KR20080112035A - Light diffusion resin composition excellent in mechanical properties and weather resistance - Google Patents
Light diffusion resin composition excellent in mechanical properties and weather resistance Download PDFInfo
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- KR20080112035A KR20080112035A KR1020070060766A KR20070060766A KR20080112035A KR 20080112035 A KR20080112035 A KR 20080112035A KR 1020070060766 A KR1020070060766 A KR 1020070060766A KR 20070060766 A KR20070060766 A KR 20070060766A KR 20080112035 A KR20080112035 A KR 20080112035A
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- South Korea
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- resin
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- acrylate rubber
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- 239000011342 resin composition Substances 0.000 title claims abstract description 37
- 238000009792 diffusion process Methods 0.000 title claims description 29
- 239000011347 resin Substances 0.000 claims abstract description 119
- 229920005989 resin Polymers 0.000 claims abstract description 119
- -1 methacrylic acid alkyl ester compound Chemical class 0.000 claims abstract description 67
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 45
- 229920001971 elastomer Polymers 0.000 claims abstract description 44
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 44
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 20
- 229920001169 thermoplastic Polymers 0.000 claims description 50
- 239000004416 thermosoftening plastic Substances 0.000 claims description 50
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000010559 graft polymerization reaction Methods 0.000 claims description 5
- 239000004431 polycarbonate resin Substances 0.000 claims description 4
- 229920005668 polycarbonate resin Polymers 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 11
- 230000000052 comparative effect Effects 0.000 description 16
- 229940114077 acrylic acid Drugs 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000004816 latex Substances 0.000 description 6
- 229920000126 latex Polymers 0.000 description 6
- 239000008188 pellet Substances 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 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
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000012963 UV stabilizer Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 229940125773 compound 10 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 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 2
- 238000005259 measurement Methods 0.000 description 2
- 125000005641 methacryl group Chemical group 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920000390 Poly(styrene-block-methyl methacrylate) Polymers 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L13/00—Compositions of rubbers containing carboxyl groups
-
- 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
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
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- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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)
Abstract
본 발명은 알킬아크릴레이트 고무 수지를 매트릭스 수지로 포함하는 광확산성 수지 조성물에 관한 것이다. 상기 알킬아크릴레이트 고무 수지에는 메타크릴산 알킬에스테르 화합물 또는 아크릴산 알킬에스테르 화합물, 방향족비닐 화합물 및 비닐시안 화합물의 단량체 혼합물 또는 그들의 공중합체가 그라프트 중합될 수 있다. 본 발명의 광확산성 수지 조성물은 내충격성, 가공성 등 기계적 물성과 내후성이 우수하다.The present invention relates to a light diffusing resin composition comprising an alkyl acrylate rubber resin as a matrix resin. In the alkyl acrylate rubber resin, a monomer mixture of a methacrylic acid alkyl ester compound or an acrylic acid alkyl ester compound, an aromatic vinyl compound and a vinyl cyan compound or a copolymer thereof may be graft polymerized. The light diffusing resin composition of the present invention is excellent in mechanical properties such as impact resistance and workability and weather resistance.
Description
본 발명은 광확산성, 충격강도, 가공성 및 내후성이 우수한 광확산성 수지 조성물에 관한 것이다. 본 발명은 직사광이나 형광등 또는 LED등의 빛을 투과시키거나 확산시키는 성능이 우수하고, 내후성, 내충격성 및 가공성이 우수한 광확산성 수지 조성물에 관한 것이다. The present invention relates to a light diffusing resin composition excellent in light diffusivity, impact strength, processability and weatherability. The present invention relates to a light diffusing resin composition having excellent performance of transmitting or diffusing light such as direct sunlight, fluorescent lamps, or LED lamps, and having excellent weather resistance, impact resistance, and workability.
일반적으로 광확산성을 갖는 수지 조성물은 조명 커버, 조명 간판, 발광식 스위치 간판 등의 재료로 널리 사용되고 있으며, 최근에 디스플레이 산업의 발전 및 조명 산업의 변화 등으로 인하여 관심이 더욱 향상되고 있다. 특히, LED조명과 같은 경우, LED가 가지는 배광이 낮은 특성을 보완하기 위하여 빛의 확산성을 최대한 높여야 하며, 빛의 손실을 막기 위하여 광투과율은 높아야 한다. 또한, 조명간판, 옥외용 광고판 등에 이용하고자 할 때는 어느 정도 이상의 충격강도를 가져야 하고, 대형물의 압사출이 가능하도록 가공성도 가지고 있어야 한다. In general, a resin composition having light diffusibility is widely used as a material such as a lighting cover, a lighting signboard, a light-emitting switch signboard, and recently, interest has been further improved due to the development of the display industry and the change of the lighting industry. In particular, in the case of LED lighting, in order to compensate for the low light distribution of the LED, the light diffusivity must be increased as much as possible, and the light transmittance must be high to prevent the loss of light. In addition, when it is to be used for lighting signboards, outdoor billboards, etc., it must have a certain degree of impact strength, and must also have workability to enable the extrusion of large objects.
상기와 같은 목적을 달성하기 위하여 일반적으로 광확산성 수지 조성물은 기초수지(매트릭스 수지)에 광확산성과 광투과성을 확보하기 위하여 광확산제를 첨가하므로써 제조된다. 상기 매트릭스 수지로는 메타크릴계 수지, 스티렌계 수지, 폴리카보네이트계 수지 등의 열가소성 투명수지가 사용되고 있다. In order to achieve the above object, generally a light-diffusion resin composition is manufactured by adding a light-diffusion agent to ensure light-diffusion and light transmittance to a base resin (matrix resin). As the matrix resin, thermoplastic transparent resins such as methacryl resin, styrene resin, and polycarbonate resin are used.
그러나, 위에 언급한 열가소성 투명수지는 수지 본연의 특성으로 인하여 사용에 제한적이다. 즉, 메타크릴계 수지와 스티렌계 수지는 충격강도가 낮아서 잘 깨지는 문제점이 있다. 이러한 단점을 극복하기 위하여 메타크릴계 수지에 아크릴계 충격보강제를 함께 사용하는 경우도 있으나, 충격강도가 3이하로 매우 제한적인 충격강도의 향상을 보여주었다(대한민국 특허출원 제10-2002-86995). However, the above-mentioned thermoplastic transparent resin is limited in use due to the nature of the resin. That is, methacryl-based resin and styrene-based resin has a problem of breaking well because of low impact strength. In order to overcome these disadvantages, an acrylic impact modifier may also be used in the methacrylic resin, but the impact strength has been improved to a very limited impact strength of 3 or less (Korean Patent Application No. 10-2002-86995).
