WO2022250314A1 - 열가소성 수지 조성물 - Google Patents
열가소성 수지 조성물 Download PDFInfo
- Publication number
- WO2022250314A1 WO2022250314A1 PCT/KR2022/006246 KR2022006246W WO2022250314A1 WO 2022250314 A1 WO2022250314 A1 WO 2022250314A1 KR 2022006246 W KR2022006246 W KR 2022006246W WO 2022250314 A1 WO2022250314 A1 WO 2022250314A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- thermoplastic resin
- resin composition
- weight
- polymer
- artificial marble
- Prior art date
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 54
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 54
- 239000000178 monomer Substances 0.000 claims abstract description 65
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 63
- 239000002928 artificial marble Substances 0.000 claims abstract description 60
- 239000002699 waste material Substances 0.000 claims abstract description 48
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 39
- 150000001993 dienes Chemical class 0.000 claims abstract description 24
- 229920001971 elastomer Polymers 0.000 claims abstract description 22
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 22
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000000428 dust Substances 0.000 description 5
- 235000019589 hardness Nutrition 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 2
- -1 2-ethylhexyl Chemical group 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-L 2-(2-methylprop-2-enoyloxy)ethyl phosphate Chemical compound CC(=C)C(=O)OCCOP([O-])([O-])=O SEILKFZTLVMHRR-UHFFFAOYSA-L 0.000 description 1
- OYUNTGBISCIYPW-UHFFFAOYSA-N 2-chloroprop-2-enenitrile Chemical compound ClC(=C)C#N OYUNTGBISCIYPW-UHFFFAOYSA-N 0.000 description 1
- RLFXJQPKMZNLMP-UHFFFAOYSA-N 2-phenylprop-2-enenitrile Chemical compound N#CC(=C)C1=CC=CC=C1 RLFXJQPKMZNLMP-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-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
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000009826 distribution Methods 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
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- ISXSFOPKZQZDAO-UHFFFAOYSA-N formaldehyde;sodium Chemical compound [Na].O=C ISXSFOPKZQZDAO-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical group CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 235000019587 texture Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- 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
-
- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08L101/08—Carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
Definitions
- the present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition having excellent scratch resistance and impact resistance.
- artificial marble is a building material that has recently been in the limelight, and it produces about 300,000 tons worldwide and has a market of about 600 billion won. Domestic production is 100,000 tons, and artificial marble currently used in Korea is made from (meth)acrylate-based monomers, (meth)acrylate-based polymers, and fillers as raw materials.
- natural marble currently used in Korea is made from (meth)acrylate-based monomers, (meth)acrylate-based polymers, and fillers as raw materials.
- scrap and dust are generated when processing to the required size, which is discarded by simple landfill or incineration because it cannot be used for other products, causing soil contamination. Therefore, research on ways to utilize waste artificial marble is being conducted.
- Patent Document 1 KR2009-0092882A
- An object to be solved by the present invention is to provide a thermoplastic resin composition having excellent scratch resistance and impact resistance.
- the present invention is a graft polymer comprising a diene-based rubbery polymer to which a (meth)acrylate-based monomer unit and a vinyl aromatic-based monomer unit are grafted; a non-grafted polymer comprising a (meth)acrylate-based monomer unit and a vinyl aromatic-based monomer unit; and 3 to 30% by weight of waste artificial marble.
- the present invention provides a thermoplastic resin composition according to (1), wherein the waste artificial marble includes a (meth)acrylate-based monomer unit.
- thermoplastic resin composition according to (1) or (2) comprising 10 to 30% by weight of the waste artificial marble.
- the present invention also provides the thermoplastic resin composition according to any one of (1) to (3) above, comprising 10 to 50% by weight of the graft polymer.
- the present invention also provides the thermoplastic resin composition according to any one of (1) to (4) above, wherein a vinyl cyanide-based monomer unit is grafted onto the diene-based rubbery polymer.
- the present invention according to any one of (1) to (5) above, wherein the graft polymer is not grafted onto the diene-based rubbery polymer, and the (meth)acrylate-based monomer unit and the vinyl aromatic-based monomer It provides a thermoplastic resin composition comprising a pre-polymer comprising a unit.
- the present invention provides the thermoplastic resin composition according to any one of (1) to (6) above, wherein the diene-based rubbery polymer has an average particle diameter of 200 to 500 nm.
- the present invention also provides the thermoplastic resin composition according to any one of (1) to (7) above, comprising 30 to 80% by weight of the non-grafted polymer.
