WO2022019408A1 - 열가소성 수지 조성물 및 이의 성형품 - Google Patents
열가소성 수지 조성물 및 이의 성형품 Download PDFInfo
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- WO2022019408A1 WO2022019408A1 PCT/KR2020/018536 KR2020018536W WO2022019408A1 WO 2022019408 A1 WO2022019408 A1 WO 2022019408A1 KR 2020018536 W KR2020018536 W KR 2020018536W WO 2022019408 A1 WO2022019408 A1 WO 2022019408A1
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- resin composition
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- thermoplastic resin
- acrylate
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- 239000011342 resin composition Substances 0.000 title claims abstract description 61
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 58
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 136
- 229920005989 resin Polymers 0.000 claims abstract description 79
- 239000011347 resin Substances 0.000 claims abstract description 79
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 56
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 239000006224 matting agent Substances 0.000 claims abstract description 18
- 238000002834 transmittance Methods 0.000 claims abstract description 15
- 229920000193 polymethacrylate Polymers 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 32
- -1 cyanide compound Chemical class 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 22
- 229920001971 elastomer Polymers 0.000 claims description 20
- 239000005060 rubber Substances 0.000 claims description 20
- 229920001577 copolymer Polymers 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 229920006122 polyamide resin Polymers 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 14
- 230000007797 corrosion Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 238000007720 emulsion polymerization reaction Methods 0.000 description 14
- 238000002347 injection Methods 0.000 description 14
- 239000007924 injection Substances 0.000 description 14
- 239000004952 Polyamide Substances 0.000 description 11
- 229920002647 polyamide Polymers 0.000 description 11
- 229920002302 Nylon 6,6 Polymers 0.000 description 10
- 230000008901 benefit Effects 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 9
- 230000003746 surface roughness Effects 0.000 description 9
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 8
- 239000004926 polymethyl methacrylate Substances 0.000 description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 7
- 229920002292 Nylon 6 Polymers 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 238000012662 bulk polymerization Methods 0.000 description 6
- 229920000572 Nylon 6/12 Polymers 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 5
- 238000010557 suspension polymerization reaction Methods 0.000 description 5
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002296 dynamic light scattering Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- DEAKWVKQKRNPHF-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enenitrile;styrene Chemical compound C=CC#N.COC(=O)C(C)=C.C=CC1=CC=CC=C1 DEAKWVKQKRNPHF-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 229920000299 Nylon 12 Polymers 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 229920006038 crystalline resin Polymers 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000010559 graft polymerization reaction Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 2
- 229920000393 Nylon 6/6T Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- IWYDHOAUDWTVEP-UHFFFAOYSA-N mandelic acid Chemical compound OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- CHNGPLVDGWOPMD-UHFFFAOYSA-N 2-ethylbutyl 2-methylprop-2-enoate Chemical compound CCC(CC)COC(=O)C(C)=C CHNGPLVDGWOPMD-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- CCMZKOAOMQSOQA-UHFFFAOYSA-N 3-methyl-2-methylidenebutanenitrile Chemical compound CC(C)C(=C)C#N CCMZKOAOMQSOQA-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003831 antifriction material Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
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- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Images
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- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- 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
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- 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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- 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
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- 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
- 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
- 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
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- 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
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- C08J2351/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
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- 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
- C08J2433/00—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
- C08J2433/04—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
- C08J2433/06—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
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Definitions
- the present invention relates to a thermoplastic resin composition and a molded article thereof, and more particularly, to a conventional ASA resin, mechanical properties, weather resistance and processability are maintained at the same or higher level, display readability is excellent, and a general mold or general mold without a separate corrosion mold It relates to a matte thermoplastic resin composition capable of injection or extrusion by a T-die extruder, and a molded article thereof.
- the acrylate compound-styrene-acrylonitrile copolymer (hereinafter referred to as 'ASA resin') has weather resistance, aging resistance, chemical resistance, rigidity, impact resistance, and processability. It is widely used in automobiles, miscellaneous goods and construction materials.
- low-gloss ASA resin was realized by injecting a crystalline resin such as nylon into ASA resin or surface treatment with a separate low-light spray.
- the readability of the display was greatly reduced, and it was difficult to secure the readability of the matte ASA resin even when processing such as extrusion/injection was performed in a separate corrosion mold.
- the present invention has excellent display readability while maintaining the same or higher mechanical properties, weather resistance and workability compared to the conventional ASA resin, and a general mold or general T-die without a separate corrosion mold
- An object of the present invention is to provide a matte thermoplastic resin composition capable of injection or extrusion in an extruder, and a molded article thereof.
- the present invention provides 100 parts by weight of a base resin comprising an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer; and 0.5 to 10 parts by weight of a matting agent having a refractive index of 1.46 to 1.53, and provides a thermoplastic resin composition characterized in that it satisfies the following Equations 1 and 2.
- the present invention provides an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising 100 parts by weight of a base resin; and 0.5 to 10 parts by weight of a matting agent having a refractive index of 1.46 to 1.53, and provides a thermoplastic resin composition, characterized in that the readability (R) calculated by the following Equation 3 is 1 to 1.4.
- Rc is the width of the numeric stroke: 2mm, final light quantity: 14 lux, LED light source: 150 lm/W, distance between light source and sheet: contact, and sheet thickness: 0.15T. It is the area of the measured brightness peak, and Ro is the area of the theoretical brightness peak with no light blur.
