyst to be added may be appropriately determined, but it is usually about 0.1 to 20 parts by mass with respect to 100 parts by mass of the siloxane mixture.
- the acid catalyst may be mixed with the siloxane mixture, the emulsifier, and water at the timing of mixing them, or the siloxane mixture, the emulsifier, and water are mixed and emulsified to form a latex (siloxane latex), and the siloxane latex is micronized. After that, it may be mixed with a finely divided siloxane latex. Since it is easy to control the particle size of the polyorganosiloxane to be obtained, it is preferable to mix the microparticulated siloxane latex and the acid catalyst after microparticulating the siloxane latex.
- the finely divided siloxane latex into the acid catalyst aqueous solution at a constant rate.
- the acid catalyst is mixed with the siloxane mixture, the emulsifier, and water, it is preferable to micronize them after mixing them.
- Siloxane latex can be microparticulated by using, for example, a homomixer or a homogenizer.
- the homomixer atomizes by shearing force due to high-speed rotation.
- the homogenizer atomizes the powder with the ejection force of the high-pressure generator.
- Methods of mixing a siloxane mixture, an emulsifier, water and an acid catalyst, and methods of mixing a finely divided siloxane latex and an acid catalyst include, for example, mixing with high-speed stirring and mixing with a high-pressure emulsifying device such as a homogenizer. .
- the method using a homogenizer is preferable because the distribution of the particle size of the polyorganosiloxane can be narrowed.
- the polymerization temperature is preferably 50°C or higher, more preferably 80°C or higher.
- the temperature of the acid catalyst aqueous solution is preferably 50° C. or higher, more preferably 80° C. or higher.
- the polymerization time is preferably 2 hours or longer, more preferably 5 hours or longer, when the acid catalyst is mixed at the same timing as the siloxane mixture, emulsifier and water are mixed.
- the finely divided siloxane latex and the acid catalyst it is preferable to drop the finely divided siloxane latex into the acid catalyst aqueous solution and then hold the mixture for about one hour.
- the average particle size of the polyorganosiloxane can be controlled by adjusting the composition of the siloxane mixture, the amount of acid catalyst used (content of the acid catalyst in the acid catalyst aqueous solution), the polymerization temperature, and the like. For example, the smaller the amount of acid catalyst used, the larger the average particle size, and the higher the polymerization temperature, the smaller the average particle size.
- alkyl (meth)acrylate polymer An alkyl (meth)acrylate polymer is a polymer having an alkyl (meth)acrylate unit.
- the alkyl (meth)acrylate polymer may further have monomer (other monomer) units other than the alkyl (meth)acrylate unit.
- Alkyl (meth)acrylates include alkyl acrylate esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate; hexyl methacrylate and 2-ethylhexyl methacrylate; , and methacrylic acid alkyl esters such as n-lauryl methacrylate. These alkyl (meth)acrylates may be used singly or in combination of two or more. Among them, n-butyl acrylate is preferred because it further improves the impact resistance of the molded article.
- monomers are not particularly limited as long as they are copolymerizable with alkyl (meth)acrylates, and aromatic vinyl compounds (eg, styrene, ⁇ -methylstyrene, p-methylstyrene, etc.), vinyl cyanide compounds. (eg, acrylonitrile, methacrylonitrile, etc.) and the like. These other monomers may be used individually by 1 type, and may be used in combination of 2 or more type.
- aromatic vinyl compounds eg, styrene, ⁇ -methylstyrene, p-methylstyrene, etc.
- vinyl cyanide compounds eg, acrylonitrile, methacrylonitrile, etc.
- the content of alkyl (meth)acrylate units in the alkyl (meth)acrylate polymer is preferably 80% by mass to 100% by mass with respect to the total mass of all monomer units in the alkyl (meth)acrylate polymer. , more preferably 90% by mass to 100% by mass.
- Alkyl (meth)acrylate polymers are obtained by polymerizing monomer components containing one or more alkyl (meth)acrylates. This monomer component may contain other monomers.
- the method for polymerizing the monomer components is not particularly limited, and can be carried out according to known methods.
- the rubber-like polymer (a) is a composite rubber in which a polyorganosiloxane and an alkyl (meth)acrylate polymer are combined.
- composite rubber may contain one or more polymers, or may be a graft polymer having a trunk polymer and a branch polymer.
- the ratio of the polyorganosiloxane to the total weight (100% by weight) of the polyorganosiloxane and the alkyl (meth)acrylate polymer is not particularly limited, but is 3% by weight or more and less than 24% by weight. is preferably If the ratio of the polyorganosiloxane in the rubber-like polymer (a) is within the above range, the resulting molded article will have better impact resistance and color development.
- the rubber-like polymer (a) is in the form of granules and is also present in the form of granules in the thermoplastic resin composition.
- the volume average particle size of the rubber-like polymer (a) is not particularly limited, it is preferably 50 nm or more and less than 120 nm. If the volume-average particle size of the rubber-like polymer (a) is within the above range, the resulting molded article will have better impact resistance and color development.
- the volume-average particle size of the rubber-like polymer (a) is calculated from the particle size distribution obtained by measuring the volume-based particle size distribution using a dynamic light scattering particle size distribution analyzer. value.
- the ratio of particles having a particle diameter of more than 200 nm to all particles in the rubber-like polymer (a) is preferably less than 5% by volume. That is, the rubber-like polymer (a) preferably has a particle size distribution (volume basis) in which particles having a particle size of more than 200 nm account for less than 5% by volume of all particles. When the proportion of particles having a particle diameter of more than 200 nm is less than 5% by volume, the molded article has more excellent color developability.
- the ratio of particles having a particle size of more than 200 nm is obtained by measuring the volume-based particle size distribution of the rubber-like polymer (a) using a dynamic light scattering particle size distribution analyzer, and from the obtained particle size distribution. It is a calculated value.
- Method for producing rubber-like polymer (a) is not particularly limited, but a method of heteroaggregating or co-expanding multiple latexes each containing polyorganosiloxane and an alkyl (meth)acrylate polymer; Examples include a method of polymerizing a monomer component forming the other polymer in the presence of a latex containing either one of the alkyl (meth)acrylate polymers to form a complex.
- volume average particle size of the rubber-like polymer (a) can be easily adjusted to be within the range described above, in the presence of latex-like polyorganosiloxane, a single compound containing one or more alkyl (meth)acrylates
- a method comprising a step of radically polymerizing the monomer components to obtain a copolymer latex (radical polymerization step) is preferred.
- the radical polymerization step is a step of radically polymerizing a monomer component containing one or more alkyl (meth)acrylates in the presence of latex-like polyorganosiloxane.
- the monomer component containing one or more alkyl (meth)acrylates may be added all at once, continuously, or intermittently to the latex-like polyorganosiloxane.
- Polymerization conditions may be, for example, 30° C. to 95° C. for 1 hour to 10 hours.
- a graft crossing agent or a cross-linking agent may be used as necessary.
- graft crossing agents or crosslinking agents include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, ethylene glycol diester dimethacrylate, propylene glycol diester dimethacrylate, 1,3-butylene glycol diester dimethacrylate, Dimethacrylic acid 1,4-butylene glycol diester and the like are included. These may be used individually by 1 type, and may be used in combination of 2 or more type.
- a radical polymerization initiator and an emulsifier are usually used for radical polymerization.
- radical polymerization initiators include peroxides, azo initiators, redox initiators in which an oxidizing agent and a reducing agent are combined, and the like.
- redox initiators are preferred, and sulfoxylate initiators obtained by combining ferrous sulfate, disodium ethylenediaminetetraacetic acid, sodium formaldehyde sulfoxylate, and hydroperoxide are particularly preferred.
- carboxylates such as sodium sarcosinate, fatty acid potassium, fatty acid sodium, dipotassium alkenyl succinate, and rosin acid soap are used because they are excellent in the stability of the latex during radical polymerization and can increase the polymerization rate. is preferred.
- dipotassium alkenyl succinate is preferable because it can suppress gas generation when the obtained graft copolymer (B) and the thermoplastic resin composition containing the same can be molded at high temperature.
- dipotassium alkenyl succinate examples include dipotassium octadecenyl succinate, dipotassium heptadecenyl succinate, and dipotassium hexadecenyl succinate. These emulsifiers may be used singly or in combination of two or more.