한편, 폴리카보네이트 수지를 사용할 경우 충격강도는 우수하나 가공성이 매우 낮기 때문에 복잡한 형태의 가공이 불가능하다. On the other hand, when the polycarbonate resin is used, the impact strength is excellent, but because the workability is very low, complicated processing is impossible.
다른 한편, 대한민국 특허등록 0511487호는 고무상 폴리머를 포함하는 메틸 메타크릴레이트 수지 또는 스티렌 수지 및 메틸 메타크릴레이트 수지 또는 스티렌 수지를 두층으로 적층하는 광확산성 적층 수지 시트에 대해 기재하고 있으나, 다층 시트를 제조하기 위해 복잡한 제조공정을 거쳐야 하는 단점이 있다.On the other hand, Korean Patent Registration No. 0511487 describes a light-diffusion laminated resin sheet in which a methyl methacrylate resin or a styrene resin containing a rubbery polymer and a methyl methacrylate resin or a styrene resin are laminated in two layers. There is a disadvantage that a complicated manufacturing process is required to produce the sheet.
또한 미국특허 제4,767,833호, 일본특허 제11-147920 및 유럽특허 제1045883호에는 ABS수지에 아크릴산 알킬에스테르나 메타크릴산 알킬에스테르를 도입하여 내충격성, 가공성 등이 우수하나, 수지의 특성상 내후성 및 내광성이 좋지 않아 옥외용으로 사용할 수 없으며, 시간이 경과함에 따라 물성이 크게 저하되는 문제점이 있다. 이러한 내후성 및 열안정성의 향상을 위하여 수지에 열안정제 및 UV안정제 등의 첨가제를 투입하여 수지를 제조하고 있으나, 근본적인 대책이 되지 못하고 있다. In addition, US Pat. No. 4,767,833, Japanese Patent No. 11-147920, and European Patent No. 1045883 introduce acrylic resins or methacrylic acid alkyl esters to ABS resins to provide excellent impact resistance and workability. This is not good and can not be used for outdoor use, there is a problem that the physical properties are greatly degraded over time. In order to improve such weather resistance and thermal stability, a resin is prepared by adding an additive such as a thermal stabilizer and a UV stabilizer to the resin, but it is not a fundamental measure.
따라서, 가공성, 충격강도 및 내후성 등 기계적 물성이 우수한 광확산성 수지의 개발이 요구되어 왔다. Therefore, there has been a demand for the development of a light diffusing resin having excellent mechanical properties such as workability, impact strength and weather resistance.
본 발명은 가공성, 충격강도 및 내후성 등 기계적 물성이 우수한 광확산성 수지 조성물을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a light diffusing resin composition having excellent mechanical properties such as workability, impact strength and weather resistance.
상기 목적에 따라,본 발명은 알킬아크릴레이트 고무 수지를 포함하는 열가소성 투명수지(A) 100중량부 및 광확산제(B) 0.1 내지 20중량부를 포함하며, 상기 열가소성 투명수지(A)와 상기 광확산제(B)의 굴절율 차이가 0.005이상인 것을 특징으로 하는 광확산성 수지 조성물을 제공한다.According to the above object, the present invention comprises 100 parts by weight of a thermoplastic transparent resin (A) and 0.1 to 20 parts by weight of a light diffusing agent (B) comprising an alkyl acrylate rubber resin, the thermoplastic transparent resin (A) and the light Provided is a light diffusing resin composition, wherein a difference in refractive index between the diffusing agent (B) is 0.005 or more.
상기 열가소성 투명수지(A)는 알킬아크릴레이트 고무 수지 5 내지 30중량부에 메타크릴산 알킬에스테르 화합물 또는 아크릴산 알킬에스테르 화합물 10 내지 90중량부 및 방향족비닐 화합물 5 내지 50중량부의 단량체 혼합물이 그라프트 중합된 것이다.The thermoplastic transparent resin (A) is a monomer mixture of 5 to 30 parts by weight of an alkyl acrylate rubber resin, a monomer mixture of 10 to 90 parts by weight of an alkyl acrylate compound or an acrylic acid alkyl ester compound and 5 to 50 parts by weight of an aromatic vinyl compound is graft-polymerized. It is.
또한, 상기 열가소성 투명수지(A)의 알킬아크릴레이트 고무 수지에 그라프트 중합되는 단량체 혼합물에는 비닐시안 화합물 1 내지 20중량부를 추가로 포함될 수 있다.In addition, the monomer mixture to be graft polymerized to the alkyl acrylate rubber resin of the thermoplastic transparent resin (A) may further include 1 to 20 parts by weight of the vinyl cyan compound.
한편, 본 발명의 광확산성 수지 조성물에 포함되는 열가소성 투명수지(A)는 알킬아크릴레이트 고무 수지에 메타크릴산 알킬에스테르 화합물 또는 아크릴산 알킬에스테르 화합물과 방향족비닐 화합물의 공중합체를 그라프트 중합시킨 것일 수 있다.On the other hand, the thermoplastic transparent resin (A) included in the light-diffusion resin composition of the present invention is one obtained by graft polymerization of an alkyl acrylate rubber resin with a copolymer of a methacrylic acid alkyl ester compound or an acrylic acid alkyl ester compound and an aromatic vinyl compound. Can be.
또한, 상기 알킬아크릴레이트 고무의 수지에 그라프트 중합되는 공중합체는 메타크릴산 알킬에스테르 화합물 또는 아크릴산 알킬에스테르 화합물, 방향족비닐 화합물 및 비닐시안 화합물의 공중합체 일 수 있다. In addition, the copolymer graft-polymerized to the resin of the alkyl acrylate rubber may be a copolymer of a methacrylic acid alkyl ester compound or an acrylic acid alkyl ester compound, an aromatic vinyl compound and a vinyl cyan compound.
본 발명의 광확산성 수지 조성물에서 열가소성 투명수지(A)내의 상기 알킬아크릴레이트 고무 수지와 메타크릴산 알킬에스테르 화합물 또는 아크릴산 알킬에스테르 화합물, 방향족비닐 화합물 및 비닐시안 화합물의 단량체 혼합물간의 굴절율 차이는 0.005 미만인 것이 바람직하다.In the light-diffusion resin composition of the present invention, the difference in refractive index between the alkyl acrylate rubber resin and the methacrylic acid alkyl ester compound or the acrylic acid alkyl ester compound, the aromatic vinyl compound, and the vinyl cyan compound in the thermoplastic transparent resin (A) is 0.005. It is preferable that it is less than.