- the readability (R) of the present description may be defined as the degree of light blur occurring at the boundary between the light emitting part and the non-emitting part of the display. Referring to FIG. If there is a gentle drop (poor) and there is little light scattering, the brightness of the emitting part drops from 240 to the brightness of the non-emitting part steeply (normal). ). Accordingly, the more severe the light blur, the lower the readability, and the higher the readability R value. In FIG. 1, an interval 5 of the x-axis position is about 1 mm.
- the brightness 160 is the brightness value of the gray film as a reference.
- the base resin is preferably acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer 10 to 70% by weight, polymethacrylate-based resin 5 to 50% by weight, and methacrylate-aromatic vinyl compound-vinyl cyan compound 10 to 50% by weight of the copolymer.
- the total light transmittance Tt is preferably 80 to 95%, and the haze Hz may be preferably 1 to 90%.
- the acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer preferably contains i) acrylate rubber having an average particle diameter of 0.05 to 0.15 ⁇ m in an amount of 40 to 60% by weight and a graft ratio of 40% or more -aromatic vinyl Compound-vinyl cyan compound graft copolymer, ii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing 40 to 60 wt% of acrylate rubber having an average particle diameter of 0.05 to 0.15 ⁇ m and having a graft rate of less than 40% , and iii) may be at least one selected from the group consisting of acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprising 40 to 60 wt% of acrylate rubber having an average particle diameter of 0.33 to 0.5 ⁇ m.
- the i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer is included in an amount of 30 to 60% by weight, and the ii) acrylate-aromatic vinyl compound-
- the vinyl cyan compound graft copolymer may be included in an amount of 35 to 65 wt%, and iii) the acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer may be included in an amount of 5 to 30 wt%.
- the polymethacrylate-based resin may preferably include 65 to 80% by weight of methacrylate and 20 to 35% by weight of a vinyl cyanide compound.
- the polymethacrylate-based resin may preferably have a weight average molecular weight of 50,000 to 200,000 g/mol.
- the polymethacrylate-based resin is preferably a) a polymethacrylate-based resin having a weight average molecular weight of 30,000 to 90,000 g/mol, b) a polymethacrylate-based resin having a weight average molecular weight of 100,000 to 200,000 g/mol , and c) may be at least one selected from the group consisting of polymethacrylate-based resins having a weight average molecular weight of greater than 200,000 g/mol to 300,000 g/mol or less.
- a) the polymethacrylate-based resin is included in 5 to 30% by weight, and b) the polymethacrylate-based resin is included in 5 to 30% by weight, , c) the polymethacrylate-based resin may be included in an amount of 10 to 50% by weight.
- the methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer may preferably include 65 to 85 wt% of methacrylate, 10 to 30 wt% of an aromatic vinyl compound, and 5 to 10 wt% of a vinyl cyan compound. .
- the methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer may preferably have a weight average molecular weight of 80,000 to 200,000 g/mol.
- the matting agent may preferably be a polyamide resin having a refractive index of 1.46 to 1.53.
- the present invention provides a molded article comprising the thermoplastic resin composition.
- the molded article may preferably be a film for a hidden display or a matte sheet material.
- the film or sheet may preferably have a thickness of 0.05 to 0.5T.
- 1 is a graph showing changes in brightness according to positions for measuring display readability.
- the top picture is a picture of a conventional high-gloss air conditioner product
- the middle picture is a conventional matte air conditioner product
- It is a photograph of the product
- the photograph at the bottom is a photograph of the air conditioner product according to the present invention.
- thermoplastic resin composition of the present disclosure and a molded article thereof will be described in detail.
- the present inventors put a certain amount of a matting agent having a refractive index within a specific range into the ASA resin, and When the gloss, haze (%) and total light transmittance (%) are adjusted in a predetermined relational expression, it has a matte appearance that does not have an artificial plastic feel, excellent display readability, and it is confirmed that injection is possible in a general mold without a separate corrosion mold And, based on this, further research was completed to complete the present invention.
- thermoplastic resin composition of the present invention comprises: 100 parts by weight of a base resin comprising an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer; And 0.5 to 10 parts by weight of a matting agent having a refractive index of 1.46 to 1.53, characterized in that it satisfies the following Equations 1 and 2, and in this case, mechanical properties, weather resistance and workability are maintained at the same level or more compared to conventional ASA resins , there is an advantage of providing a matte thermoplastic resin composition that has excellent display readability and can be injected in a general mold without a separate corrosion mold, and a molded article thereof.
- thermoplastic resin composition may satisfy the following Equation 1a as a specific example, and in this case, mechanical properties, weather resistance, processability, etc. are maintained at the same or higher level, display readability is excellent, and injection can be performed in a general mold without a separate corrosion mold. have.
- the Tt is preferably 80 or more, more preferably 85 or more, and the Hz is preferably 10 or less.
- thermoplastic resin composition of the present invention includes 100 parts by weight of a base resin comprising an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer; and 0.5 to 10 parts by weight of a matting agent having a refractive index of 1.46 to 1.53, and is characterized in that the readability (R) calculated by the following Equation 3 is 1 to 1.4, and even in this case, mechanical properties, weather resistance and There is an advantage of providing a matte thermoplastic resin composition and a molded article thereof that are excellent in display readability and can be injected in a general mold without a separate corrosion mold while maintaining processability and the like at the same or higher level.
- Rc is the area of the brightness peak measured under the conditions of width of numeric stroke: 2 mm, final light quantity: 14 lux, LED light source: 150 lm/W, light source and sheet distance: contact, and sheet thickness: 0.15T, and Ro is the area of the theoretical brightness peak with no light bleed.
- the brightness was calculated using the RGB values of the photographed image in the paint board, and the brightness values measured according to positions were displayed with reference to FIG. 1 below to obtain a graph of the change in brightness according to positions.