- Vinyl monomer mixture (m1) The vinyl-based monomer mixture (m1) may contain one or more vinyl-based monomers, but is preferably a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound. In addition, other monomers copolymerizable with these may be included as long as the effects of the present invention are not impaired.
- aromatic vinyl compounds examples include styrene, ⁇ -methylstyrene, o-, m- or p-methylstyrene, vinylxylene, pt-butylstyrene, ethylstyrene and the like. Styrene and ⁇ -methylstyrene are preferred from the viewpoints of the fluidity of the thermoplastic resin composition, the color developability of the molded article, and the impact resistance.
- An aromatic vinyl compound may be used individually by 1 type, and may be used in combination of 2 or more type.
- vinyl cyanide compounds examples include acrylonitrile and methacrylonitrile.
- a vinyl cyanide compound may be used individually by 1 type, and may be used in combination of 2 or more type.
- Other monomers include, for example, acrylates (methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, etc.), methacrylates (methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid butyl, etc.), maleimide monomers (N-cyclohexylmaleimide, N-phenylmaleimide, etc.), and the like. Other monomers may be used singly or in combination of two or more.
- the aromatic vinyl compound is preferably 65% by mass to 82% by mass, more preferably 73% by mass to 80% by mass, and even more preferably 75% by mass to 80% by mass.
- the content of the aromatic vinyl compound is within the above range, the impact resistance and color developability of the molded product are further improved.
- the content of the vinyl cyanide compound is preferably 18% by mass to 35% by mass, more preferably 20% by mass to 27% by mass, relative to the total mass (100% by mass) of the vinyl monomer mixture (m1). , 20% by mass to 25% by mass is more preferable.
- the content of the vinyl cyanide compound is within the above range, the impact resistance and color developability of the molded article are further improved.
- the graft copolymer (A) is a copolymer obtained by polymerizing the vinyl-based monomer mixture (m1) in the presence of the rubber-like polymer (a).
- the graft copolymer (A) it is difficult to specify how the vinyl-based monomer mixture (m1) is polymerized in the presence of the rubber-like polymer (a). That is, there are circumstances (impossible/impractical circumstances) where it is impossible or almost impractical to directly specify the graft copolymer (A) by its structure or properties. Therefore, it is more appropriate to define the graft copolymer (A) as "obtained by polymerizing the vinyl-based monomer mixture (m1) in the presence of the rubber-like polymer (a)".
- the mass ratio of the rubber-like polymer (a) to the vinyl-based monomer mixture (m1) containing one or more vinyl-based monomers is 20% by mass to 80% by mass of the rubber-like polymer (a), 1 80% by mass to 20% by mass of a vinyl monomer mixture (m1) of at least one species, 30% to 70% by mass of a rubber-like polymer (a), and one or more vinyl monomer mixtures (m1) is preferably 70% by mass to 30% by mass (provided that the total of the rubber-like polymer (a) and the one or more vinyl monomer mixture (m1) is 100% by mass).
- the rubber-like polymer (a) is less than 20% by mass, the impact resistance of the molded article is poor, and if it exceeds 80% by mass, the molded article is inferior in color developability and the fluidity of the thermoplastic resin composition is poor. tend to decline.
- the graft copolymer (A) is obtained by polymerizing the vinyl-based monomer mixture (m1) in the presence of the rubber-like polymer (a).
- the polymerization method is not particularly limited, but emulsion polymerization is preferred because it can be controlled so that the reaction proceeds stably.
- the process is performed in two or more stages, it is also possible to change the types and composition ratios of the monomers constituting the vinyl-based monomer mixture (m1) in each stage.
- a radical polymerization initiator and an emulsifier are usually used for emulsion polymerization.
- these radical polymerization initiators and emulsifiers include the radical polymerization initiators and emulsifiers exemplified above in the description of the method for producing the rubber-like polymer (a).
- various known chain transfer agents may be added in order to control the molecular weight and graft ratio of the resulting graft copolymer (A).
- Polymerization conditions may be, for example, 30° C. to 95° C. for 1 hour to 10 hours.
- the graft copolymer (A) obtained by emulsion polymerization is usually in the form of latex.
- a method for recovering the graft copolymer (A) from the latex of the graft copolymer (A) for example, the latex of the graft copolymer (A) is put into hot water in which a coagulant is dissolved. a wet method in which a latex of the graft copolymer (A) is sprayed in a heated atmosphere to recover the graft copolymer (A) semi-directly; and the like.
- the coagulant used in the wet method includes inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid; metal salts such as calcium chloride, calcium acetate, and aluminum sulfate, and is selected according to the emulsifier used in the polymerization.
- inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid
- metal salts such as calcium chloride, calcium acetate, and aluminum sulfate
- emulsifier used in the polymerization for example, when only carboxylic acid soaps such as fatty acid soaps and rosin acid soaps are used as emulsifiers, one or more of the coagulants described above can be used.
- an emulsifier such as sodium alkylbenzenesulfonate that exhibits stable emulsifying power even in an acidic region is used as the emulsifier, a metal salt is suitable as the coagulant.
- a wet method yields a slurry-like graft copolymer (A).
- a method for obtaining the dry graft copolymer (A) from the slurry-like graft copolymer (A) first, the remaining emulsifier residue is eluted in water and washed, and then the slurry is subjected to centrifugal or press dehydration.
- the washing conditions are not particularly limited, it is preferable to wash under conditions such that the amount of emulsifier residue contained in 100% by mass of the graft copolymer (A) after drying is in the range of 0.3% by mass to 2% by mass. .
- the emulsifier residue in the graft copolymer (A) is 0.3% by mass or more, the flowability of the obtained graft copolymer (A) and the thermoplastic resin composition containing the same tends to be further improved.
- the emulsifier residue in the graft copolymer (A) is 2% by mass or less, gas generation can be suppressed when the thermoplastic resin composition is molded at high temperature.
- the emulsifier residue amount can be adjusted by, for example, washing time.
- the drying temperature may be, for example, 50°C to 90°C.
- the volume-average particle size and the volume-based particle size distribution of the rubber-like polymer (a) in the obtained graft copolymer (A) were compared with those of the rubber-like polymer ( It is the same as the volume-average particle size and volume-based particle size distribution of the rubber-like polymer (a) in the latex of a).
- the graft copolymer (A) discharged from the dehydrator or extruder may be sent directly to an extruder or molding machine for producing a resin composition to form a molded article.
- the vinyl-based monomer mixture (m2) is a monomer mixture containing at least an alkyl (meth)acrylate-based monomer.
- the vinyl-based monomer mixture (m2) may contain, in addition to the alkyl (meth)acrylate-based monomers, other monomers copolymerizable therewith within a range that does not impair the effects of the present invention.
- alkyl (meth)acrylate monomers examples include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-methacrylate, Butyl, amyl methacrylate, isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, methyl acrylate, ethyl acrylate, acrylic Examples include propyl acid and butyl acrylate.
- alkyl(meth)acrylate-based monomer an alkyl(meth)acrylate-based monomer having a hydrocarbon group of 1 to 8 carbon atoms is preferred. At least one of methyl methacrylate and ethyl methacrylate is preferred because the heat resistance and impact resistance of the molded article are further improved.
- Alkyl (meth)acrylate monomers may be used alone or in combination of two or more.
- Examples of other monomers include the aromatic vinyl compounds and vinyl cyanide compounds exemplified above in the description of the vinyl-based monomer mixture (m1). Other monomers may be used singly or in combination of two or more.
- the ratio of the alkyl (meth)acrylate monomer contained in the vinyl monomer mixture (m2) is not particularly limited, the total mass (100% by mass) of the vinyl monomer mixture (m2) is
- the (meth)acrylate monomer content is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.
- the content of the alkyl (meth)acrylate monomer is within the above range, the impact resistance and color developability of the molded article are further improved.
- Vinyl-based copolymer (B) The vinyl copolymer (B) is a polymer obtained by polymerizing the vinyl monomer mixture (m2).
- the vinyl-based copolymer (B) is a polymer of the vinyl-based monomer mixture (m2).
- the vinyl copolymer (B) contains at least units derived from alkyl (meth)acrylate monomers.