상기 알킬아크릴레이트 고무 수지는 평균 입경이 600Å 내지 5000Å인 것이 바람직하다.It is preferable that the said alkyl acrylate rubber resin is 600 kPa-5000 kPa of average particle diameters.
그리고, 상기 광확산제(B)는 평균 입경 0.1~100 마이크론 미터의 구상인 것이 바람직하다.And it is preferable that the said light-diffusion agent (B) is spherical of 0.1-100 micrometers of average particle diameters.
상기 광확산제(B)는 탄산칼슘, 황산바륨, 이산화티탄, 수산화알루미늄, 실리카, 유리, 활석, 운모, 화이트카본, 산화마그네슘 및 산화아연으로 이루어지는 그룹에서 선택되는 1종 이상일 수 있다.The light diffusing agent (B) may be at least one selected from the group consisting of calcium carbonate, barium sulfate, titanium dioxide, aluminum hydroxide, silica, glass, talc, mica, white carbon, magnesium oxide and zinc oxide.
본 발명의 광확산성 수지 조성물에 포함되는 열가소성 투명수지(A)와 광확산 제(B)의 굴절율 차이는 0.005이상인 것이 바람직하다.It is preferable that the refractive index difference of the thermoplastic transparent resin (A) and the light-diffusion agent (B) contained in the light-diffusion resin composition of this invention is 0.005 or more.
본 발명의 광확산성 수지 조성물에 포함되는 열가소성 투명수지(A)는 메타크릴산 알킬에스테르 화합물 또는 아크릴산 알킬에스테르 화합물 10 내지 90중량부 및 방향족비닐 화합물 5 내지 60중량부를 공중합시키는 제1단계; 및 상기 공중합체를 알킬아크릴레이트 고무 5 내지 30중량부와 그라프트 중합시키는 제2단계로부터 제조되는 것일 수 있다.Thermoplastic transparent resin (A) contained in the light-diffusion resin composition of the present invention comprises the first step of copolymerizing 10 to 90 parts by weight of the methacrylic acid alkyl ester or acrylic acid alkyl ester compound and 5 to 60 parts by weight of the aromatic vinyl compound; And it may be prepared from the second step of graft polymerization of the copolymer with 5 to 30 parts by weight of alkyl acrylate rubber.
또한, 상기 제1단계에서 공중합시키는 화합물에는 비닐시안 화합물 1 내지 20중량부가 추가로 포함될 수 있다.In addition, the compound copolymerized in the first step may further include 1 to 20 parts by weight of the vinyl cyan compound.
또한, 상기 제 2 단계의 상기 알킬아크릴레이트 고무는 메타크릴산 알킬에스테르 화합물 또는 아크릴산 알킬에스테르 화합물, 및 방향족비닐 화합물과의 공중합체일 수 있다.In addition, the alkyl acrylate rubber of the second step may be a copolymer of a methacrylic acid alkyl ester compound or an acrylic acid alkyl ester compound, and an aromatic vinyl compound.
본 발명을 상세히 설명하면 다음과 같다.The present invention is described in detail as follows.
본 발명의 광확산성 수지 조성물은 매트릭스 수지로서 알킬아크릴레이트 고무 수지를 포함하는 열가소성 투명수지(A) 100중량부 및 도메인으로서 광확산제(B) 0.1 ~ 20중량부를 포함하고 상기 열가소성 투명수지와 상기 광확산제의 굴절율의 차이가 0.005 이상인 것을 특징으로 한다.The light diffusing resin composition of the present invention comprises 100 parts by weight of a thermoplastic transparent resin (A) containing an alkyl acrylate rubber resin as a matrix resin and 0.1 to 20 parts by weight of a light diffusing agent (B) as a domain. The difference in refractive index of the light diffusing agent is characterized in that 0.005 or more.
이하 상기 열가소성 투명수지(A) 및 광확산제(B)에 대해 설명한다.Hereinafter, the thermoplastic transparent resin (A) and the light diffusing agent (B) will be described.
(A) 열가소성 투명수지(A) Thermoplastic Transparent Resin
본 발명의 광확산성 수지 조성물은 매트릭스 수지로서 알킬아크릴레이트 고 무 수지를 포함하는 열가소성 투명수지(A)를 포함한다. The light-diffusion resin composition of this invention contains the thermoplastic transparent resin (A) containing an alkylacrylate rubber resin as a matrix resin.
본 발명의 열가소성 투명수지(A)는 상기 알킬아크릴레이트 고무 수지를 주쇄로 하여, 메타크릴산 알킬에스테르 화합물 또는 아크릴산 알킬에스테르 화합물, 방향족 비닐화합물 및 비닐시안 화합물의 단량체 혼합물을 그라프트 중합시킨 형태이다.The thermoplastic transparent resin (A) of the present invention is a form obtained by graft polymerization of a monomer mixture of a methacrylic acid alkyl ester compound or an acrylic acid alkyl ester compound, an aromatic vinyl compound and a vinyl cyan compound, using the alkyl acrylate rubber resin as a main chain. .
또는 상기 열가소성 투명수지(A)는 메타크릴산 알킬에스테르 화합물 또는 아크릴산 알킬에스테르 화합물, 방향족 비닐화합물 및 비닐시안 화합물의 단량체 화합물들의 단량체 혼합물을 미리 공중합시킨 후, 상기 공중합체를 알킬아크릴레이트 고무 수지에 그라프트 중합시킨 것일 수 있다.Alternatively, the thermoplastic transparent resin (A) may be a copolymer of a monomer mixture of a methacrylic acid alkyl ester compound or an acrylic acid alkyl ester compound, an aromatic vinyl compound and a monomer compound of a vinyl cyan compound in advance, and then the copolymer is added to an alkyl acrylate rubber resin. It may be graft polymerized.
본 발명의 광확산성 수지 조성물에서 열가소성 투명수지(A)로 사용되는 알킬아크릴레이트 고무 수지는 평균 입경이 600Å 내지 5000Å 범위의 것이 바람직하다. 알킬아크릴레이트 고무 수지의 입경이 상기 범위를 벗어날 경우, 내충격성 및 가공성 면에서 바람직한 결과를 가져오지 못하기 때문이다. 따라서, 상기 범위의 입경을 갖는 알킬아크릴레이트 고무 수지를 사용하여 본 발명의 광확산성 수지 조성물을 제공한다.The alkyl acrylate rubber resin used as the thermoplastic transparent resin (A) in the light-diffusion resin composition of the present invention preferably has an average particle diameter in the range of 600 kPa to 5000 kPa. If the particle diameter of the alkyl acrylate rubber resin is out of the above range, it is because the impact resistance and processability is not brought about a desirable result. Therefore, the light-diffusion resin composition of this invention is provided using the alkylacrylate rubber resin which has the particle diameter of the said range.