- the present invention also provides the thermoplastic resin composition according to any one of (1) to (8) above, wherein the non-grafted polymer contains a vinyl cyanide-based monomer unit.
- thermoplastic resin composition comprises 5 to 20% by weight of the diene rubber polymer; 20 to 70% by weight of the (meth)acrylate-based monomer units; Provided is a thermoplastic resin composition comprising 10 to 30% by weight of the vinyl aromatic monomer unit and 3 to 30% by weight of the waste artificial marble.
- thermoplastic resin composition of the present invention can implement excellent scratch resistance and impact resistance.
- the 'diene-based rubbery polymer' may refer to a polymer prepared by cross-linking a diene-based monomer alone or a diene-based monomer and a comonomer copolymerizable therewith.
- the diene-based monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and piperylene, among which 1,3-butadiene is preferred.
- the comonomer include aromatic vinyl monomers, vinyl cyanide monomers, and olefin monomers.
- the diene-based rubber polymer may be at least one selected from the group consisting of a butadiene rubber polymer, a butadiene-styrene rubber polymer, a butadiene-acrylonitrile rubber polymer, and an ethylene-propylene rubber polymer.
- the '(meth)acrylate-based monomer' may be a C 1 to C 10 alkyl (meth)acrylate-based monomer, and the C 1 to C 10 alkyl (meth)acrylate-based monomer is methyl (meth) It may be at least one selected from the group consisting of acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and decyl (meth) acrylate, among which methyl methacryl rate is preferred.
- the 'vinyl aromatic monomer' may be at least one selected from the group consisting of styrene, ⁇ -methyl styrene, ⁇ -ethyl styrene, and p-methyl styrene, of which styrene is preferred.
- the 'vinyl cyanide-based monomer' may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, phenylacrylonitrile, and ⁇ -chloroacrylonitrile, of which acrylonitrile is preferred. do.
- the 'average particle diameter' may mean the arithmetic average particle diameter in the particle size distribution measured by dynamic light scattering, specifically, the scattering intensity average particle diameter.
- the average particle diameter can be measured using Nicomp 370HPL equipment (product name, manufacturer: PSS Nicomp).
- thermoplastic resin composition includes a graft polymer including a diene-based rubbery polymer to which a (meth)acrylate-based monomer unit and a vinyl aromatic-based monomer unit are grafted; a non-grafted polymer comprising a (meth)acrylate-based monomer unit and a vinyl aromatic-based monomer unit; and 3 to 30% by weight of waste artificial marble.
- artificial marble can create various textures, colors, and patterns, so it has good decorative effects, is easy to grind and precisely process, has excellent chemical resistance, stain resistance, heat resistance, workability, and impact resistance, and is easy to maintain. It is used in various fields.
- waste artificial marble such as scrap and dust is generated.
- waste artificial marble is pyrolyzed and used as a raw material, or pulverized and recycled as a raw material for artificial marble.
- thermoplastic resin composition according to an embodiment of the present invention may include 3 to 30% by weight of the waste artificial marble, preferably 10 to 30% by weight. If included below the above conditions, the effect of improving scratch resistance is not realized. If the above conditions are exceeded, processability deteriorates and injection molding is impossible.
- the thermoplastic resin composition may include 10 to 50% by weight, preferably 20 to 40% by weight of the graft polymer. If the above conditions are satisfied, a thermoplastic resin composition having excellent impact resistance can be prepared.
- the thermoplastic resin composition may include 30 to 80% by weight of the matrix polymer, preferably 35 to 70% by weight. If the above conditions are satisfied, a thermoplastic resin composition having excellent processability can be produced.
- thermoplastic resin composition may include 5 to 20% by weight of the diene-based rubber polymer, preferably 10 to 15% by weight. When the above conditions are satisfied, the impact resistance and surface gloss characteristics of the thermoplastic resin composition may be improved.
- thermoplastic resin composition may include 20 to 70% by weight of the (meth)acrylate-based monomer units, preferably 30 to 50% by weight. If the above conditions are satisfied, the impact resistance and processability of the thermoplastic resin composition can be improved.
- thermoplastic resin composition may include 10 to 30% by weight of the vinyl aromatic monomer unit, preferably 15 to 30% by weight. When the above conditions are satisfied, the processability of the thermoplastic resin composition can be improved.
- thermoplastic resin composition may include 3 to 30% by weight of the waste artificial marble, preferably 10 to 30% by weight.
- scratch resistance may be improved while minimizing a decrease in impact resistance of the thermoplastic resin composition.