- the ratio of units derived from the alkyl (meth)acrylate monomer contained in the vinyl copolymer (B) is not particularly limited, the total mass (100% by mass) of the vinyl monomer mixture (m2) , preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, derived from the alkyl (meth)acrylate monomer.
- the content of the units derived from the alkyl (meth)acrylate monomer is within the above range, the impact resistance and color developability of the molded article are further improved.
- the weight average molecular weight (Mw) of the vinyl copolymer (B) may be, for example, 5,000 to 500,000.
- the mass average molecular weight of the vinyl copolymer (B) is a value converted to standard polystyrene measured using gel permeation chromatography (GPC).
- the vinyl copolymer (B) may be used alone or in combination of two or more.
- a vinyl-based copolymer (B) is obtained by polymerizing a vinyl-based monomer mixture (m2).
- a method for polymerizing the vinyl-based monomer mixture (m2) is not particularly limited. Examples of the polymerization method include known polymerization methods (emulsion polymerization method, suspension polymerization method, solution polymerization method, etc.).
- the obtained vinyl-based copolymer (B) is typically It is a random copolymer in which units are randomly arranged.
- a method for producing the vinyl copolymer (B) by emulsion polymerization for example, a vinyl monomer mixture (m2), an emulsifier, a polymerization initiator and a chain transfer agent are charged into a reactor and heated.
- a method of polymerizing to obtain an aqueous dispersion containing the vinyl copolymer (B) and recovering the vinyl copolymer (B) from the aqueous dispersion by a precipitation method can be mentioned.
- Polymerization conditions for the emulsion polymerization may be, for example, 30° C. to 95° C. for 1 hour to 10 hours.
- emulsifier examples include common emulsifiers for emulsion polymerization (potassium rosinate, sodium alkylbenzenesulfonate, etc.).
- Polymerization initiators include organic and inorganic oxide-based initiators.
- Chain transfer agents include mercaptans, ⁇ -methylstyrene dimers, terpenes and the like.
- precipitation method the same method as used for recovering the graft copolymer (A) from the latex of the graft copolymer (A) can be employed.
- a method for producing the vinyl-based copolymer (B) by suspension polymerization for example, a vinyl-based monomer mixture (m2), a suspension agent, a suspension aid, a polymerization initiator, and a chain transfer agent are placed in a reactor. agents are charged, heated and polymerized, and the slurry is dehydrated and dried to recover the vinyl copolymer (B).
- the polymerization conditions for suspension polymerization may be, for example, 60° C. to 150° C. for 1 hour to 20 hours.
- Suspending agents include tricalcium phosphite, polyvinyl alcohol and the like.
- Suspension aids include sodium alkylbenzenesulfonate and the like.
- Polymerization initiators include organic peroxides and the like. Chain transfer agents include mercaptans, ⁇ -methylstyrene dimers, terpenes and the like.
- Metal component (C) is an alkali metal. Among alkali metals, sodium (Na) and potassium (K) are preferred. More preferably, the metal component (C) contains potassium.
- the metal component (C) may be derived from a compound containing a metal component used in the production of the graft copolymer (A) or the vinyl-based copolymer (B). It may be blended as a compound containing a metal component during production of the composition.
- thermoplastic resins include, for example, polycarbonate, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyvinyl chloride, polystyrene, polyacetal, modified polyphenylene ether (modified PPE), ethylene-vinyl acetate copolymer, poly Arylate, liquid crystalline polyester, polyethylene, polypropylene, fluororesin, polyamide (nylon) and the like.
- additives include antioxidants, lubricants, processing aids, pigments, dyes, fillers, silicone oils, paraffin oils, and the like.
- the content of the graft copolymer (A) in the thermoplastic resin composition is preferably 20 parts by mass to 80 parts by mass with respect to the total mass (100 parts by mass) of the thermoplastic resin composition, and 30 parts by mass. It is more preferably from 40 parts by mass to 70 parts by mass, and even more preferably from 40 parts by mass to 60 parts by mass. If the content of the graft copolymer (A) is at least the above lower limit, the mechanical properties of the molded article will be good. If the content of the graft copolymer (A) is equal to or less than the above upper limit, the molded article will have good color developability and molded appearance.
- the content of the metal component (C) is 60 ppm or more, preferably 100 ppm or more, more preferably 100 ppm to 700 ppm, and further 100 ppm to 400 ppm, relative to the total mass of the thermoplastic resin composition. preferable. If the content of the metal component (C) is less than 60 ppm, the effect of suppressing thermal discoloration cannot be obtained. If the content of the metal component (C) is 100 ppm or more, the effect of suppressing thermal discoloration is more excellent, and if it is less than 700 ppm, the appearance of the molded product is good. In this specification, the content of the metal component (C) is a value measured by the method described in Examples below.
- the content of the metal component (C) is determined by quantifying the metal component using a fluorescent X-ray device (“MagiX PRO” manufactured by Spectris Co., Ltd.), and determining the metal component contained in the thermoplastic resin composition ( It is a value obtained by measuring the content of C).
- thermoplastic resin composition The method for producing the thermoplastic resin composition is not particularly limited.
- the graft copolymer (A), the vinyl copolymer (B), the metal component (C), and, if necessary, other components (other thermoplastic resins, additives) are mixed in a V-type blender. or a Henschel mixer, etc., and the resulting mixture is melt-kneaded using a melt-kneader such as a screw extruder, a Banbury mixer, a pressure kneader, or a mixing roll to form a thermoplastic resin composition. manufactured.
- the melt-kneaded product may be pelletized using a pelletizer or the like, if necessary.
- the graft copolymer (A), the vinyl copolymer (B), and the metal component (C) are included, and the metal component (C ) is 60 ppm or more based on the total mass of the thermoplastic resin composition, and the graft copolymer (A) is a rubber-like polymer (a ) Graft polymer obtained by polymerizing 80% to 20% by mass of a vinyl monomer mixture containing one or more vinyl monomers in the presence of 20% to 80% by mass (m1), vinyl A vinyl-based copolymer in which the copolymer (B) is obtained by polymerizing a vinyl-based monomer mixture (m2) containing an alkyl (meth)acrylate-based monomer, and a metal in which the metal component (C) is an alkali metal Since it is a thermoplastic resin composition, it is possible to obtain a molded article having excellent resistance to heat discoloration.
- a molded article according to one embodiment of the present invention is composed of the thermoplastic resin composition of the present embodiment.
- the molded article of the present embodiment is obtained by molding the thermoplastic resin composition of the present embodiment by a known molding method.
- molding methods include injection molding, press molding, extrusion molding, vacuum molding, and blow molding.
- Applications of the molded product include vehicle interior and exterior parts, office equipment, home appliances, building materials, etc. Vehicle exterior parts are preferred.
- thermoplastic resin composition of the present embodiment is used in the molded article of the present embodiment described above, it is excellent in resistance to heat discoloration.
- Pellets of the thermoplastic resin composition are molded using a 30-ton injection molding machine ("NEX30W-3E" manufactured by Nissei Plastic Industry Co., Ltd.) under the conditions of cylinder set temperatures of 230 ° C. and 280 ° C. and mold temperature of 60 ° C., A molded article having a length of 80 mm, a width of 55 mm and a thickness of 2 mm was obtained. For both the obtained 230 ° C. and 280 ° C.
- b * showing the intensity of color from blue to yellow using a UV-visible near-red spectrophotometer (manufactured by JASCO Corporation "V-670") was measured by the SCE method, and the thermal discoloration index ⁇ b* was calculated from the following formula (1).
- ⁇ b* b* (280°C) -b* (230°C) (1)
- b* (230°C) is the b* value of the 230°C molded product
- b* (280°C) is the b* value of the 280°C molded product.
- the metal component was quantified using a fluorescent X-ray device (“MagiX PRO” manufactured by Spectris Co., Ltd.), and sodium (Na) and potassium contained in the thermoplastic resin composition The concentration of (K) was measured.
- ⁇ Polyorganosiloxane (s)> (Production of polyorganosiloxane (s-1)) 98 parts of octamethylcyclotetrasiloxane and 2 parts of ⁇ -methacryloyloxypropyldimethoxymethylsilane were mixed to obtain 100 parts of a siloxane mixture. To this, an aqueous solution consisting of 0.67 parts of sodium dodecylbenzenesulfonate and 300 parts of ion - exchanged water was added. A stable premixed organosiloxane latex was obtained.