본 발명의 광확산성 수지 조성물 중 매트릭스 수지는 상기 알킬아크릴레이트 고무 수지 5 내지 30중량부(고형분 기준), 메타크릴산 알킬에스테르 화합물 또는 아크릴산 알킬에스테르 화합물 10 내지 90중량부 및 방향족비닐 화합물 5 내지 60중량부의 공중합체일 수 있다. 또한, 상기 매트릭스 수지는 비닐시안 화합물 1 내지 20중량부를 추가로 포함하는 공중합체일 수 있다. Matrix resin in the light-diffusion resin composition of the present invention is 5 to 30 parts by weight of the alkyl acrylate rubber resin (based on solids), methacrylic acid alkyl ester compound or acrylic acid alkyl ester compound 10 to 90 parts by weight and aromatic vinyl compound 5 to 60 parts by weight of copolymer. In addition, the matrix resin may be a copolymer further comprising 1 to 20 parts by weight of a vinyl cyan compound.
특히, 상기 매트릭스 수지의 공중합체는 알킬아크릴레이트 고무 수지를 주쇄로 하여 나머지 화합물 즉, 메타크릴산 알킬에스테르 화합물 또는 아크릴산 알킬에스테르 화합물, 방향족 비닐화합물 및 비닐시안 화합물이 그라프트 중합된 형태이다. 상기 그라프트 중합되는 화합물들은 단량체로서 알킬아크릴레이트 고무 수지의 주쇄에 직접 그라프트 중합될 수 있거나, 미리 중합된 상태로 제공되어 그라프트 중합될 수 있다.In particular, the copolymer of the matrix resin is a form in which the remaining compound, that is, methacrylic acid alkyl ester compound or acrylic acid alkyl ester compound, aromatic vinyl compound, and vinyl cyan compound are graft-polymerized with an alkyl acrylate rubber resin as a main chain. The graft polymerized compounds may be graft polymerized directly into the main chain of the alkyl acrylate rubber resin as a monomer, or may be provided in a prepolymerized state to be graft polymerized.
한편, 상기 알킬아크릴레이트 고무 수지는 불용성 성분을 포함하는 라텍스 형태의 중합체 용액으로 제공되므로, 본 발명에서 매트릭스 수지 제조에 사용되는 알킬아크릴레이트 고무 수지는 상기 라텍스 중합체에서의 불용성 고형분 즉, 겔 함량으로서 그 조성비를 나타낸 것이다.On the other hand, since the alkyl acrylate rubber resin is provided as a polymer solution in the form of a latex containing an insoluble component, the alkyl acrylate rubber resin used for preparing the matrix resin in the present invention is insoluble solids in the latex polymer, that is, the gel content It shows the composition ratio.
알킬아크릴레이트 고무 수지를 5중량부 미만으로 포함하면 광확산성 조성물은 내충격면에서 열악하여 깨지기 쉽고, 30중량부를 초과하여 포함하면 광확산성 조성물로부터 생산되는 완제품이 부드러워 손상되기 쉽다. When the content of the alkyl acrylate rubber resin is less than 5 parts by weight, the light-diffusion composition is poor in terms of impact resistance and is easily broken, and when it contains more than 30 parts by weight, the finished product produced from the light-diffusion composition is soft and easily damaged.
또한, 메타크릴산 알킬에스테르 화합물 또는 아크릴산 알킬에스테르 화합물 10 내지 90중량부 및 방향족비닐 화합물 5 내지 60중량부의 범위를 벗어날 경우 단량체 혼합물들로부터 제조되는 그라프트 중합체의 굴절율이 알킬아크릴레이트 고무 수지의 굴절율과 차이가 나, 열가소성 투명수지의 투명도에 영향을 미치므로 본 발명에 적합하지 않다.In addition, the refractive index of the graft polymer prepared from the monomer mixture when the methacrylic acid alkyl ester compound or acrylic acid alkyl ester compound 10 to 90 parts by weight and the aromatic vinyl compound 5 to 60 parts by weight is out of the range of the refractive index of the alkyl acrylate rubber resin It is not suitable for the present invention because it affects the transparency of the thermoplastic transparent resin.
본 발명의 열가소성 투명수지는 선택적으로 비닐시안 화합물을 1 내지 20중량부로 포함할 수 있다. 상기 비닐시안 화합물이 1중량부 미만일 경우 충격강도 향 상 효과가 적으며, 20중량부를 초과할 경우 색상이 노랗게 변하여 최종제품의 색상에 나쁜 영향을 미친다.The thermoplastic transparent resin of the present invention may optionally contain 1 to 20 parts by weight of a vinyl cyan compound. When the vinyl cyan compound is less than 1 part by weight, the effect of improving impact strength is small, and when it exceeds 20 parts by weight, the color turns yellow, which adversely affects the color of the final product.
본 발명의 광확산성 수지 조성물에서 매트릭스 수지는 알킬아크릴레이트 고무 수지를 주쇄로 메타크릴산 알킬에스테르 화합물 또는 아크릴산 알킬에스테르 화합물 및 방향족비닐 화합물의 혼합물, 또는 여기에 추가로 비닐시안 화합물의 단량체가 그라프트 중합되거나, 상기 화합물들의 단량체 혼합물들로부터 미리 제조된 공중합체가 그라프트 중합된 형태일 수 있다.In the light-diffusion resin composition of the present invention, the matrix resin is a methacrylic acid alkyl ester compound or a mixture of an acrylic acid alkyl ester compound and an aromatic vinyl compound with an alkyl acrylate rubber resin as a main chain, or a monomer of a vinyl cyan compound Or a copolymer previously prepared from monomer mixtures of the compounds may be in graft polymerized form.
이때 주쇄 알킬아크릴레이트 고무 수지에 그라프트 중합되는 메타크릴산 알킬에스테르 화합물 또는 아크릴산 알킬에스테르 화합물, 방향족비닐 화합물 및 비닐시안 화합물들의 혼합물 또는 그로부터 제조되는 공중합체의 굴절율은 열가소성 투명수지(A)의 투명성에 절대적으로 영향을 미친다. 즉, 그라프트 중합되는 화합물들의 성분 및 조성에 따라 열가소성 투명수지(A)의 투명성이 결정된다. In this case, the refractive index of the methacrylic acid alkyl ester compound or the acrylic acid alkyl ester compound, the aromatic vinyl compound, and the vinyl cyan compound mixture or copolymer prepared therefrom is grafted to the main chain alkyl acrylate rubber resin. Absolutely affects. That is, the transparency of the thermoplastic transparent resin (A) is determined according to the components and the composition of the compounds to be graft polymerized.