- the brightness value ranges from 0 to 240, where 0 means black and 240 means white.
- thermoplastic resin composition of the present disclosure will be described in detail as follows.
- the base resin of the present substrate preferably includes an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, a polymethacrylate-based resin and a methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer, more preferably acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer 10 to 70% by weight, polymethacrylate-based resin 5 to 50% by weight, and methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer 10 to 50 % by weight.
- the acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer of the present disclosure preferably contains i) 40 to 60% by weight of an acrylate rubber having an average particle diameter of 0.05 to 0.15 ⁇ m, and an acrylate having a graft ratio of 40% or more.
- -Aromatic vinyl compound-vinyl cyan compound graft copolymer ii) acrylate rubber having an average particle diameter of 0.05 to 0.15 ⁇ m in an amount of 40 to 60% by weight and a graft rate of less than 40%-aromatic vinyl compound-vinyl cyan compound graft It may be at least one selected from the group consisting of an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer, and iii) an acrylate rubber having an average particle diameter of 0.33 to 0.5 ⁇ m in an amount of 40 to 60% by weight, and , in this case, there is an excellent effect in processability, elongation, surface quality, weather resistance and transparency.
- the i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer of the present disclosure is preferably 30 to 60% by weight, more preferably 40 to 60% by weight, based on 100% by weight of the total base resin, More preferably, it is included in an amount of 40 to 55% by weight, and most preferably 45 to 55% by weight, and there is an excellent effect in workability, elongation, surface quality, weather resistance and transparency within this range.
- the i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer preferably has a graft ratio of 40% to 55%, more preferably 40% to 50%, and still more preferably 40% to 45%. In this range, workability, elongation, surface quality, weather resistance and transparency are excellent.
- the graft rate is determined by dissolving the graft copolymer powder in acetone, stirring for 24 hours, centrifuging at 20000 rpm for 3 hours to separate the insoluble and soluble components, then drying the separated insoluble component for 24 hours and measuring the following math It can be calculated by Equation 4.
- Graft rate (%) [(measured insoluble content - rubber content of graft copolymer)/rubber content of graft copolymer]*100
- the i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer preferably contains 40 to 60 wt% of an acrylate rubber having an average particle diameter of 0.05 to 0.15 ⁇ m, 20 to 40 wt% of an aromatic vinyl compound, and 10 wt% of a vinyl cyanide compound to 20% by weight, and there is an excellent effect in workability, elongation, surface quality, weather resistance and transparency within this range.
- the i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprises 45 to 55 wt% of an acrylate rubber, 30 to 40 wt% of an aromatic vinyl compound, and 10 to 20 wt% of a vinyl cyan compound It can be made, and there is an excellent effect in weather resistance, fluidity, tensile strength and impact strength within this range.
- a polymer including a certain compound means a polymer polymerized including the compound, and a unit in the polymerized polymer is derived from the compound.
- the i) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, chemical resistance, weather resistance, fluidity, tensile strength and impact strength are excellent.
- the emulsion polymerization is not particularly limited if the emulsion graft polymerization method is commonly carried out in the art to which the present invention belongs.
- the acrylate may be, for example, at least one selected from the group consisting of alkyl acrylates having 2 to 8 carbon atoms in the alkyl group, preferably an alkyl acrylate having 4 to 8 carbon atoms in the alkyl group, more preferably butyl acrylate or ethylhexyl acrylate.
- the aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene and p-tert-butylstyrene, and is preferably styrene.
- the vinyl cyan compound may be, for example, at least one selected from the group consisting of acrylonitrile, methnitrolonitrile, ethyl acrylonitrile and isopropyl acrylonitrile, and is preferably acrylonitrile.
- the acrylate rubber of the i) graft copolymer preferably has an average particle diameter of 0.1 to 0.15 ⁇ m, more preferably 0.12 to 0.15 ⁇ m, and still more preferably 0.12 to 0.14 ⁇ m, within this range, the finally produced thermoplastic Excellent weather resistance, colorability, impact strength, chemical resistance and surface gloss properties can be imparted to the resin composition.
- the average particle diameter may be measured using dynamic light scattering, and in detail, may be measured using Nicomp 380 equipment (product name, manufacturer: PSS).
- the average particle diameter may mean an arithmetic average particle diameter in a particle size distribution measured by a dynamic light scattering method, specifically, an average particle diameter of scattering intensity.
- the sample is prepared by diluting 0.1 g of Latex (TSC 35-50 wt%) 1,000-5,000 times with distilled water, and the measurement method is auto-dilution and measured with a flow cell, and the measurement mode is dynamic light scattering ( Dynamic light scattering) method/Intensity 300KHz/Intensity-weight Gaussian Analysis can be used, and the setting value can be measured at a temperature of 23°C, a measurement wavelength of 632.8nm, and a channel width of 10 ⁇ sec.
- TSC 35-50 wt% Latex
- the measurement method is auto-dilution and measured with a flow cell
- the measurement mode is dynamic light scattering ( Dynamic light scattering) method/Intensity 300KHz/Intensity-weight Gaussian Analysis can be used, and the setting value can be measured at a temperature
- acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer of the present disclosure is preferably 35 to 65% by weight, more preferably 40 to 65% by weight, based on 100% by weight of the total base resin, More preferably, 50 to 65% by weight, and most preferably 55 to 65% by weight, there is an excellent effect in workability, elongation, surface quality, weather resistance and transparency within this range.
- the ii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer preferably has a graft rate of 20% to 39%, more preferably 25% to 35%, and still more preferably 25% to 30%. And within this range, there is an excellent effect in workability, elongation, surface quality, weather resistance and transparency.