- the graft polymer is a component that improves the impact resistance of the thermoplastic resin composition.
- the graft polymer includes a diene-based rubbery polymer to which a (meth)acrylate-based monomer unit and a vinyl aromatic monomeric unit are grafted, and is not grafted onto the diene-based rubbery polymer, and a (meth)acrylate-based monomer unit and A free polymer containing a vinyl aromatic monomer unit may be further included.
- the graft polymer may include 20 to 70% by weight, preferably 30 to 60% by weight of the diene-based rubbery polymer.
- the (meth)acrylate-based monomer unit and the vinyl aromatic-based monomer are grafted to the diene-based rubber polymer at an appropriate level to prepare a graft polymer having excellent impact resistance and excellent surface gloss properties. have.
- the average particle diameter of the diene-based rubbery polymer may be 200 to 500 nm, preferably 250 to 400 nm.
- a graft polymer having excellent impact resistance and surface gloss properties can be prepared.
- the graft polymer may include 20 to 60% by weight, preferably 30 to 50% by weight of (meth)acrylate-based monomer units. If the above conditions are satisfied, a graft polymer capable of maximizing the improvement of scratch resistance and impact resistance, which is an effect of the waste artificial marble, can be prepared because it has excellent compatibility with the waste artificial marble, which will be described later, as well as the non-grafted polymer. can
- the graft polymer may include 3 to 30% by weight, preferably 5 to 20% by weight of the vinyl aromatic monomer unit. When the above conditions are satisfied, a graft polymer with improved processability can be prepared.
- a (meth)acrylate-based monomer unit and a vinyl aromatic-based monomer unit as well as a vinyl cyanide-based monomer may be grafted to the diene-based rubbery polymer.
- the graft polymer may include 7% by weight or less of the vinyl cyanide-based monomer unit. If the above conditions are satisfied, a graft polymer with improved chemical resistance can be prepared while minimizing yellowing. In addition, it is possible to minimize the generation of solid content (congeal) during the manufacturing process of the graft polymer.
- the graft polymer may be produced by emulsion polymerization, suspension polymerization, and bulk polymerization, but among these, it is preferable to manufacture the graft polymer by emulsion polymerization capable of producing a graft polymer excellent in both impact resistance and surface gloss properties.
- the non-grafted polymer is a component that improves the processability of the thermoplastic resin composition.
- the non-grafted polymer includes a (meth)acrylate-based monomer unit and a vinyl aromatic-based monomer unit.
- the non-grafted polymer may include 60 to 85% by weight of (meth)acrylate-based monomer units, preferably 65 to 80% by weight. If the above conditions are satisfied, it is possible to prepare a non-grafted polymer that has excellent compatibility with waste artificial marble as well as the non-grafted polymer, which will be described later, and can maximize the improvement effect of scratch resistance and impact resistance, which are effects of the waste artificial marble. can
- the non-grafted polymer may include 15 to 40% by weight of the vinyl aromatic monomer unit, preferably 20 to 35% by weight. If the above conditions are satisfied, a non-grafted polymer having excellent processability can be produced.
- the non-grafted polymer may further include a vinyl cyanide-based monomer to improve chemical resistance.
- a vinyl cyanide-based monomer to improve chemical resistance.
- the non-grafted polymer may be prepared by at least one method selected from the group consisting of emulsion polymerization, suspension polymerization, and bulk polymerization, and among these, it is preferably produced by bulk polymerization capable of producing a high-purity polymer.
- Waste artificial marble is included to improve the scratch resistance of the thermoplastic resin composition.
- artificial marble is a waste of artificial marble, it can be manufactured in the same way as artificial marble.
- artificial marble may use a composition for artificial marble including a (meth)acrylate-based monomer, a (meth)acrylate-based polymer, an initiator, and a filler as a raw material.
- the composition for artificial marble may be extruded, cured by press molding, and then demolded and post-treated.
- post-processing may mean cooling, polishing, and sanding.
- the (meth)acrylate-based polymer which is a component of the composition for artificial marble, may be polymethyl methacrylate.
- the initiator is t-butylperbenzoate, t-butylperoxybenzoate, t-butylperoxy isopropyl carbonate, t-butylperoxy-2-ethylhexanoate and 1,1-bis(t-butylper It may be one or more selected from the group consisting of oxy)-3,3,5-trimethylcyclohexane.
- the filler may be one or more selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium carbonate, silica, alumina, and potassium aluminic acid.
- the waste artificial marble may include a (meth)acrylate-based monomer unit.