열가소성 투명수지(A)가 투명성을 가지기 위해서는 그라프트 중합체의 주쇄로 사용되는 알킬아크릴레이트 고무 수지의 굴절율과 상기 알킬아크릴레이트 고무 수지에 그라프트 중합되는 단량체 혼합물 또는 그들 중합체의 굴절율이 0.005 미만 이어야 하며, 바람직하게는 굴절율이 일치하는 것이다. In order for the thermoplastic transparent resin (A) to have transparency, the refractive index of the alkyl acrylate rubber resin used as the main chain of the graft polymer and the monomer mixture graft-polymerized on the alkyl acrylate rubber resin or those polymers should be less than 0.005. Preferably, the refractive index is the same.
반면, 알킬아크릴레이트 고무 수지의 굴절율과 그라프트 중합되는 단량체 혼합물 또는 그들 중합체의 굴절율 간의 차이가 0.005이상이면 열가소성 투명 수지(A)가 더 이상 투명성을 가지지 못하게 되어 바람직하지 않다. On the other hand, if the difference between the refractive index of the alkyl acrylate rubber resin and the refractive index of the graft polymerized monomer mixture or those polymers is 0.005 or more, the thermoplastic transparent resin (A) no longer has transparency, which is not preferable.
본 발명의 광확산성 수지 조성물 중 열가소성 투명수지(A)는 유화중합 또는 유화중합 및 괴상중합의 복합방법으로 제조될 수 있다. The thermoplastic transparent resin (A) in the light diffusing resin composition of the present invention may be prepared by an emulsion polymerization or a complex method of emulsion polymerization and bulk polymerization.
상기 유화중합법은 5 내지 30중량부의 알킬아크릴레이트 고무 수지에 메타크릴산 알킬에스테르 화합물 또는 아크릴산 알킬에스테르 화합물 10 내지 90중량부, 방향족비닐 화합물 5 내지 60중량부를 그라프트 중합시키는 것이다. 또한, 추가로 비닐시안 화합물을 1 내지 20중량부 그라프트 중합시킬 수 있다. 상기 제조방법으로 수득된 중합체는 라텍스 형태로서, 응집, 탈수 및 건조의 공정으로 드라이 파우더 형태로 회수할 수 있다.In the emulsion polymerization method, 10 to 90 parts by weight of a methacrylic acid alkyl ester compound or an acrylic acid alkyl ester compound and 5 to 60 parts by weight of an aromatic vinyl compound are graft polymerized to 5 to 30 parts by weight of an alkyl acrylate rubber resin. In addition, the vinyl cyan compound may be further subjected to 1 to 20 parts by weight graft polymerization. The polymer obtained by the above production method is in the form of latex, can be recovered in the form of dry powder by the process of flocculation, dehydration and drying.
한편, 열가소성 투명수지(A) 제조를 위한 유화중합 및 괴상중합의 복합법은 상술한 유화중합법으로 드라이 파우더 형태의 중합체를 제조하고, 다른 한편으로 상기 중합체와 동일한 굴절율을 가지도록 메타크릴산 알킬 에스테르, 방향족비닐 및 비닐시안 화합물의 공중합체를 제조한다. 그런 다음, 상기 드라이 파우더 형태의 중합체와 상기 공중합체를 압출기를 통하여 혼련하므로써 열가소성 투명수지(A)를 제조하는 것이다. On the other hand, the composite method of emulsion polymerization and bulk polymerization for the preparation of the thermoplastic transparent resin (A) is to produce a polymer in dry powder form by the above-mentioned emulsion polymerization method, on the other hand alkyl methacrylate to have the same refractive index as the polymer Copolymers of esters, aromatic vinyls and vinyl cyan compounds are prepared. Then, by mixing the polymer in the dry powder form and the copolymer through an extruder to prepare a thermoplastic transparent resin (A).
상기 유화중합 및 괴상중합의 복합법은 유화중합법에 비해 제조과정이 복잡하고 초기설비가 이루어져야 하는 단점이 있지만, 열가소성 투명수지(A) 내의 알킬아크릴레이트 고무 수지의 함량을 조절하기 용이하고 제조원가가 절감되는 장점이 있다.The complex method of the emulsion polymerization and the bulk polymerization has a disadvantage in that the manufacturing process is complicated compared to the emulsion polymerization method and the initial equipment has to be made, but it is easy to control the content of the alkyl acrylate rubber resin in the thermoplastic transparent resin (A) and the manufacturing cost It has the advantage of being saved.
본 발명의 광확산성 수지 조성물 중 열가소성 투명수지(A)에 포함되는 알킬아크릴레이트 단량체로는 메틸아크릴레이트, 에틸아크릴레이트, 프로필아크릴레이트, 부틸아크릴레이트 등의 알킬아크릴레이트로는 어떠한 것도 사용할 수 있으나, 부틸아크릴레이트가 주로 사용된다. As the alkyl acrylate monomer included in the thermoplastic transparent resin (A) in the light diffusing resin composition of the present invention, any of alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate can be used. However, butyl acrylate is mainly used.
또한 방향족 비닐 화합물은 스티렌, α-메틸스티렌, p-메틸스티렌 및 비닐톨루엔 중에서 선택되는 1종 이상일 수 있다. 특히 스티렌이 바람직하다. In addition, the aromatic vinyl compound may be at least one selected from styrene, α-methylstyrene, p-methylstyrene, and vinyltoluene. Styrene is particularly preferred.
또한, 비닐시안 화합물은 아크릴로니트릴 또는 메타크릴로니트릴일 수 있다.In addition, the vinyl cyan compound may be acrylonitrile or methacrylonitrile.
또한, (메타)아크릴산 알킬에스테르 화합물은 (메타)아크릴산 메틸에스테르, (메타)아크릴산 에틸에스테르, (메타)아크릴산 프로필에스테르, (메타)아크릴산 2-에틸헥실에스테르, (메타)아크릴산 데실에스테르 및 (메타)아크릴산 라우릴에스테르 중에서 선택되는 1종 이상일 수 있다. 특히 (메타)아크릴산 메틸에스테르인 메틸 메타크릴레이트가 바람직하다.Moreover, the (meth) acrylic-acid alkylester compound is a (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid decyl ester, and (meth) It may be one or more selected from lauryl ester. In particular, methyl methacrylate which is (meth) acrylic acid methyl ester is preferable.