- the ii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer preferably contains 40 to 60 wt% of an acrylate rubber having an average particle diameter of 0.05 to 0.15 ⁇ m, 20 to 40 wt% of an aromatic vinyl compound, and 10 wt% of a vinyl cyanide compound to 20% by weight, and there is an excellent effect in workability, elongation, surface quality, weather resistance and transparency within this range.
- the ii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer comprises 45 to 55 wt% of an acrylate rubber, 30 to 40 wt% of an aromatic vinyl compound, and 10 to 20 wt% of a vinyl cyan compound It can be made, and there is an excellent effect in weather resistance, fluidity, tensile strength and impact strength within this range.
- the ii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, chemical resistance, weather resistance, fluidity, tensile strength and impact strength are excellent.
- the emulsion polymerization is not particularly limited if the emulsion graft polymerization method is commonly carried out in the art to which the present invention belongs.
- the acrylate rubber of the graft copolymer preferably has an average particle diameter of 0.1 to 0.15 ⁇ m, more preferably 0.12 to 0.15 ⁇ m, even more preferably 0.12 to 0.14 ⁇ m, within this range, the finally manufactured thermoplastic Excellent weather resistance, colorability, impact strength, chemical resistance and surface gloss properties can be imparted to the resin composition.
- acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer of the present disclosure is preferably 5 to 30% by weight, more preferably 10 to 30% by weight, based on 100% by weight of the total base resin, More preferably, it is included in an amount of 10 to 25% by weight, and most preferably 15 to 20% by weight, and there is an excellent effect in weather resistance, fluidity, tensile strength and impact strength within this range.
- the iii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer is preferably 40 to 60 wt% of an acrylate rubber having an average particle diameter of 0.33 to 0.5 ⁇ m, 25 to 45 wt% of an aromatic vinyl compound, and 10 wt% of a vinyl cyanide compound to 20% by weight, and has excellent effects in weather resistance, fluidity, tensile strength and impact strength within this range.
- the acrylate rubber of the graft copolymer may preferably have an average particle diameter of 0.35 to 0.5 ⁇ m, more preferably 0.38 to 0.5 ⁇ m, still more preferably 0.4 to 0.5 ⁇ m, and weather resistance within this range. Although good, it has excellent mechanical strength such as fluidity, tensile strength and impact strength.
- the iii) graft copolymer may include 45 to 55% by weight of an acrylate rubber, 30 to 40% by weight of an aromatic vinyl compound, and 10 to 20% by weight of a vinyl cyanide compound, and weather resistance within this range; It has excellent fluidity, tensile strength and impact strength.
- the iii) acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer may be included in an amount of preferably 5 to 15% by weight, more preferably 10 to 15% by weight, within this range weather resistance, fluidity, and tensile strength. It has excellent strength and impact strength.
- the iii) graft copolymer may be prepared by, for example, emulsion polymerization, and in this case, it has excellent effects in weather resistance, fluidity, tensile strength and impact strength.
- the emulsion polymerization is not particularly limited if the emulsion graft polymerization method is commonly carried out in the art to which the present invention belongs.
- the polymethacrylate of the present disclosure preferably contains at least 65% by weight, more preferably at least 70% by weight, and still more preferably at least 75% by weight of a methacrylate compound, within this range, gloss, hardness, weather resistance and There is an effect excellent in transparency and the like.
- the polymethacrylate-based resin may preferably include 65 to 80% by weight of methacrylate and 20 to 35% by weight of a vinyl cyanide compound, and excellent effects such as gloss, hardness, weather resistance and transparency within this range there is
- the polymethacrylate-based resin may have a weight average molecular weight of preferably 50,000 to 200,000 g/mol, more preferably 100,000 to 150,000 g/mol, and has excellent gloss, hardness, weather resistance and transparency within this range. It works.
- the polymethacrylate-based resin is preferably a) a polymethacrylate-based resin having a weight average molecular weight of 30,000 to 90,000 g/mol, b) a polymethacrylate-based resin having a weight average molecular weight of 100,000 to 200,000 g/mol , and c) may be at least one selected from the group consisting of polymethacrylate-based resins having a weight average molecular weight of greater than 200,000 g/mol to 300,000 g/mol or less, and in this case, excellent effects such as gloss, hardness, weather resistance and transparency there is
- the weight average molecular weight may be measured using GPC (Gel Permeation Chromatography, waters breeze), and as a specific example, GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as the eluent ) can be measured as a relative value with respect to a standard PS (standard polystyrene) sample.
- GPC Gel Permeation Chromatography, waters breeze
- THF tetrahydrofuran
- solvent THF
- column temperature 40°C
- flow rate 0.3ml/min
- sample concentration 20mg/ml
- injection amount 5 ⁇ l
- column model 1xPLgel 10 ⁇ m MiniMix-B (250x4.6mm) + 1xPLgel 10 ⁇ m MiniMix-B (250x4.6mm) + 1xPLgel 10 ⁇ m MiniMix-B Guard (50x4.6mm)
- equipment name Agilent 1200 series system
- Refractive index detector Agilent G1362 RID
- RI temperature 35°C
- data processing Agilent ChemStation S/W
- test method Mn, Mw and PDI
- the a) polymethacrylate-based resin is preferably 5 to 30% by weight, more preferably 10 to 30% by weight, more preferably 10 to 25% by weight, based on 100% by weight of the total base resin, Most preferably, it is included in an amount of 10 to 20% by weight, and there is an excellent effect of gloss, hardness, weather resistance and transparency within this range.