- the compatibility between the graft polymer and the non-graft polymer described above is excellent, and as a result, while minimizing the decrease in impact resistance, the thermoplastic resin composition The scratch resistance can be remarkably improved.
- the waste artificial marble may be at least one selected from the group consisting of scraps and dust generated during processing of artificial marble, and may be a processed product obtained by pulverizing it, but since waste artificial marble can be used regardless of its shape, it is not particularly limited. .
- the scratch resistance of the thermoplastic resin composition can be significantly improved because the compatibility between the graft polymer and the non-graft polymer described above is excellent due to the raw material characteristics of the waste artificial marble. have.
- the waste artificial marble is preferably 2 mm or less in consideration of the ease of processing of the thermoplastic resin composition, and preferably has a powder form. Waste artificial marble having a desired particle diameter can be obtained using a mesh.
- This graft polymer latex was put into an aqueous solution containing 2 parts by weight of magnesium acetate and 0.5 part by weight of formic acid, and then coagulated by applying mechanical shear (Mechanical Coagulation). Thereafter, aging, washing, dehydration and drying were carried out to obtain a graft polymer powder.
- mechanical shear Mechanical Coagulation
- a mixture of 68 parts by weight of methyl methacrylate, 22 parts by weight of styrene, 7 parts by weight of acrylonitrile, 3 parts by weight of methacrylic acid, 30 parts by weight of toluene and 0.15 part by weight of t-dodecyl mercaptan was mixed with a raw material having an average residence time of 3 Polymerization was performed while being continuously introduced into the reactor so as to allow time. At this time, the temperature of the reactor was maintained at 148 °C. The polymer solution continuously discharged from the reactor was heated in a pre-heating tank, and unreacted monomers were volatilized in a volatilization tank. Subsequently, while maintaining the temperature of the polymerization solution at 210 °C, non-grafted polymer pellets were prepared using a polymer transfer pump extrusion processor.
- thermoplastic resin composition was prepared by mixing the graft polymer of Preparation Example 1, the non-graft polymer of Preparation Example 2, and the waste artificial marble of Preparation Example 3 in the contents shown in Table 1 below.
- thermoplastic resin composition was prepared by mixing the graft polymer of Preparation Example 1, the non-graft polymer of Preparation Example 2, and the waste artificial marble of Preparation Example 3 in the contents shown in Table 2 below.
- Graft polymer (ABS, manufacturer: LG Chem, trade name: DP270) containing styrene and acrylonitrile grafted butadiene rubbery polymer having an average particle diameter of 250 nm, styrene/acrylonitrile polymer (SAN, manufacturer: Co., Ltd. LG Chem, trade name: 92HR) and the waste artificial marble powder of Preparation Example 3 were mixed in the contents shown in Table 2 below to prepare a thermoplastic resin composition.
- ABS manufacturer: LG Chem, trade name: DP270
- Graft polymer (ABS, manufacturer: LG Chem, trade name: DP270) containing styrene and acrylonitrile grafted butadiene rubbery polymer having an average particle diameter of 250 nm, styrene/acrylonitrile polymer (SAN, manufacturer: Co., Ltd. LG Chem, trade name: 92HR) was mixed in the contents shown in Table 2 below to prepare a thermoplastic resin composition.
- thermoplastic resin compositions of Examples and Comparative Examples After mixing 100 parts by weight of the thermoplastic resin compositions of Examples and Comparative Examples, 0.5 parts by weight of a lubricant (N,N'-ethylenebis (stearamide)), and 0.3 parts by weight of an antioxidant, extrusion and injection were performed to prepare specimens. The physical properties of the specimen were evaluated by the method described below, and the results are shown in Tables 1 and 2 below.
- a lubricant N,N'-ethylenebis (stearamide)
- Pencil hardness In accordance with ASTM D3363, a specimen of 10 cm ⁇ 10 cm ⁇ 3 mm left for 48 hours at 23 ° C. and 50% relative humidity was tested with various hardnesses under a load of 500 g at 23 ° C. After scratching with a pencil 5 times, the degree of scratching was visually evaluated. When pencil scratch marks occurred more than once on the surface of the specimen, the pencil hardness grade was classified as follows.
- Izod impact strength (kgf cm/cm, 1/4 In): measured according to ASTM D256-10 at 25°C.