(B)광확산제(B) light diffusing agent
다음으로, 본 발명의 광확산성 수지 조성물은 도메인으로서 광확산제를 포함한다. Next, the light-diffusion resin composition of this invention contains a light-diffusion agent as a domain.
상기 광확산제(B)로서 유기 또는 무기 광확산제를 단독 또는 병행하여 사용할 수 있다. As the light diffusing agent (B), an organic or inorganic light diffusing agent may be used alone or in combination.
본 발명의 광확산성 수지 조성물에 포함되는 광확산제(B)는 평균 입경이 1 내지 100마이크론 미터일 수 있다. 100마이크론 미터 이상의 입경을 가진 광확산제(B)를 사용할 경우, 바람직한 광확산도가 얻어지지 않기 때문이다. 바람직하게 상기 광확산제(B)는 평균 입경이 1 내지 10마이크론 미터이다. The light diffusing agent (B) included in the light diffusing resin composition of the present invention may have an average particle diameter of 1 to 100 microns. This is because when the light diffusing agent (B) having a particle diameter of 100 microns or more is used, a preferable light diffusing degree is not obtained. Preferably the light diffusing agent (B) has an average particle diameter of 1 to 10 microns.
본 발명의 광확산성 수지 조성물에 포함되는 무기 광확산제는 특별한 제한을 두지 않으며 탄산칼슘, 황산바륨, 이산화티탄, 수산화알루미늄, 실리카, 유리, 활석, 운모, 화이트카본, 산화마그네슘 및 산화아연으로 이루어진 그룹에서 선택된 1종 이상일 수 있다. The inorganic light diffusing agent included in the light diffusing resin composition of the present invention is not particularly limited and includes calcium carbonate, barium sulfate, titanium dioxide, aluminum hydroxide, silica, glass, talc, mica, white carbon, magnesium oxide, and zinc oxide. It may be one or more selected from the group consisting of.
상기 무기 광확산제는 평균 입경이 0.1 내지 20 마이크론 미터일 수 있고, 본 발명의 광확산성 수지 조성물 내의 함량은 열가소성 투명수지(A) 100중량부에 0.1 내지 20중량부로 사용될 수 있다. The inorganic light diffusing agent may have an average particle diameter of 0.1 to 20 microns, and the content in the light diffusing resin composition of the present invention may be used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the thermoplastic transparent resin (A).
본 발명의 광확산성 수지 조성물에 포함되는 유기 광확산제는 아크릴계 수지, 실록산계 수지, 폴리카보네이트계 수지 또는 스티렌계 수지일 수 있다. 상기 유기 광확산제의 평균입경은 1 내지 100마이크론 미터일 수 있고, 본 발명의 광확산성 수지 조성물 내의 함량은 열가소성 투명수지(A) 100중량부에 대하여 0.1 내지 20중량부로 사용될 수 있다.The organic light diffusing agent included in the light diffusing resin composition of the present invention may be an acrylic resin, a siloxane resin, a polycarbonate resin, or a styrene resin. The average particle diameter of the organic light diffusing agent may be 1 to 100 microns, the content in the light diffusing resin composition of the present invention may be used in 0.1 to 20 parts by weight based on 100 parts by weight of the thermoplastic transparent resin (A).
0.1중량부 미만의 광확산제를 사용하는 경우 원하는 수준의 광확산도를 얻을 수 없고, 20중량부를 초과하여 사용할 경우에는 광확산성 수지 조성물 중 열가소성 투명수지(A)의 상대적인 농도가 낮아져 제품의 내충격성이 감소되는 결과를 가져온다. 또한, 광투과율이 현저히 낮아지는 결과를 가져온다.When using a light diffusing agent of less than 0.1 parts by weight can not obtain the desired level of light diffusion, when used in excess of 20 parts by weight the relative concentration of the thermoplastic transparent resin (A) in the light diffusing resin composition is lowered in the product This results in reduced impact. In addition, it results in a significantly lower light transmittance.
본 발명의 광확산성 수지 조성물에서 열가소성 투명수지(A)와 광확산제(B)의 굴절율 차이는 0.005이상인 것이 바람직하며, 굴절율의 차이가 0.01이상인 것이 더욱 바람직하다. In the light diffusing resin composition of the present invention, the difference in refractive index between the thermoplastic transparent resin (A) and the light diffusing agent (B) is preferably 0.005 or more, and more preferably 0.01 or more.
굴절율의 차이가 0.005미만일 경우 광확산성이 떨어져서 많은 양의 광확산제를 사용해야 하는 문제가 발생하기 때문이다. This is because when the difference in refractive index is less than 0.005, light diffusivity is poor and a large amount of light diffusing agent needs to be used.
본 발명의 광확산성 조성물에는 상기 (A) 열가소성 투명수지 및 (B)광확산제 외에 그 물성에 영향을 주지 않는 범위에서 열안정제, UV안정제, 형광증백제 등이 포함될 수 있다. 상기 조성물을 일축 압출기, 이축 압출기 또는 밴버리 믹서 등을 사용하여 균일하게 분산시킨다. 그 다음, 수조를 통과시키고, 절단하여 펠렛 형태의 광확산성 수지를 제조한다. The light diffusing composition of the present invention may include a heat stabilizer, a UV stabilizer, a fluorescent brightener, etc. in a range that does not affect the physical properties other than the (A) thermoplastic transparent resin and (B) the light diffusing agent. The composition is uniformly dispersed using a single screw extruder, twin screw extruder or Banbury mixer or the like. Then, the tank is passed through and cut to prepare a light diffusing resin in pellet form.
이하, 본 발명을 실시예를 들어 더욱 상세히 설명하고자 하나 이는 발명의 구체적 이해를 돕기 위한 것으로, 본 발명이 하기 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, which are intended to help a specific understanding of the present invention, and the present invention is not limited to the following Examples.