- the polymethacrylate-based resin is preferably 5 to 30% by weight, more preferably 10 to 30% by weight, even more preferably 10 to 25% by weight, based on 100% by weight of the total base resin, Most preferably, it is included in an amount of 10 to 20% by weight, and there is an excellent effect of gloss, hardness, weather resistance and transparency within this range.
- the polymethacrylate-based resin is preferably 10 to 50% by weight, more preferably 10 to 45% by weight, even more preferably 15 to 45% by weight, based on 100% by weight of the total base resin, Most preferably, it is included in an amount of 15 to 40% by weight, and there is an excellent effect of gloss, hardness, weather resistance and transparency within this range.
- the methacrylate compound may be preferably an alkyl methacrylate having 1 to 15 carbon atoms in the alkyl group, and preferred examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylbutyl methacrylate. It may be at least one selected from the group consisting of acrylate, 2-ethylhexyl methacrylate and lauryl methacrylate, and more preferably an alkyl methacrylate containing a chain alkyl group having 1 to 4 carbon atoms, further Preferably, it may be methyl methacrylate.
- the polymethacrylate-based resin may be prepared by, for example, solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, and the solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization are each commonly used in the art to which the present invention pertains. In the case of emulsion polymerization and suspension polymerization to be carried out, it is not particularly limited.
- the methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer of the present disclosure is preferably composed of 65 to 85% by weight of methacrylate, 10 to 30% by weight of an aromatic vinyl compound, and 5 to 10% by weight of a vinyl cyanide compound. and more preferably 65 to 75% by weight of methacrylate, 15 to 25% by weight of an aromatic vinyl compound, and 5 to 10% by weight of a vinyl cyan compound, and has better weather resistance within this range, It has excellent fluidity, tensile strength and impact strength, and has an emotionally soft effect due to its low surface roughness value.
- the methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer may be preferably a methyl methacrylate-styrene-acrylonitrile copolymer, and in this case, the weather resistance is more excellent, the surface roughness value is low, and emotionally soft It works.
- the methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer may preferably have a weight average molecular weight of 80,000 to 200,000 g/mol, more preferably 100,000 to 150,000 g/mol, still more preferably It may be 120,000 to 140,000 g/mol, and within this range, the weather resistance is more excellent, the fluidity, the tensile strength and the impact strength are excellent, and the surface roughness value is low and there is an emotionally soft effect.
- the methacrylate-aromatic vinyl compound-vinyl cyan compound copolymer is preferably a methyl methacrylate-styrene-acrylonitrile copolymer having a weight average molecular weight of 70,000 to 90,000 g/mol, and a weight average molecular weight of 120,000 to 140,000 It may be at least one selected from the group consisting of g/mol of methyl methacrylate-styrene-acrylonitrile copolymer, and in this case, transparency and weather resistance are excellent.
- the methyl methacrylate-styrene-acrylonitrile copolymer may be prepared by, for example, solution polymerization, bulk polymerization, emulsion polymerization or suspension polymerization, and the solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization are each of the present invention In the case of emulsion polymerization and suspension polymerization methods commonly carried out in the art, it is not particularly limited.
- the matting agent of the present substrate may have a refractive index of, for example, 1.46 to 1.53, preferably 1.47 to 1.53, more preferably 1.50 to 1.53, still more preferably 1.51 to 1.53, and within this range, mechanical compared to conventional ASA resins While physical properties, weather resistance and processability are maintained at the same or higher level, display readability is excellent, and injection can be performed in a general mold without a separate corrosion mold.
- the refractive index may be measured with REICHERT MARK 2 PLUS, at 25° C., by ASTM Method D 542-50.
- the matting agent is preferably at least one selected from the group consisting of a PMMA-based matting agent and polyamide, more preferably polyamide, and the polyamide means a thermoplastic polymer including an amide bond
- polyamide 6, polyamide 66 (PA 6.6), polyamide 46, polyamide ll, polyamide 12, polyamide 610, polyamide 612, polyamide 6/66, polyamide 6/612, polyamide MXD6, polyamide MXD6 Amide 6/MXD6, Polyamide 66/MXD6, Polyamide 6T, Polyamide 6I, Polyamide 6/6T, Polyamide 6/6I, Polyamide 66/6T, Polyamide 66/6I, Polyamide 6/6T/6I , polyamide 66/6T/6I, polyamide 9T, polyamide 9I, polyamide 6/9T, polyamide 6/9I, polyamide 66/9T, polyamide 6/12/9T, polyamide 66/12/9I and polyamide 66/12/6I may be at least one selected from the group consisting of a P
- the polyamide may have a melting point of, for example, 230 °C or higher, preferably 240 °C or higher, more preferably 250 °C or higher, and even more preferably 260 to 270 °C.
- the polyamide has, for example, a relative viscosity (96% sulfuric acid solution) of 2.0 to 4.0, preferably 2.0 to 3.5, more preferably 2.0 to 3.0, and still more preferably 2.4 to 2.7.
- the relative viscosity can be measured with an Ubbelohde viscometer by the ISO 307 sulfuric acid method.
- the matting agent preferably comprises 1 to 10% by weight, more preferably 2 to 10% by weight, still more preferably 3 to 8% by weight, most preferably 3 to 5% by weight, within this range.
- the PMMA-based matting agent is not particularly limited if it is a PMMA-based matting agent commonly used in the art to which the present invention belongs, provided that it has a refractive index according to the present invention.
- the method for preparing the PMMA-based matting agent and polyamide is not particularly limited as long as it is a polymerization method commonly carried out in the art to which the present invention belongs, and is commercially available if it meets the definitions of the PMMA-based matting agent and polyamide according to the present invention. It is free to purchase and use.