- the reactant was then neutralized to pH 7.0 with a 10% aqueous sodium hydroxide solution to obtain a latex of polyorganosiloxane (s-1).
- a portion of the polyorganosiloxane (s-1) latex was dried at 180° C. for 30 minutes to obtain a solid content of 18.2%.
- the mass-based average particle diameter dispersed in the latex was 30 nm.
- ⁇ Graft copolymer (A)> (Production of graft copolymer (A-1)) 6.0 parts of polyorganosiloxane (s-1) latex in terms of solid content and 0.5 parts of sodium alkyldiphenyl ether disulfonate were placed in a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirring device. was charged, and 190 parts of ion-exchanged water was added and mixed. Thereafter, 44.0 parts of n-butyl acrylate, 0.2 parts of allyl methacrylate, and 1,3-butylene dimethacrylate were added as monomers constituting the alkyl (meth)acrylate rubbery polymer (a-1).
- a mixture of 0.06 part glycol diester and 0.1 part t-butyl hydroperoxide was added.
- the atmosphere was replaced with nitrogen by passing a stream of nitrogen through the reactor, and the temperature was raised to 60°C.
- 0.0001 part of ferrous sulfate, 0.0003 part of ethylenediaminetetraacetic acid disodium salt and 0.2 part of Rongalit were dissolved in 10 parts of ion-exchanged water.
- An aqueous solution was added to initiate radical polymerization.
- the liquid temperature rose to 78°C due to the polymerization of the alkyl (meth)acrylate component.
- Vinyl-based copolymer (B) > (Vinyl-based copolymer (B-1)) Polymethyl methacrylate “Acrypet VH5” (manufactured by Mitsubishi Chemical Corporation, 98 parts of methyl methacrylate, 2 parts of methacrylic acid, and a weight average molecular weight (Mw) of 7 ⁇ 10 3 ) as a vinyl copolymer (B-1) used.
- Metal component (C) As a compound containing potassium, an aqueous solution of dipotassium alkenylsuccinate (trade name: Latemul ASK, manufactured by Kao Corporation) was used.
- Metal component (C)> Metal component (C-2)
- Anhydrous sodium pyrophosphate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used as the sodium-containing compound.
- Method (C)> Metal component (C-3)
- Sodium acetate trihydrate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used as a sodium-containing compound.
- Example 1 45 parts of the graft copolymer (A-1), 55 parts of the vinyl copolymer (B-1), 0.4 parts of the metal component (C-1), 0.5 parts of ethylenebisstearylamide, 0.3 parts of ADEKA STAB LA-36 (manufactured by ADEKA Corporation), 0.3 parts of ADEKA STAB LA-63P (manufactured by ADEKA Corporation), and 5 parts of titanium oxide as a coloring agent were mixed using a Henschel mixer.
- pellets are obtained using a pelletizer (“SH type pelletizer” manufactured by Soken Co., Ltd.).
- a thermoplastic resin composition was obtained.
- various molded articles were produced, and thermal discoloration and molded appearance were evaluated.
- the amount of the metal component (C) and the amount of the additive and colorant are percentages relative to the total mass (100 parts) of the graft copolymer (A) and the vinyl copolymer (B). Tables 1 and 2 show the results.
- the compounding amount of the metal component (C) represents the compounding amount of the compound containing the metal component (C).
- thermoplastic resin composition was prepared in the same manner as in Example 1 except for changing the formulation shown in Tables 1 and 2, various molded articles were produced, and thermal discoloration and molded appearance were evaluated. Tables 1 and 2 show the results.
- thermoplastic resin compositions of Examples 1 to 9 are excellent in resistance to heat discoloration. Therefore, it can be seen that a molded article having excellent resistance to heat discoloration can be obtained by using the thermoplastic resin composition of the present invention.
- molded articles obtained from the thermoplastic resin compositions of Examples 1 to 3, 5 and 9 are also excellent in molding appearance.
- the molded articles obtained from the thermoplastic resin compositions of Comparative Examples 1 and 2 are inferior in resistance to heat discoloration.