제조예 1Preparation Example 1
부틸아크릴레이트 라텍스 중합체 20중량부(용매에 녹지 않는 겔 함량 70%, 평균 입경 0.3㎛)에 이온교환수 90중량부, 올레인산나트륨 유화제 0.2 중량부, 메틸메타크릴레이트 63중량부, 스티렌 14중량부, 아크릴로니트릴 3 중량부, 3급 도데실 메르캅탄 0.25 중량부, 피로인산나트륨 0.048중량부, 덱스토로즈 0.012중량부, 황화제1철 0.001중량부 및 큐멘하이드로퍼옥사이드 0.10중량부를 73℃에서 5시간 동안 연속적으로 투여하고 반응을 시켰다. 반응 후 76℃로 승온한 후 1시간 동안 숙성 시키고 반응을 종료시켰다. 이때 중합 전환율은 99.5%이었고 고형 응고분은 0.1%였다. 90 parts by weight of ion-exchanged water, 0.2 parts by weight of sodium oleate emulsifier, 63 parts by weight of methyl methacrylate, 14 parts by weight of butyl acrylate latex polymer (70% of solvent-insoluble gel content, average particle diameter of 0.3 μm) 3 parts by weight of acrylonitrile, 0.25 parts by weight of tertiary dodecyl mercaptan, 0.048 parts by weight of sodium pyrophosphate, 0.012 parts by weight of dextrose, 0.001 parts of ferrous sulfide and 0.10 parts of cumene hydroperoxide at 73 ° C. Continuous administration for 5 hours and reaction. After the reaction was raised to 76 ℃ aging for 1 hour and the reaction was terminated. At this time, the polymerization conversion was 99.5% and the solidified content was 0.1%.
다음으로 염화칼슘 수용액으로 응고시키고 세척하여 분말상의 열가소성 투명 수지(A-1)를 얻었다. 얻어진 열가소성 투명수지의 굴절율은 1.508이었고, 중량 평균 분자량은 120,000이었다Next, it solidified and wash | cleaned with the calcium chloride aqueous solution, and obtained powdery thermoplastic transparent resin (A-1). The refractive index of the obtained thermoplastic transparent resin was 1.508, and the weight average molecular weight was 120,000.
제조예 2Preparation Example 2
(1) 부틸아크릴레이트 라텍스 중합체 30중량부(용매에 녹지 않는 겔 함량 70%, 평균 입경이 0.3㎛), 메틸메타크릴레이트 56중량부, 스티렌 12 중량부, 아크릴로니트릴 2중량부 를 사용하는 것을 제외하고 상기 제조예 1과 동일한 방법으로 열가소성 투명수지를 합성하였다. (1) 30 parts by weight of a butyl acrylate latex polymer (70% insoluble gel content, average particle diameter of 0.3 μm), 56 parts by weight of methyl methacrylate, 12 parts by weight of styrene, and 2 parts by weight of acrylonitrile A thermoplastic transparent resin was synthesized in the same manner as in Preparation Example 1, except that.
(2) 메틸메타아크릴레이트 75중량부, 스티렌15 중량부, 아크릴로니트릴 10중량부에 용매로서 톨루엔 30중량부와 분자량 조절제로서 디터셔리 도데실 메르캅탄 0.15중량부를 혼합한 원료를 평균 반응 시간이 3시간 되도록 반응조에 연속적으로 투입하여 반응 온도를 148℃로 유지하였다. 반응조에서 배출된 중합액은 예비 가열조에서 가열하고 휘발조에서 미반응 단량체를 휘발시켰다. (2) The average reaction time of a raw material obtained by mixing 75 parts by weight of methyl methacrylate, 15 parts by weight of styrene and 10 parts by weight of acrylonitrile was mixed with 30 parts by weight of toluene as a solvent and 0.15 parts by weight of dodecyl mercaptan as a molecular weight regulator. The reaction temperature was continuously added to the reactor for 3 hours to maintain the reaction temperature at 148 ° C. The polymerization liquid discharged from the reactor was heated in a preheating bath and volatilized unreacted monomer in a volatilization bath.
다음으로 210℃의 온도가 유지되도록 하여 폴리머 이송 펌프 압출 가공기를 이용하여 펠렛 형태의 공중합체를 제조하였다. Next, to maintain the temperature of 210 ℃ to prepare a copolymer in pellet form using a polymer transfer pump extrusion machine.
(3) 상기 (1)의 열가소성 투명수지 66중량부 및 (2)의 공중합체 34중량부를 믹서에서 혼합한 후, 220℃의 실린더 온도에서 2축 압출 혼련기를 사용하여 펠렛 형태의 열가소성 투명수지(A-2)를 제조하였다. 제조된 공중합체의 중량 평균 분자량은 120,000이었으며, 굴절율은 1.508이었다.(3) After mixing 66 parts by weight of the thermoplastic transparent resin of (1) and 34 parts by weight of the copolymer of (2) in a mixer, using a twin screw extrusion kneader at a cylinder temperature of 220 ℃ using a pellet-shaped thermoplastic transparent resin ( A-2) was prepared. The weight average molecular weight of the prepared copolymer was 120,000, the refractive index was 1.508.
제조예 3Preparation Example 3
메틸메타아크릴레이트 100중량부로 사용하고, 스티렌 및 아크릴로니트릴은 사용하지 않는 것을 제외하고 제조예 2(2)와 동일한 방법으로 열가소성 투명수지(A-3)를 제조하였다. 얻어진 열가소성 투명수지의 중량 평균 분자량은 130,000였으며, 굴절율은 1.49이었다.A thermoplastic transparent resin (A-3) was prepared in the same manner as in Preparation Example 2 (2), except that 100 parts by weight of methyl methacrylate was used and styrene and acrylonitrile were not used. The weight average molecular weight of the obtained thermoplastic transparent resin was 130,000, and the refractive index was 1.49.
제조예 4Preparation Example 4
(1) 부타디엔 라텍스 중합체 20 중량부(용매에 녹지 않는 겔 함량 70%, 평균 입경이 0.3㎛), 메틸메타크릴레이트 55중량부, 스티렌 20중량부, 아크릴로니트릴 5중량부를 사용하는 것을 제외하고 상기 제조예 1과 동일한 방법으로 열가소성 투명수지(A-4)를 합성하였다. 제조된 공중합체의 중량 평균 분자량은 100,000이었으며, 굴절율은 1.517이었다.(1) 20 parts by weight of butadiene latex polymer (70% insoluble gel content, average particle diameter of 0.3 μm), 55 parts by weight of methyl methacrylate, 20 parts by weight of styrene, and 5 parts by weight of acrylonitrile are used. In the same manner as in Preparation Example 1, a thermoplastic transparent resin (A-4) was synthesized. The copolymer had a weight average molecular weight of 100,000 and a refractive index of 1.517.
실시예 1 내지 3 및 비교예 1 내지 6Examples 1 to 3 and Comparative Examples 1 to 6
상기 제조예 1 내지 4의 열가소성 투명수지(A)와 하기 표 1의 광확산제(B)를 하기 표 2와 같은 비율로 혼합하고, 활제 0.1 중량부 및 산화 방지제 0.2 중량부를 투여하여 220℃의 실린더 온도에서 2축 압출 혼련기를 사용하여 펠렛 형태로 제조하였다. The thermoplastic transparent resin (A) of Preparation Examples 1 to 4 and the light diffusing agent (B) of Table 1 were mixed in the same ratio as in Table 2 below, and 0.1 parts by weight of lubricant and 0.2 parts by weight of antioxidant were administered at 220 ° C. Prepared in pellet form using a twin screw extruder at cylinder temperature.