- Example 2 Example 3
- Example 4 Example 5 graft polymer Preparation Example 1
- 30 30
- 30 30
- 30 30
- non-grafted polymers Preparation Example 2 67 65
- 50 40 waste artificial marble
- Preparation Example 3 3 5
- 10 20
- Comparative Example 4 and Comparative Example 5 containing an excessive amount of waste artificial marble could not be injected, so specimens could not be prepared.
- Comparative Example 6 including the diene-based graft polymer and waste artificial marble had improved scratch resistance compared to Comparative Example 7 not containing waste artificial marble, but the improvement effect was insignificant.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
구분 | 실시예 1 | 실시예 2 | 실시예 3 | 실시예 4 | 실시예 5 | |
그라프트 중합체 | 제조예 1 | 30 | 30 | 30 | 30 | 30 |
비그라프트 중합체 | 제조예 2 | 67 | 65 | 60 | 50 | 40 |
폐인조대리석 | 제조예 3 | 3 | 5 | 10 | 20 | 30 |
연필경도 | 2H | 2H | 3H | 3H | 4H | |
충격강도 | 16 | 14 | 12 | 11 | 10 |
구분 | 비교예 1 | 비교예 2 | 비교예 3 | 비교예 4 | 비교예 5 | 비교예 6 | 비교예 7 | |
그라프트 중합체 | 제조예 1 | 30 | 30 | 30 | 30 | 30 | 0 | 0 |
ABS | 0 | 0 | 0 | 0 | 0 | 30 | 30 | |
비그라프트 중합체 | 제조예 2 | 70 | 69 | 68 | 39 | 30 | 0 | 0 |
SAN | 0 | 0 | 0 | 0 | 0 | 60 | 70 | |
폐인조대리석 | 제조예 3 | 0 | 1 | 2 | 31 | 40 | 10 | 0 |
연필경도 | F | F | F | 가공 불가 |
가공 불가 |
H | F | |
충격강도 | 16 | 16 | 16 | 6 | 15 |
Claims (10)
- (메트)아크릴레이트계 단량체 단위 및 비닐 방향족계 단량체 단위가 그라프트된 디엔계 고무질 중합체를 포함하는 그라프트 중합체;(메트)아크릴레이트계 단량체 단위 및 비닐 방향족계 단량체 단위를 포함하는 비그라프트 중합체; 및폐인조대리석 3 내지 30 중량%를 포함하는 열가소성 수지 조성물.
- 청구항 1에 있어서,상기 폐인조대리석은 (메트)아크릴레이트계 단량체 단위를 포함하는 것인 열가소성 수지 조성물.
- 청구항 1에 있어서,상기 폐인조대리석을 10 내지 30 중량%로 포함하는 것인 열가소성 수지 조성물.
- 청구항 1에 있어서,상기 그라프트 중합체 10 내지 50 중량%를 포함하는 것인 열가소성 수지 조성물.
- 청구항 1에 있어서,상기 디엔계 고무질 중합체에는 비닐 시아나이드계 단량체 단위가 그라프트된 것인 열가소성 수지 조성물.
- 청구항 1에 있어서,상기 그라프트 중합체는 상기 디엔계 고무질 중합체에 그라프트되지 않고 (메트)아크릴레이트계 단량체 단위 및 비닐 방향족계 단량체 단위를 포함하는 프리 중합체를 포함하는 것인 열가소성 수지 조성물.
- 청구항 1에 있어서,상기 디엔계 고무질 중합체는 평균입경이 200 내지 500 ㎚인 열가소성 수지 조성물.
- 청구항 1에 있어서,상기 비그라프트 중합체 30 내지 80 중량%를 포함하는 것인 열가소성 수지 조성물.
- 청구항 1에 있어서,상기 비그라프트 중합체는 비닐 시아나이드계 단량체 단위를 포함하는 것인 열가소성 수지 조성물.