- thermoplastic resin composition of the present disclosure preferably satisfies the following Equations 1 and 2, and in this case, mechanical properties, weather resistance and processability are maintained at the same or higher level compared to conventional ASA resins, and display readability is excellent, and a separate corrosion mold It has the advantage of being able to perform injection in a general mold without it.
- thermoplastic resin composition may satisfy the following Equations 1a and 2a as specific examples.
- thermoplastic resin composition may satisfy the following Equations 1b and 2a as a more specific example.
- the thermoplastic resin composition has a total light transmittance Tt of preferably 80 to 95%, more preferably 85 to 95%, still more preferably 87 to 91%, and the haze Hz is preferably 1 to 90%, more preferably Preferably, it may be 2 to 90%, more preferably 2 to 88%, and within this range, mechanical properties, weather resistance, and processability are maintained at the same level or higher compared to conventional ASA resins, and display readability is excellent and separate corrosion There is an advantage that injection can be performed in a general mold without a mold.
- the thermoplastic resin composition preferably has a readability (R) calculated by the following formula (3) of 1 to 1.4, more preferably 1.0 to 1.3, still more preferably 1.0 to 1.2, and within this range, mechanical compared to conventional ASA resins While physical properties, weather resistance and workability are maintained at the same or higher level, there is an effect of excellent display readability.
- R readability
- Rc is the area of the brightness peak measured under the conditions of width of numeric stroke: 2 mm, final light quantity: 14 lux, LED light source: 150 lm/W, light source and sheet distance: contact, and sheet thickness: 0.15T, and Ro is the area of the theoretical brightness peak with no light bleed.
- the thermoplastic resin composition preferably has an average surface roughness (Ra) of 0.5 to 3, more preferably 1 to 2.7, still more preferably 1.5 to 2.6, measured at 5 points with an optical profiler system, and even more Preferably, it is 1.8 to 2.3, and while the matte effect is well expressed within this range, there is an excellent effect in softness, luxury and naturalness.
- Ra average surface roughness
- the surface roughness (Ra) is obtained by preparing the thermoplastic resin composition as a sheet of 0.15T as in the following example, and then using the optical profiler system (NV-2700, Nanosystem Co., Ltd.), 10 times the objective lens X 1 times the eyepiece ( FOV: 628 ⁇ m X 471 ⁇ m), mode: WSI Envelope, Scan range: It is an average value measured at 5 points under the analysis conditions of ⁇ 10 ⁇ m, and its unit is ⁇ m.
- the optical profiler system NV-2700, Nanosystem Co., Ltd.
- 10 times the objective lens X 1 times the eyepiece FOV: 628 ⁇ m X 471 ⁇ m
- mode WSI Envelope
- Scan range It is an average value measured at 5 points under the analysis conditions of ⁇ 10 ⁇ m, and its unit is ⁇ m.
- the thermoplastic resin composition may have a weather resistance ( ⁇ E) of 5.0 or less, preferably 4.9 or less, more preferably 4.0 or less, still more preferably 3.5 or less, measured by the SAE J1960 method for 2000 hours.
- ⁇ E weather resistance
- the thermoplastic resin composition has, for example, a flow index (MI) (220°C, load 10 kg) according to ASTM D1238 of 4 g/10 min or more, preferably 5 g/10 min or more, and more preferably 6 g/10 min or more. and more preferably 9 g/10 min or more, and may be 4 to 15 g/10 min as a specific example.
- MI flow index
- the thermoplastic resin composition may preferably have an elongation (1/8 inch) of 20 or more according to ASTM D638, more preferably 25 or more, and specifically 20 to 40, preferably 29 to 38.
- the thermoplastic resin composition preferably has a hardness of 70 or more according to ASTM D785, more preferably 75 or more, and may be 70 to 120, preferably 78 to 116 as a specific example.
- the thermoplastic resin composition preferably has an injection gloss (3.17T) measured at 60° with a gloss meter VG7000 of 50 or less, more preferably 45 or less, and specifically 20 to 50, preferably 23 to 42 can be
- the thermoplastic resin composition preferably has an Izod impact strength (1/4 inch) according to ASTM 256 of 4 kg ⁇ cm/cm or more, and may be 4 to 7 kg ⁇ cm/cm as a specific example.
- thermoplastic resin composition is optionally used as a heat stabilizer, light stabilizer, dye, pigment, colorant, mold release agent, antistatic agent, antibacterial agent, processing aid, metal deactivator, flame retardant, flame retardant, dripping inhibitor, anti-friction agent and abrasion-resistant agent, if necessary.
- At least one selected from the group consisting of 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.5 to 1 parts by weight may further include, within this range, the original properties of the thermoplastic resin composition of the present invention
- the thermoplastic resin composition may contain, for example, 0 to 35% by weight of the aromatic vinyl polymer, preferably 10 to 35% by weight, more preferably less than 10% by weight, even more preferably Preferably, it contains less than 5% by weight, and most preferably does not contain it. Within this range, the weather resistance is excellent, and the surface roughness value is significantly lowered, so that the gloss is even and the hand feels soft when touched.
- the method for preparing the thermoplastic resin composition of the present invention includes, for example, 100 parts by weight of a base resin comprising an acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer; and 0.5 to 10 parts by weight of a matting agent having a refractive index of 1.46 to 1.53, and then mixing to prepare pellets using an extrusion kneader under 220 to 280° C. conditions, wherein the prepared thermoplastic resin composition is prepared by the following Equations 1 and 2
- thermoplastic resin composition shares all the technical characteristics of the aforementioned thermoplastic resin composition. Therefore, a description of the overlapping portion will be omitted.