- thermoplastic resin composition of the present invention are useful as vehicle interior and exterior parts, office equipment, home appliances, building materials, etc., and are particularly useful as vehicle exterior parts.
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Abstract
Description
本願は、2021年3月31日に、日本に出願された特願2021-059491号に基づき優先権を主張し、その内容をここに援用する。
ポリアルキルアクリレート系ゴムに芳香族アルケニル化合物およびシアン化ビニル化合物を重合したグラフト共重合体(A1)と、ポリメチルメタクリレート樹脂(B)とを含む熱可塑性樹脂組成物(例えば、特許文献1参照)。
[1]下記グラフト共重合体(A)と、下記ビニル系共重合体(B)と、下記金属成分(C)と、を含み、下記金属成分(C)の含有量が、熱可塑性樹脂組成物の総質量に対し、60ppm以上である、熱可塑性樹脂組成物。
(A):ポリオルガノシロキサンとアルキル(メタ)アクリレート系重合体とから得られるゴム状重合体(a)20質量%~80質量%の存在下に、1種以上のビニル系単量体を含むビニル系単量体混合物(m1)80質量%~20質量%(ただし、前記ゴム状重合体(a)と前記ビニル系単量体混合物(m1)との合計を100質量%とする。)を重合してなるグラフト重合体
(B):アルキル(メタ)アクリレート系単量体を含有するビニル系単量体混合物(m2)を重合してなるビニル系共重合体
(C):アルカリ金属である金属成分
[2]前記金属成分(C)の含有量が、熱可塑性樹脂組成物の総質量に対し、100ppm~400ppmである、[1]に記載の熱可塑性樹脂組成物。
[3]前記金属成分(C)がカリウムを含む、[1]または[2]に記載の熱可塑性樹脂組成物。
[4]前記グラフト重合体(A)の含有量が、熱可塑性樹脂組成物の総質量に対し、20質量部~80質量部である、[1]~[3]のいずれか1項に記載の熱可塑性樹脂組成物。
[5]前記グラフト共重合体(A)の含有量が、熱可塑性樹脂組成物の総質量に対し、20質量部~80質量部であることが好ましく、30質量部~70質量部であることがより好ましく、40質量部~60質量部であることがさらに好ましい、[1]~[4]のいずれか1項に記載の熱可塑性樹脂組成物。
[6]前記金属成分(C)の含有量は、熱可塑性樹脂組成物の総質量に対し、60ppm以上であり、100ppm以上が好ましく、100ppm~700ppmがより好ましく、100ppm~400ppmがさらに好ましい、[1]~[5]のいずれか1項に記載の熱可塑性樹脂組成物。
[7]前記ポリオルガノシロキサンが、ビニル重合性官能基を含有するポリオルガノシロキサン(ビニル重合性官能基含有ポリオルガノシロキサン)が好ましく;ビニル重合性官能基含有シロキサン単位と、ジメチルシロキサン単位とを有するポリオルガノシロキサンがより好ましく;ビニル重合性官能基含有シロキサン単位と、ジメチルシロキサン単位とを有し、前記ビニル重合性官能基含有シロキサン単位が前記ジメチルシロキサン単位とシロキサン結合を介して結合しているポリオルガノシロキサンがさらに好ましい、[1]~[6]のいずれか1項に記載の熱可塑性樹脂組成物。
[8]前記ゴム状重合体(a)は、前記ポリオルガノシロキサンと前記アルキル(メタ)アクリレート系重合体とが複合した複合ゴムであることが好ましく;幹ポリマーとしてのポリオルガノシロキサン由来の構造と、枝ポリマーとしてのアルキル(メタ)アクリレート系重合体由来の構造とを有するグラフト重合体であることがより好ましい、[1]~[6]のいずれか1項に記載の熱可塑性樹脂組成物。
[9]前記ゴム状重合体(a)において、前記アルキル(メタ)アクリレート系重合体の側鎖間で架橋していることが好ましい、[1]~[8]のいずれか1項に記載の熱可塑性樹脂組成物。
[10]前記ゴム状重合体(a)において、前記ポリオルガノシロキサンと前記アルキル(メタ)アクリレート系重合体との合計質量(100質量%)に対するポリオルガノシロキサンの割合が、3質量%以上24質量%未満であることが好ましく、5質量%以上20質量%以下であることがより好ましく、7質量%以上15質量%以下であることがさらに好ましい、[1]~[9]のいずれか1項に記載の熱可塑性樹脂組成物。
[11]前記ビニル系単量体混合物(m1)が芳香族ビニル化合物を含み、前記芳香族ビニル化合物の含有率が、前記ビニル系単量体混合物(m1)の総質量(100質量%)に対し、65質量%~82質量%が好ましく、73質量%~80質量%がより好ましく、75質量%~80質量%がさらに好ましい、[1]~[10]のいずれか一項に記載の熱可塑性樹脂組成物。
[12]前記ビニル系単量体混合物(m1)がシアン化ビニル化合物を含み、前記シアン化ビニル化合物の含有率が、前記ビニル系単量体混合物(m1)の総質量(100質量%)に対し、18質量%~35質量%が好ましく、20質量%~27質量%がより好ましく、20質量%~25質量%がさらに好ましい、[1]~[11]のいずれか一項に記載の熱可塑性樹脂組成物。
[13]前記金属成分(C)が、アルカリ金属を含むことが好ましく:ナトリウム、及びカリウムからなる群から選択される少なくとも1種を含むことが好ましい、[1]~[12]のいずれか一項に記載の熱可塑性樹脂組成物。
[14]後述の実施例に記載の方法で特定される熱変色の指標Δb*が、1.0以下であることが好ましく、0.8以下であることがより好ましく、0.7以下であることがさらに好ましい、[1]~[13]のいずれか一項に記載の熱可塑性樹脂組成物。
[15]前記熱可塑性樹脂組成物が、樹脂を含み、前記樹脂が実質的にグラフト共重合体(A)と、下記ビニル系共重合体(B)とからなる、[1]~[14]のいずれか一項に記載の熱可塑性樹脂組成物。
[16]前記熱可塑性樹脂組成物が、樹脂を含み、前記樹脂がグラフト共重合体(A)と、前記ビニル系共重合体(B)とからなる、[1]~[14]のいずれか一項に記載の熱可塑性樹脂組成物。
[16][1]~[16]のいずれか1項に記載の熱可塑性樹脂組成物から形成される、成形品。
[17]ラテックス状のポリオルガノシロキサンの存在下で、1種以上のアルキル(メタ)アクリレートを含む単量体成分をラジカル重合させて共重合体ラテックスを得る工程(ラジカル重合工程)を有する、ゴム状重合体(a)の製造方法。
[18]ジメチルシロキサンオリゴマーとビニル重合性官能基含有シロキサンとを含むシロキサン混合物を、金属成分(C)を含む乳化剤存在下で重合して前記ラテックス状のポリオルガノシロキサンを得る工程を有する、[17]に記載のゴム状重合体(a)の製造方法。
[19]前記乳化剤の使用量が、シロキサン混合物100質量部に対して0.05質量部~5質量部が好ましく、0.1質量部~3質量部がより好ましく、0.3質量部~2.0質量部がさらに好ましい、[18]に記載のゴム状重合体(a)の製造方法。
[20]前記金属成分(C)が、アルカリ金属を含むことが好ましく:ナトリウム、及びカリウムからなる群から選択される少なくとも1種を含むことが好ましい、[17]~[19]のいずれか一項に記載のゴム状重合体(a)の製造方法。
[21][17]~[20]のいずれか一項に記載のゴム状重合体(a)の製造方法で得られたゴム状重合体(a)の存在下に、ビニル系単量体混合物(m1)を重合してグラフト共重合体(A)を得る工程を有する、グラフト共重合体(A)の製造方法。
[22][21]に記載のグラフト共重合体(A)の製造方法で得られたグラフト共重合体(A)と、ビニル系共重合体(B)と、金属成分(C)とを混合して熱可塑性樹脂組成物を得る工程を含む、熱可塑性樹脂組成物の製造方法。
「(メタ)アクリレート」とは、アクリレートまたはメタクリレートを意味する。
「成形品」とは、熱可塑性樹脂組成物を成形してなるものを意味する。
数値範囲を示す「~」は、その前後に記載された数値を下限値および上限値として含むことを意味する。
本発明の一実施形態に係る熱可塑性樹脂組成物は、グラフト共重合体(A)と、ビニル系共重合体(B)と、金属成分(C)と、を含む。本実施形態の熱可塑性樹脂組成物は、必要に応じて、本発明の効果を損なわない範囲内で、その他の熱可塑性樹脂、各種の添加剤を含んでいてもよい。
ビニル系共重合体(B)は、アルキル(メタ)アクリレート系単量体を含有するビニル系単量体混合物(m2)を重合して得られたものである。
金属成分(C)は、アルカリ金属である。
以下、各成分((A)~(C)、(m1)、(m2)等)について説明する。
ポリオルガノシロキサンとしては、特に制限されないが、ビニル重合性官能基を含有するポリオルガノシロキサン(ビニル重合性官能基含有ポリオルガノシロキサン)が好ましく、ビニル重合性官能基含有シロキサン単位と、ジメチルシロキサン単位とを有するポリオルガノシロキサンがより好ましい。
ビニル重合性官能基含有シロキサン単位は、ビニル重合性官能基以外の他の有機基を有していてもよい。他の有機基としては、例えばメチル基等のアルキル基、フェニル基等が挙げられる。