- 청구항 1에 있어서,상기 열가소성 수지 조성물은상기 디엔계 고무질 중합체 5 내지 20 중량%;상기 (메트)아크릴레이트계 단량체 단위 20 내지 70 중량%;상기 비닐 방향족계 단량체 단위 10 내지 30 중량% 및상기 폐인조대리석 3 내지 30 중량%를 포함하는 열가소성 수지 조성물.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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US18/034,044 US20230391999A1 (en) | 2021-05-24 | 2022-05-02 | Thermoplastic resin composition |
CN202280007199.3A CN116368192A (zh) | 2021-05-24 | 2022-05-02 | 热塑性树脂组合物 |
EP22811507.7A EP4215584A4 (en) | 2021-05-24 | 2022-05-02 | THERMOPLASTIC RESIN COMPOSITION |
JP2023523280A JP2023546443A (ja) | 2021-05-24 | 2022-05-02 | 熱可塑性樹脂組成物 |
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KR1020210066306A KR20220158464A (ko) | 2021-05-24 | 2021-05-24 | 열가소성 수지 조성물 |
KR10-2021-0066306 | 2021-05-24 |
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US (1) | US20230391999A1 (ko) |
EP (1) | EP4215584A4 (ko) |
JP (1) | JP2023546443A (ko) |
KR (1) | KR20220158464A (ko) |
CN (1) | CN116368192A (ko) |
TW (1) | TW202311427A (ko) |
WO (1) | WO2022250314A1 (ko) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09207134A (ja) * | 1995-11-28 | 1997-08-12 | Toto Ltd | 熱可塑性樹脂素材の成形材料及びその製造方法 |
JP2006175718A (ja) * | 2004-12-22 | 2006-07-06 | Kubota Matsushitadenko Exterior Works Ltd | 成形品の製造方法 |
JP2007039640A (ja) * | 2005-06-29 | 2007-02-15 | Kubota Matsushitadenko Exterior Works Ltd | 樹脂成形品 |
KR20080078241A (ko) * | 2007-02-22 | 2008-08-27 | 주식회사 엘지화학 | 인조대리석 폐기물의 분쇄물을 포함하는 바닥재 및 그제조방법 |
KR20090092882A (ko) | 2008-02-28 | 2009-09-02 | 조선대학교산학협력단 | 인조대리석 폐분말과 콜애시를 이용한 난연화 조성물 및이의 제조방법 |
KR20190047185A (ko) * | 2017-10-27 | 2019-05-08 | 주식회사 엘지화학 | 그라프트 공중합체, 이를 포함하는 열가소성 수지 조성물 및 이의 제조방법 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20120121003A (ko) * | 2011-04-26 | 2012-11-05 | 주식회사 라이온켐텍 | 아크릴 인조대리석 폐분진을 재활용한 bmc 상판의 제조 |
CN110229417B (zh) * | 2019-07-03 | 2022-02-18 | 海南蓝岛环保产业股份有限公司 | 一种基于人造大理石废渣填料的塑料制品及制备方法 |
-
2021
- 2021-05-24 KR KR1020210066306A patent/KR20220158464A/ko active Search and Examination
-
2022
- 2022-05-02 WO PCT/KR2022/006246 patent/WO2022250314A1/ko active Application Filing
- 2022-05-02 JP JP2023523280A patent/JP2023546443A/ja active Pending
- 2022-05-02 CN CN202280007199.3A patent/CN116368192A/zh active Pending
- 2022-05-02 EP EP22811507.7A patent/EP4215584A4/en active Pending
- 2022-05-02 US US18/034,044 patent/US20230391999A1/en active Pending
- 2022-05-09 TW TW111117273A patent/TW202311427A/zh unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09207134A (ja) * | 1995-11-28 | 1997-08-12 | Toto Ltd | 熱可塑性樹脂素材の成形材料及びその製造方法 |
JP2006175718A (ja) * | 2004-12-22 | 2006-07-06 | Kubota Matsushitadenko Exterior Works Ltd | 成形品の製造方法 |
JP2007039640A (ja) * | 2005-06-29 | 2007-02-15 | Kubota Matsushitadenko Exterior Works Ltd | 樹脂成形品 |
KR20080078241A (ko) * | 2007-02-22 | 2008-08-27 | 주식회사 엘지화학 | 인조대리석 폐기물의 분쇄물을 포함하는 바닥재 및 그제조방법 |
KR20090092882A (ko) | 2008-02-28 | 2009-09-02 | 조선대학교산학협력단 | 인조대리석 폐분말과 콜애시를 이용한 난연화 조성물 및이의 제조방법 |
KR20190047185A (ko) * | 2017-10-27 | 2019-05-08 | 주식회사 엘지화학 | 그라프트 공중합체, 이를 포함하는 열가소성 수지 조성물 및 이의 제조방법 |
Non-Patent Citations (1)
Title |
---|
See also references of EP4215584A4 |
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TW202311427A (zh) | 2023-03-16 |
EP4215584A4 (en) | 2024-05-15 |
JP2023546443A (ja) | 2023-11-02 |
US20230391999A1 (en) | 2023-12-07 |
KR20220158464A (ko) | 2022-12-01 |
CN116368192A (zh) | 2023-06-30 |
EP4215584A1 (en) | 2023-07-26 |
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