- the step of preparing the pellets using the extrusion kneader may be preferably carried out under 220 to 280 °C, more preferably under 220 to 250 °C, wherein the temperature means the temperature set in the cylinder.
- the extrusion kneader is not particularly limited if it is an extrusion kneader commonly used in the art to which the present invention belongs, and may preferably be a twin-screw extrusion kneader.
- the molded article of the present base material is characterized in that it contains the thermoplastic resin composition of the present base material, and in this case, mechanical properties, weather resistance and processability are maintained at the same or higher level, while display readability is excellent.
- the molded article may be, for example, an extrusion-molded article or an injection-molded article, and preferably a film or sheet material for a hidden display.
- the film or sheet may preferably have a thickness of 0.05 to 0.5T, more preferably 0.1 to 0.5T, and there is an effect of excellent matte properties and display readability within this range.
- the molded article may preferably be manufactured including the step of extruding or injecting the thermoplastic resin composition of the present invention at a molding temperature of 190 to 250 °C, preferably at 210 to 240 °C, and within this range, without a separate corrosion mold It can be manufactured in a general mold, and there is an advantage in that the matte characteristics and display readability are well expressed in the product.
- thermoplastic resin composition of the present invention its manufacturing method and molded article, other conditions or equipment not explicitly described can be appropriately selected within the range commonly practiced in the art, and it is specified that there is no particular limitation do.
- A-1) Graft copolymer of emulsion polymerization (50 wt% of butyl acrylate polymer unit having an average particle diameter of 500 nm, 35 wt% of styrene-derived unit, 15 wt% of acrylonitrile-derived unit)
- Emulsion polymerization type graft copolymer (50% by weight of butyl acrylate polymer-derived units having an average particle diameter of 90 nm, 35% by weight of styrene-derived units, 15% by weight of acrylonitrile-derived units, and 30% graft rate)
- A-3) Graft copolymer of emulsion polymerization 50 wt% of butyl acrylate polymer-derived units with an average particle diameter of 80 nm, 35 wt% of styrene-derived units, 15 wt% of acrylonitrile-derived units, and 40% graft rate
- PMMA resin weight average molecular weight 40,000 g/mol, MMA-derived units 95 wt%, MA-derived units 5 wt%)
- PMMA resin weight average molecular weight 230,000 g/mol, MMA-derived units 97% by weight, MA-derived units 3% by weight
- each of the components and contents listed in Table 1 below were prepared into pellets using an extrusion kneader in a 36 pie standard at 280° C. in a twin-screw extruder.
- the produced pellets are uniformly manufactured into sheets with a thickness of 0.15T through a film extruder, and haze (Hz), total light transmittance (Tt), readability, sheet gloss, and surface roughness (Ra) are used as samples. ) and the like were measured by the following method.
- the film extruder uses a single screw extruder for sheet molding (manufactured by Collin, E20T product, 20 pie, L/D:25), and the temperature conditions are 50, 200, 210, 210 ° C.
- the die part temperature was set to 220, 220, 230 °C.
- the pellets were dried sufficiently in an oven at 80° C. for 3 hours or more before input into the film extruder to remove the moisture influence, and then put into the inlet of the film extruder to uniformly produce a sheet with a thickness of 0.15T.
- the temperature of the used rear roller was set to 85° C. using water as a medium, and as shown in FIG. 3 below, a type in which only one side of the resin extruded through the T-die was in contact with the roller was used.
- the RPM of the film extruder screw was fixed at 100 and the linear speed of the roll was adjusted so that the thickness of the sheet was 0.15T.
- haze (Hz), total light transmittance (Tt), readability, sheet gloss, and surface roughness (Ra), etc. were measured for the surface of the extruded sheet surface in contact with the first roll.
- a difference in surface roughness may occur.
- the prepared pellets were injected at a molding temperature of 220° C. to prepare a specimen for measuring physical properties, and impact strength, elongation, hardness, and injection gloss were measured using this.
- MI Melt index
- Sheet gloss (0.15T) was measured at 60 ° with a gloss meter (gloss meter) VG7000.
- R Readability
- the brightness was measured using the RGB value of the photographed image, and with reference to Figure 1 below, the measured brightness value was displayed according to the location to obtain a graph of the brightness change according to the location, It was calculated using Equation 3 below.
- Rc is the area of the measured brightness peak under the conditions of width of number stroke: 2mm
- final light quantity 14 lux
- LED light source 150 lm/W
- distance between light source and sheet contact
- sheet thickness 0.15T
- Ro is Theoretically, it is the area of the brightness peak.
- the measured brightness has a value in the range of 0 to 240, a value of 0 means black, and a value of 240 means white. Referring to FIG.
- Total light transmittance (Tt) and haze (Hz) Measured by ASTM D1003 method. Specifically, using a haze meter (model name: HM-150) of MURAKAMI, the total light transmittance and haze values were measured at 23° C. in accordance with ASTM D1003 for the sheet specimen.
- thermoplastic resin composition according to the present invention (see the bottom photo of Examples 1 to 4 and FIG. 2) according to the present invention relates to sheet gloss, haze (%) and total light transmittance (%) according to the present invention.
- Comparative Examples 1 to 4 which do not conform to the relational expression, mechanical properties such as impact strength and workability are maintained at the same or higher level, and the weather resistance is excellent.
- the conventional high-gloss air conditioner product (see the top photo) has a good display readability, but has an artificial plastic feel, and has a matte appearance so as not to have such an artificial plastic feeling. It can be seen that the changed conventional air conditioner product (see the middle photo) has very poor display readability.