よって、発色性がより良好となり、成形品の耐衝撃性もより向上する。
ここで、ポリオルガノシロキサンの平均粒子径は、動的光散乱方式の粒度分布測定器を用いて質量基準の粒子径分布を測定し、得られた粒子径分布より算出される値(質量平均粒子径)である。
ポリオルガノシロキサンは、例えばジメチルシロキサンオリゴマーとビニル重合性官能基含有シロキサンとを含むシロキサン混合物を重合することで得られる。
ビニル重合性官能基を含有するアルコキシシラン化合物として具体的には、β-メタクリロイルオキシエチルジメトキシメチルシラン、γ-メタクリロイルオキシプロピルジメトキシメチルシラン、γ-メタクリロイルオキシプロピルメトキシジメチルシラン、γ-メタクリロイルオキシプロピルトリメトキシシラン、γ-メタクリロイルオキシプロピルエトキシジエチルシラン、γ-メタクリロイルオキシプロピルジエトキシメチルシラン、δ-メタクリロイルオキシブチルジエトキシメチルシラン等のメタクリロイルオキシシロキサン;テトラメチルテトラビニルシクロテトラシロキサン、p-ビニルフェニルジメトキシメチルシラン等のビニルシロキサン;等が挙げられる。これらビニル重合性官能基含有シロキサンは、1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。
乳化剤としてはアニオン系乳化剤が好ましい。具体的には、アルキルベンゼンスルホン酸ナトリウム、ラウリルスルホン酸ナトリウム、ポリオキシエチレンノニルフェニルエーテル硫酸エステルナトリウム等が挙げられる。これらの中でも、アルキルベンゼンスルホン酸ナトリウム、ラウリルスルホン酸ナトリウム等のスルホン酸系の乳化剤が好ましい。
これら乳化剤は、1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。
乳化剤の使用量は、シロキサン混合物100質量部に対して0.05質量部~5質量部が好ましい。乳化剤の使用量が0.05質量部以上であれば、シロキサン混合物の分散状態が安定しやすく、微小な粒子径の乳化状態を保持しやすくなる。一方、乳化剤の使用量が5質量部以下であれば、乳化剤に起因する成形品の着色を抑制できる。
これらの中でも、後述するシロキサンラテックスの安定化作用にも優れている点で、脂肪族置換ベンゼンスルホン酸が好ましく、n-ドデシルベンゼンスルホン酸が特に好ましい。また、n-ドデシルベンゼンスルホン酸と硫酸等の鉱酸とを併用すると、ポリオルガノシロキサンの製造に用いた乳化剤の色が成形品の色に与える影響を小さく抑えることができる。
酸触媒の添加量は適宜決めればよいが、通常、シロキサン混合物100質量部に対して0.1質量部~20質量部程度である。
得られるポリオルガノシロキサンの粒子径を制御しやすいことから、シロキサンラテックスを微粒子化した後に、微粒子化したシロキサンラテックスと酸触媒とを混合することが好ましい。特に、微粒子化したシロキサンラテックスを酸触媒水溶液中に一定速度で滴下することが好ましい。
酸触媒をシロキサン混合物と乳化剤と水とを混合するタイミングで混合する場合は、これらを混合した後に微粒子化することが好ましい。
シロキサン混合物と乳化剤と水と酸触媒とを混合する方法や、微粒子化したシロキサンラテックスと酸触媒とを混合する方法としては、例えば高速攪拌による混合、ホモジナイザー等の高圧乳化装置による混合等が挙げられる。中でも、ポリオルガノシロキサンの粒子径の分布を小さくできる点から、ホモジナイザーを使用した方法が好適である。
なお、微粒子化したシロキサンラテックスを酸触媒水溶液中に滴下する場合、酸触媒水溶液の温度は50℃以上が好ましく、80℃以上がさらに好ましい。
ポリオルガノシロキサンの平均粒子径は、シロキサン混合物の組成、酸触媒の使用量(酸触媒水溶液中の酸触媒の含有量)、重合温度等を調整することで制御できる。
例えば、酸触媒の使用量が少なくなるほど平均粒子径は大きくなる傾向にあり、重合温度が高くなるほど平均粒子径は小さくなる傾向にある。
アルキル(メタ)アクリレート系重合体は、アルキル(メタ)アクリレート単位を有する重合体である。
アルキル(メタ)アクリレート系重合体は、アルキル(メタ)アクリレート単位以外の単量体(他の単量体)単位をさらに有していてもよい。
アルキル(メタ)アクリレートとしては、例えばアクリル酸メチル、アクリル酸エチル、アクリル酸n-プロピル、アクリル酸n-ブチル、アクリル酸2-エチルヘキシル等のアクリル酸アルキルエステル;メタクリル酸ヘキシル、メタクリル酸2-エチルヘキシル、メタクリル酸n-ラウリル等のメタクリル酸アルキルエステル等が挙げられる。
これらアルキル(メタ)アクリレートは、1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。中でも、成形品の耐衝撃性がより向上する点で、アクリル酸n-ブチルが好ましい。
単量体成分の重合方法は特に制限されず、公知の方法に従って行うことができる。
ゴム状重合体(a)は、ポリオルガノシロキサンとアルキル(メタ)アクリレート系重合体とが複合した複合ゴムである。本明細書において「複合ゴム」とは、1種以上の重合体を含むものであってもよく、幹ポリマーと枝ポリマーとを有するグラフト重合体であってもよい。
ゴム状重合体(a)の体積平均粒子径は特に制限されないが、50nm以上120nm未満であることが好ましい。ゴム状重合体(a)の体積平均粒子径が前記範囲内であれば、得られる成形品の耐衝撃性と発色性がより良好となる。
ここで、ゴム状重合体(a)の体積平均粒子径は、動的光散乱方式の粒度分布測定器を用いて体積基準の粒子径分布を測定し、得られた粒子径分布より算出される値である。
粒子径が200nm超である粒子の割合は、動的光散乱方式の粒度分布測定器を用いてゴム状重合体(a)の体積基準の粒子径分布を測定し、得られた粒子径分布より算出される値である。
ゴム状重合体(a)の製造方法としては、特に制限されないが、ポリオルガノシロキサンとアルキル(メタ)アクリレート系重合体を各々含む複数のラテックスをヘテロ凝集もしくは共肥大化する方法;ポリオルガノシロキサンおよびアルキル(メタ)アクリレート系重合体のいずれか一方を含むラテックスの存在下で、他方の重合体を形成する単量体成分を重合させて複合化させる方法等が挙げられる。
ゴム状重合体(a)の体積平均粒子径を上述した範囲内となるように容易に調整できることから、ラテックス状のポリオルガノシロキサンの存在下で、1種以上のアルキル(メタ)アクリレートを含む単量体成分をラジカル重合させて共重合体ラテックスを得る工程(ラジカル重合工程)を有する方法が好ましい。
重合条件は、例えば、30℃~95℃で1時間~10時間であってよい。
グラフト交叉剤または架橋剤としては、例えばメタクリル酸アリル、シアヌル酸トリアリル、イソシアヌル酸トリアリル、ジビニルベンゼン、ジメタクリル酸エチレングリコールジエステル、ジメタクリル酸プロピレングリコールジエステル、ジメタクリル酸1,3-ブチレングリコールジエステル、ジメタクリル酸1,4-ブチレングリコールジエステル等が挙げられる。これらは、1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。
ラジカル重合開始剤としては、過酸化物、アゾ系開始剤、酸化剤と還元剤とを組み合わせたレドックス系開始剤等が挙げられる。これらの中では、レドックス系開始剤が好ましく、特に硫酸第一鉄とエチレンジアミン四酢酸二ナトリウム塩とナトリウムホルムアルデヒドスルホキシレートとハイドロパーオキサイドとを組み合わせたスルホキシレート系開始剤が好ましい。
ビニル系単量体混合物(m1)は、1種以上のビニル系単量体を含んでいればよいが、芳香族ビニル化合物およびシアン化ビニル化合物を含む単量体混合物であることが好ましい。
また、これらと共重合可能な他の単量体を、本発明の効果を損なわない範囲で含んでもよい。
グラフト共重合体(A)は、ゴム状重合体(a)の存在下に、ビニル系単量体混合物(m1)を重合して得られる共重合体である。
なお、グラフト共重合体(A)においては、ゴム状重合体(a)の存在下にビニル系単量体混合物(m1)がどのように重合しているか特定することは困難である。すなわち、グラフト共重合体(A)をその構造または特性により直接特定することが不可能であるか、またはおよそ実際的ではないという事情(不可能・非実際的事情)が存在する。したがって、グラフト共重合体(A)は「ゴム状重合体(a)の存在下に、ビニル系単量体混合物(m1)を重合して得られる」と規定することがより適切とされる。
グラフト共重合体(A)は、ゴム状重合体(a)の存在下に、ビニル系単量体混合物(m1)を重合して得られる。
重合を行う方法としては特に制限されないが、反応が安定して進行するように制御可能であることから乳化重合が好ましい。具体的には、ゴム状重合体(a)のラテックスにビニル系単量体混合物(m1)を一括して仕込んだ後に重合する方法;ゴム状重合体(a)のラテックスにビニル系単量体混合物(m1)の一部を先に仕込み、随時重合させながら残りを重合系に滴下する方法;ゴム状重合体(a)のラテックスにビニル系単量体混合物(m1)の全量を滴下しながら随時重合する方法等が挙げられ、これらを1段ないしは2段以上に分けて行うことができる。2段以上に分けて行う場合、各段におけるビニル系単量体混合物(m1)を構成する単量体の種類や組成比を変えて行うことも可能である。