- the matte air conditioner product according to the present invention (refer to the bottom photo) is matte, natural and luxurious, and the display readability is very excellent.
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Abstract
Description
Claims (16)
- 아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체를 포함하는 베이스 수지 100 중량부; 및 굴절률 1.46 내지 1.53의 소광제 0.5 내지 10 중량부를 포함하고,하기 수학식 1 및 2를 만족하는 것을 특징으로 하는열가소성 수지 조성물.[수학식 1]G ≤ 20(여기에서 G는 60°에서 글로스미터로 측정한 0.15T 크기의 시트 광택이다.)[수학식 2]Hz < Tt(여기에서 Hz 및 Tt는 각각 0.15T 크기의 시트의 헤이즈(%) 및 전광선 투과율(%)이다.)
- 제 1항에 있어서,상기 열가소성 수지 조성물은 하기 수학식 3으로 계산된 가독성(R)이 1 내지 1.4인 것을 특징으로 하는열가소성 수지 조성물.[수학식 1]R = Rc/Ro(여기에서 Rc는 여기에서 Rc는 숫자 획의 너비: 2mm, 최종 광량: 14 lux, LED 광원: 150 lm/W, 광원과 시트의 거리: 접촉, 및 시트 두께: 0.15T 조건에서 측정된 명도 피크의 면적이고 Ro는 빛 번짐이 전혀 없는 이론상 명도 피크의 면적이다.)
- 제 1항에 있어서,상기 베이스 수지는 아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체 10 내지 70 중량%, 폴리메타크릴레이트계 수지 5 내지 50 중량% 및 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체 10 내지 50 중량%를 포함하는 것을 특징으로 하는열가소성 수지 조성물.
- 제 1항에 있어서,상기 전광선 투과율 Tt는 80 내지 95%이고, 상기 헤이즈 Hz은 1 내지 90%인 것을 특징으로 하는열가소성 수지 조성물.
- 제 1항에 있어서,상기 아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체는 i)평균입경 0.05 내지 0.15 ㎛의 아크릴레이트 고무를 40 내지 60 중량%로 포함하고 그라프트율이 40% 이상인 아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체, ii)평균입경 0.05 내지 0.15 ㎛의 아크릴레이트 고무를 40 내지 60 중량%로 포함하고 그라프트율이 40% 미만인 아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체, 및 iii)평균입경 0.33 내지 0.5 ㎛의 아크릴레이트 고무를 40 내지 60 중량%로 포함하는 아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는열가소성 수지 조성물.
- 제 5항에 있어서,베이스 수지 총 100 중량%를 기준으로, 상기 i)아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체는 30 내지 60 중량%로 포함되고, 상기 ii)아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체는 35 내지 65 중량%로 포함되며, 및 iii)아크릴레이트-방향족 비닐 화합물-비닐시안 화합물 그라프트 공중합체는 5 내지 30 중량%로 포함되는 것을 특징으로 하는열가소성 수지 조성물.
- 제 3항에 있어서,상기 폴리메타크릴레이트계 수지는 메타크릴레이트 65 내지 80 중량% 및 비닐시안 화합물 20 내지 35 중량%를 포함하여 이루어지는 것을 특징으로 하는열가소성 수지 조성물.
- 제 3항에 있어서,상기 폴리메타크릴레이트계 수지는 중량평균 분자량이 50,000 내지 200,000 g/mol인 것을 특징으로 하는열가소성 수지 조성물.
- 제 3항에 있어서,상기 폴리메타크릴레이트계 수지는 a) 중량평균 분자량이 30,000 내지 90,000 g/mol의 폴리메타크릴레이트계 수지, b) 중량평균 분자량이 100,000 내지 200,000 g/mol의 폴리메타크릴레이트계 수지, 및 c)중량평균 분자량이 200,000 g/mol 초과 내지 300,000 g/mol 이하의 폴리메타크릴레이트계 수지로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는열가소성 수지 조성물.
- 제 9항에 있어서,베이스 수지 총 100 중량%를 기준으로, 상기 a) 폴리메타크릴레이트계 수지는 5 내지 30 중량%로 포함되고, 상기 b) 폴리메타크릴레이트계 수지는 5 내지 30 중량%로 포함되며, 상기 c) 폴리메타크릴레이트계 수지는 10 내지 50 중량%로 포함되는 것을 특징으로 하는열가소성 수지 조성물.
- 제 3항에 있어서,상기 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체는 메타크릴레이트 65 내지 85 중량%, 방향족 비닐 화합물 10 내지 30 중량% 및 비닐시안 화합물 5 내지 10 중량%를 포함하여 이루어지는 것을 특징으로 하는열가소성 수지 조성물.
- 제 3항에 있어서,상기 메타크릴레이트-방향족 비닐 화합물-비닐시안 화합물 공중합체는 중량평균 분자량이 80,000 내지 200,000 g/mol인 것을 특징으로 하는열가소성 수지 조성물.
- 제 1항에 있어서,상기 소광제는 굴절률 1.46 내지 1.53의 폴리아마이드 수지인 것을 특징으로 하는열가소성 수지 조성물.
- 제1항 내지 제13항 중 어느 한 항의 열가소성 수지 조성물을 포함하는 것을 특징으로 하는성형품.
- 제14항에 있어서,상기 성형품은 히든(hidden) 디스플레이용 필름 또는 시트 재료인 것을 특징으로 하는성형품.
- 제15항에 있어서,상기 필름 또는 시트는 두께가 0.05 내지 0.5T인 것을 특징으로 하는성형품.
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