重合の際には、得られるグラフト共重合体(A)の分子量やグラフト率を制御するため、各種公知の連鎖移動剤を添加してもよい。
重合条件は、例えば、30℃~95℃で1時間~10時間であってよい。
グラフト共重合体(A)のラテックスからグラフト共重合体(A)を回収する方法としては、例えば、グラフト共重合体(A)のラテックスを、凝固剤を溶解させた熱水中に投入することによってスラリー状に凝析する湿式法;加熱雰囲気中にグラフト共重合体(A)のラテックスを噴霧することによって半直接的にグラフト共重合体(A)を回収するスプレードライ法等が挙げられる。
スラリー状のグラフト共重合体(A)から乾燥状態のグラフト共重合体(A)を得る方法としては、まず残存する乳化剤残渣を水中に溶出させて洗浄し、次いで、このスラリーを遠心またはプレス脱水機等で脱水した後に気流乾燥機等で乾燥する方法;圧搾脱水機や押出機等で脱水と乾燥とを同時に実施する方法等が挙げられる。かかる方法によって、粉体または粒子状の乾燥グラフト共重合体(A)が得られる。
乾燥温度は、例えば、50℃~90℃であってよい。
得られたグラフト共重合体(A)中のゴム状重合体(a)の体積平均粒子径および体積基準の粒子径分布は、グラフト共重合体(A)の製造に用いたゴム状重合体(a)のラテックスにおけるゴム状重合体(a)の体積平均粒子径および体積基準の粒子径分布と同じである。
なお、圧搾脱水機や押出機から排出されたグラフト共重合体(A)を回収せず、直接、樹脂組成物を製造する押出機や成形機に送って成形品とすることも可能である。
ビニル系単量体混合物(m2)は、少なくともアルキル(メタ)アクリレート系単量体を含む単量体混合物である。
ビニル系単量体混合物(m2)は、アルキル(メタ)アクリレート系単量体の他に、これらと共重合可能な他の単量体を、本発明の効果を損なわない範囲で含んでもよい。
ビニル系共重合体(B)は、ビニル系単量体混合物(m2)を重合して得られる重合体である。
ビニル系共重合体(B)は、ビニル系単量体混合物(m2)の重合体である。ビニル系共重合体(B)は、少なくともアルキル(メタ)アクリレート系単量体由来の単位を含む。
ビニル系共重合体(B)の質量平均分子量は、ゲルパーミエーションクロマトグラフィ(GPC)を用いて測定された、標準ポリスチレン換算の値である。
ビニル系共重合体(B)は、1種を単独で使用してもよく、2種以上を組み合わせて使用してもよい。
なお、ビニル系単量体混合物(m2)が2種以上の単量体を含む場合、得られるビニル系共重合体(B)は、典型的には、これら2種以上の単量体由来の単位がランダムに配列したランダム共重合体である。
乳化重合の重合条件は、例えば、30℃~95℃で1時間~10時間であってよい。
乳化剤としては、通常の乳化重合用乳化剤(ロジン酸カリウム、アルキルベンゼンスルホン酸ナトリウム等)が挙げられる。
重合開始剤としては、有機、無機の酸化物系開始剤が挙げられる。
連鎖移動剤としては、メルカプタン類、α-メチルスチレンダイマー、テルペン類等が挙げられる。
析出法としては、グラフト共重合体(A)のラテックスからグラフト共重合体(A)を回収するときと同様の方法を採用できる。
懸濁重合の重合条件は、例えば、60℃~150℃で1時間~20時間であってよい。
懸濁剤としては、トリカルシウムフォスファイト、ポリビニルアルコール等が挙げられる。
懸濁助剤としては、アルキルベンゼンスルホン酸ナトリウム等が挙げられる。
重合開始剤としては、有機ペルオキシド類等が挙げられる。
連鎖移動剤としては、メルカプタン類、α-メチルスチレンダイマー、テルペン類等が挙げられる。
金属成分(C)は、アルカリ金属である。アルカリ金属の中でも、ナトリウム(Na)、カリウム(K)が好ましい。金属成分(C)は、カリウムを含むことがより好ましい。なお、金属成分(C)は、グラフト共重合体(A)やビニル系共重合体(B)の製造時に使用される金属成分を含む化合物由来のものであってもよく、後述する熱可塑性樹脂組成物の製造時に、金属成分を含む化合物として配合するものであってもよい。
他の熱可塑性樹脂としては、例えば、ポリカーボネート、ポリブチレンテレフタレート(PBT)、ポリエチレンテレフタレート(PET)、ポリ塩化ビニル、ポリスチレン、ポリアセタール、変性ポリフェニレンエーテル(変性PPE)、エチレン-酢酸ビニル共重合体、ポリアリレート、液晶ポリエステル、ポリエチレン、ポリプロピレン、フッ素樹脂、ポリアミド(ナイロン)等が挙げられる。
添加剤としては、例えば、酸化防止剤、滑剤、加工助剤、顔料、染料、充填剤、シリコーンオイル、パラフィンオイル等が挙げられる。
熱可塑性樹脂組成物中、グラフト共重合体(A)の含有量は、熱可塑性樹脂組成物の総質量(100質量部)に対して、20質量部~80質量部であることが好ましく、30質量部~70質量部であることがより好ましく、40質量部~60質量部であることがさらに好ましい。グラフト共重合体(A)の含有量が前記下限値以上であれば、成形品の機械的物性が良好となる。グラフト共重合体(A)の含有量が前記上限値以下であれば、成形品の発色性および成形外観が良好となる。
本明細書において、金属成分(C)の含有量は、後述の実施例に記載の方法で測定した値である。具体的には、金属成分(C)の含有量は、蛍光X線装置(スペクトリス株式会社製「MagiX PRO」を用いて金属成分の定量を行い、熱可塑性樹脂組成物中に含まれる金属成分(C)の含有量を測定して得られた値である。
熱可塑性樹脂組成物の製造方法は特に限定されない。例えば、グラフト共重合体(A)とビニル系共重合体(B)と金属成分(C)と、必要に応じてこれら以外の成分(その他の熱可塑性樹脂、添加剤)とを、V型ブレンダやヘンシェルミキサー等により混合分散させ、これにより得られた混合物をスクリュー式押出機、バンバリーミキサ、加圧ニーダ、ミキシングロール等の溶融混練機等を用いて溶融混練することにより熱可塑性樹脂組成物が製造される。溶融混練後に、必要に応じてペレタイザー等を用いて、溶融混練物をペレット化してもよい。
以上説明した本実施形態の熱可塑性樹脂組成物にあっては、グラフト共重合体(A)と、ビニル系共重合体(B)と、金属成分(C)と、を含み、金属成分(C)の含有量が、熱可塑性樹脂組成物の総質量に対し、60ppm以上であり、グラフト共重合体(A)がポリオルガノシロキサンとアルキル(メタ)アクリレート系重合体を含むゴム状重合体(a)20質量%~80質量%の存在下に1種以上のビニル系単量体を含むビニル系単量体混合物(m1)80質量%~20質量%を重合してなるグラフト重合体、ビニル系共重合体(B)がアルキル(メタ)アクリレート系単量体を含有するビニル系単量体混合物(m2)を重合してなるビニル系共重合体、金属成分(C)がアルカリ金属である金属成分である、熱可塑性樹脂組成物であるため、耐熱変色性に優れる成形品を得ることができる。
本発明の一実施形態に係る成形品は、本実施形態の熱可塑性樹脂組成物から構成される。言い換えれば、本実施形態の成形品は、本実施形態の熱可塑性樹脂組成物を公知の成形方法によって成形加工して得られる。
成形方法としては、例えば、射出成形法、プレス成形法、押出成形法、真空成形法、ブロー成形法等が挙げられる。
成形品の用途としては、車輌内外装部品、事務機器、家電、建材等が挙げられ、車輌外装部品が好適である。
以下に記載の「%」は「質量%」、「部」は「質量部」を意味する。
以下の実施例および比較例における各種測定および評価方法は、以下の通りである。
熱可塑性樹脂組成物のペレットを、30トン射出成形機(日精樹脂工業株式会社製「NEX30W-3E」)を用い、シリンダー設定温度230℃および280℃、金型温度60℃の条件で成形し、長さ80mm、幅55mm、厚み2mmの成形品を得た。
得られた230℃、280℃の両成形品について、紫外可視近赤分光光度計(日本分光株式会社製「V-670」)を用いて青から黄にかけての色味の強さを示すb*を、SCE方式にて測定し、熱変色の指標Δb*を下記式(1)から算出した。Δb*が小さいほど熱変色が抑制され良好である。
Δb*=b*(280℃)-b*(230℃) (1)
ただし、上記式(1)において、b*(230℃)は230℃成形品のb*値、b*(280℃)は280℃成形品のb*値である。
熱可塑性樹脂組成物のペレットを、85トン射出成形機(株式会社日本製鋼所製「J85AD-110H」)を用い、シリンダー設定温度280℃、金型温度60℃の条件でISO 178試験で用いるダンベル試験片を成形し、得られた試験片にシルバーストリークが発生するか否かを目視で判定した。評価の基準を以下に示す。
A:シルバーストリークの発生無し
B:軽微なシルバーストリークが1~2か所発生
C:シルバーストリークが3か所以上発生
上記、熱変色を評価した成形品について、蛍光X線装置(スペクトリス株式会社製「MagiX PRO」を用いて金属成分の定量を行い、熱可塑性樹脂組成物中に含まれるナトリウム(Na)、およびカリウム(K)の濃度を測定した。
(ポリオルガノシロキサン(s-1)の製造)
オクタメチルシクロテトラシロキサン98部、γ-メタクリロイルオキシプロピルジメトキシメチルシラン2部を混合してシロキサン混合物100部を得た。これに、ドデシルベンゼンスルホン酸ナトリウム0.67部、イオン交換水300部からなる水溶液を添加し、ホモミキサーにて10000回転/分で2分間撹拌した後、ホモジナイザーに300kg/cm2の圧力で2回通し、安定な予備混合オルガノシロキサンラテックスを得た。別途、試薬注入容器、冷却管、ジャケット加熱機および攪拌装置を備えた反応器内に、ドデシルベンゼンスルホン酸10部と、イオン交換水90部とを投入し、10%のドデシルベンゼンスルホン酸水溶液(酸触媒水溶液)を調製した。この酸触媒水溶液を85℃に加熱した状態で、予備混合オルガノシロキサンラテックスを2時間にわたって滴下し、滴下終了後3時間その温度を維持した後、40℃以下に冷却した。次いで、この反応物を10%水酸化ナトリウム水溶液でpH7.0に中和して、ポリオルガノシロキサン(s-1)のラテックスを得た。ポリオルガノシロキサン(s-1)のラテックスの一部を180℃で30分乾燥して固形分を求めたところ18.2%であった。また、ラテックス中に分散している質量基準の平均粒子径は30nmであった。
(グラフト共重合体(A-1)の製造)
試薬注入容器、冷却管、ジャケット加熱器および撹拌装置を備えた反応器内に、ポリオルガノシロキサン(s-1)のラテックスを固形分換算で6.0部、アルキルジフェニルエーテルジスルホン酸ナトリウム0.5部を仕込み、イオン交換水190部を添加し、混合した。その後、アルキル(メタ)アクリレート系ゴム状重合体(a-1)を構成する単量体としてアクリル酸n-ブチル44.0部、メタクリル酸アリル0.2部、ジメタクリル酸1,3-ブチレングリコールジエステル0.06部、およびt-ブチルヒドロペルオキシド0.1部からなる混合物を添加した。この反応器に窒素気流を通じることによって、雰囲気の窒素置換を行い、60℃まで昇温した。反応器の内部の温度が60℃になった時点で、硫酸第一鉄0.0001部、エチレンジアミン四酢酸二ナトリウム塩0.0003部およびロンガリット0.2部をイオン交換水10部に溶解させた水溶液を添加し、ラジカル重合を開始させた。アルキル(メタ)アクリレート成分の重合により、液温は78℃まで上昇した。1時間この状態を維持し、重合発熱が確認されなくなるまで重合を継続し、複合ゴム状重合体(a-1)のラテックスを得た。ラテックスに分散しているアルキル(メタ)アクリレート系ゴム状重合体(a-1)の体積平均粒子径は88nmであった。
(ビニル系共重合体(B-1))
ポリメタクリル酸メチル「アクリペットVH5」(三菱ケミカル株式会社製、メタクリル酸メチル98部、メタクリル酸2部、質量平均分子量(Mw)7×103)をビニル系共重合体(B-1)として使用した。
(金属成分(C-1))
カリウムを含む化合物として、アルケニルコハク酸ジカリウム水溶液(商品名:ラテムルASK、花王株式会社製)を使用した。
(金属成分(C-2))
ナトリウムを含む化合物として、無水ピロリン酸ナトリウム(富士フィルム和光純薬株式会社製)を使用した。
(金属成分(C-3))
ナトリウムを含む化合物として、酢酸ナトリウム・3水和物(富士フィルム和光純薬株式会社製)を使用した。
グラフト共重合体(A-1)45部と、ビニル系共重合体(B-1)55部と、金属成分(C-1)0.4部と、エチレンビスステアリルアミド0.5部と、アデカスタブLA-36(株式会社ADEKA製)0.3部と、アデカスタブLA-63P(株式会社ADEKA製)0.3部と、着色剤として酸化チタン5部とをヘンシェルミキサーを用いて混合した。28mmφの真空ベント付き2軸押出機(株式会社日本製鋼所製「TEX-28V」)で、シリンダー温度240℃にて溶融混練後に、ペレタイザー(創研社製「SH型ペレタイザー」)を用いてペレット化した熱可塑性樹脂組成物を得た。得られた熱可塑性樹脂組成物を用いて、各種成形品を作製し、熱変色と成形外観を評価した。
なお、金属成分(C)の配合量、添加剤および着色剤の配合量は、グラフト共重合体(A)とビニル系共重合体(B)の合計質量(100部)に対する割合である。
結果を表1、表2に示す。なお、表1において金属成分(C)の配合量は、金属成分(C)を含む化合物の配合量を表す。
表1、表2に示す配合処方に変更した以外は、実施例1と同様にして熱可塑性樹脂組成物を調製し、各種成形品を作製し、熱変色と成形外観を評価した。結果を表1、表2に示す。
したがって、本発明の熱可塑性樹脂組成物を用いると、耐熱変色性に優れる成形品が得られることが分かる。
また、実施例1~実施例3、実施例5、実施例9の熱可塑性樹脂組成物から得られた成形品は、成形外観にも優れる。
一方、比較例1、比較例2の熱可塑性樹脂組成物から得られた成形品は、耐熱変色性に劣る。
Claims (5)
- 下記グラフト共重合体(A)と、下記ビニル系共重合体(B)と、下記金属成分(C)と、を含み、
下記金属成分(C)の含有量が、熱可塑性樹脂組成物の総質量に対し、60ppm以上である、熱可塑性樹脂組成物。
(A):ポリオルガノシロキサンとアルキル(メタ)アクリレート系重合体とから得られるゴム状重合体(a)20質量%~80質量%の存在下に、1種以上のビニル系単量体を含むビニル系単量体混合物(m1)80質量%~20質量%(ただし、前記ゴム状重合体(a)と前記ビニル系単量体混合物(m1)との合計を100質量%とする。)を重合してなるグラフト重合体
(B):アルキル(メタ)アクリレート系単量体を含有するビニル系単量体混合物(m2)を重合してなるビニル系共重合体
(C):アルカリ金属である金属成分 - 前記金属成分(C)の含有量が、熱可塑性樹脂組成物の総質量に対し、100ppm~400ppmである、請求項1に記載の熱可塑性樹脂組成物。
- 前記金属成分(C)がカリウムを含む、請求項1または2に記載の熱可塑性樹脂組成物。
- 前記グラフト重合体(A)の含有量が、熱可塑性樹脂組成物の総質量に対し、20質量部~80質量部である、請求項1~3のいずれか1項に記載の熱可塑性樹脂組成物。
- 請求項1~4のいずれか1項に記載の熱可塑性樹脂組成物から形成される、成形品。
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BR112023019548A BR112023019548A2 (pt) | 2021-03-31 | 2022-03-25 | Composição de resina termoplástica, e, artigo moldado |
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US18/278,705 US11976189B2 (en) | 2021-03-31 | 2022-03-25 | Thermoplastic resin composition and molded article |
EP22780630.4A EP4317310A1 (en) | 2021-03-31 | 2022-03-25 | Thermoplastic resin composition and molded article |
CN202280024816.0A CN117083343A (zh) | 2021-03-31 | 2022-03-25 | 热塑性树脂组合物、成型品 |
MX2023011491A MX2023011491A (es) | 2021-03-31 | 2022-03-25 | Composicion de resina termoplastica y el articulo moldeado de la misma. |
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- 2022-03-25 CA CA3213530A patent/CA3213530A1/en active Pending
- 2022-03-25 MX MX2023011491A patent/MX2023011491A/es unknown
- 2022-03-25 BR BR112023019548A patent/BR112023019548A2/pt unknown
- 2022-03-25 JP JP2022554299A patent/JP7242971B2/ja active Active
- 2022-03-25 EP EP22780630.4A patent/EP4317310A1/en active Pending
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CN117083343A (zh) | 2023-11-17 |
MX2023011491A (es) | 2023-10-16 |
EP4317310A1 (en) | 2024-02-07 |
US11976189B2 (en) | 2024-05-07 |
JPWO2022210417A1 (ja) | 2022-10-06 |
CA3213530A1 (en) | 2022-10-06 |
US20240043678A1 (en) | 2024-02-08 |
BR112023019548A2 (pt) | 2023-10-31 |
JP7242971B2 (ja) | 2023-03-20 |
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