[표 1] TABLE 1
[표 2]TABLE 2
상기 펠렛을 사출하여 시편을 제조하고 하기의 방법으로 물성을 측정하였다.The pellet was injected to prepare a specimen and the physical properties were measured by the following method.
1. 광확산도 1. Light Diffusion
ASTM D-1003를 사용하여 2 mm의 시트(sheet)의 헤이즈 값(Haze Value)을 측정하는 것으로 광 확산도를 측정하였다.Light diffusivity was measured by measuring the Haze Value of a sheet of 2 mm using ASTM D-1003.
2. 광 투과율 (Total Transmittance)2. Total Transmittance
ASTM D-1003를 사용하여 2 mm의 시트(sheet)의 전광선 투과율을 측정하였다.The total light transmittance of a sheet of 2 mm was measured using ASTM D-1003.
3. 충격 강도 (Notched Izod Impact Strength)3. Notched Izod Impact Strength
ASTM D-256를 사용하여 1/8" 시편의 나치드 아이조드(Notched Izod) 충격 강도를 측정하였다.Notched Izod impact strength of 1/8 "specimens was measured using ASTM D-256.
4. 유동성 (Melt Index)4. Melt Index
ASTM D-1238을 사용하여 220℃ 및 10 kg의 조건에서 압출된 펠렛의 유동성을 측정하였다.The flowability of the extruded pellets was measured at 220 ° C. and 10 kg using ASTM D-1238.
5. 표면 광택 5.surface polished
ASTM D528(45°각도)방법을 사용하여 측정하였다. Measurements were made using the ASTM D528 (45 ° Angle) method.
6. 내후성6. Weather resistance
웨더-o-미터(Weatherometer,ATLAS사 Ci35A)에 83℃, 워터 스프레이 싸이클(water spray cycle) 18분/120분으로 하여 수지를 400시간 방치 후 After leaving the resin at 400 ° C for 18 hours / 120 minutes at 83 ° C in a weather-o-meter (Weatherometer, AT35 Ci35A)
광택을 측정하였다. Gloss was measured.
상기 물성 측정 결과를 하기 표3에 기재하였다.The physical property measurement results are shown in Table 3 below.
[표 3] TABLE 3
실시예 1 내지 3의 경우 광확산성(haze value)와 전광선 투과율(Tt)이 높으면서, 충격강도 및 가공성도 높은 것으로 나타났다.In Examples 1 to 3, the haze value and the total light transmittance (Tt) were high, and the impact strength and the workability were also high.
반면, 비교예 1의 경우 열가소성 투명수지(A)와 광확산제(B)의 굴절율 차이가 0.004로서 굴절율의 차이가 너무 작아 원하는 수준의 광확산 특성을 얻지 못하 였다.On the other hand, in Comparative Example 1, the difference in refractive index between the thermoplastic transparent resin (A) and the light diffusing agent (B) was 0.004, and the difference in refractive index was too small to obtain a desired level of light diffusion.
비교예 2의 경우 광확산제(B)의 평균입경이 너무 커서 원하는 수준의 광확산 특성을 얻지 못하였다.In Comparative Example 2, the average particle diameter of the light diffusing agent (B) was too large to obtain a desired level of light diffusing characteristics.
비교예 3은 광확산제(B)의 과도한 사용으로 충격강도가 낮고, 광 투과율이 매우 낮아졌다.In Comparative Example 3, the impact strength was low due to excessive use of the light diffusing agent (B), and the light transmittance was very low.
비교예 4의 경우 열가소성 투명수지로 폴리메틸메타크릴레이트를 사용함으로써 원하는 수준의 충격강도를 얻지 못하였다.In Comparative Example 4, the use of polymethyl methacrylate as the thermoplastic transparent resin did not obtain a desired level of impact strength.
비교예 5로 사용된 공액디엔계 수지의 경우 충격강도 및 가공성 등은 우수하지만 내후성이 좋지 않았다. The conjugated diene-based resin used in Comparative Example 5 was excellent in impact strength and workability, but poor in weatherability.
본 발명에 의하면 알킬아크릴레이트 고무 수지를 매트릭스 수지로 사용하는 것에 의해 제조공정이 간단하면서 내충격성 및 가공성이 향상된 광확산성 수지 조성물을 제공할 수 있다.According to the present invention, by using an alkyl acrylate rubber resin as a matrix resin, it is possible to provide a light-diffusion resin composition having a simple manufacturing process and improved impact resistance and workability.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011081426A3 (en) * | 2009-12-29 | 2011-12-01 | 제일모직주식회사 | Acrylic resin having excellent transparency, fluidity and scratch-resistant property |
| KR101378187B1 (en) * | 2011-05-19 | 2014-03-26 | 주식회사 엘지화학 | Light diffusion resin composition with improved weatherability and surface contamination |
| KR20140147225A (en) * | 2013-06-19 | 2014-12-30 | 주식회사 엘지화학 | Light diffusing composition and light diffusing resin composition comprising thereof |
| CN104672879A (en) * | 2015-02-13 | 2015-06-03 | 厦门市天宇塑料工业有限公司 | Stress-crack-resistant light diffusion PC material for LED aluminum-coated lamp cup and preparation method of PC material |
| WO2018110938A1 (en) * | 2016-12-14 | 2018-06-21 | 롯데첨단소재(주) | Thermoplastic resin composition and molded article produced therefrom |
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| CN109906247B (en) | 2016-12-27 | 2021-10-29 | 乐天尖端材料株式会社 | Thermoplastic resin compositions and articles made therefrom |
| WO2018124639A2 (en) * | 2016-12-27 | 2018-07-05 | 롯데첨단소재(주) | Thermoplastic resin composition and article produced therefrom |
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| GB9314604D0 (en) | 1993-07-14 | 1993-08-25 | Dow Deutschland Inc | Light diffuser composition |
| JPH11105207A (en) * | 1997-10-02 | 1999-04-20 | Sumitomo Chem Co Ltd | Light diffusing laminated resin plate |
| KR100358234B1 (en) * | 1998-12-08 | 2003-02-19 | 주식회사 엘지화학 | Transparent thermoplastic resin composition excellent in weather resistance and a method of manufacturing the same |
| JP2000296581A (en) * | 1999-04-16 | 2000-10-24 | Asahi Chem Ind Co Ltd | Light diffusing resin panel excellent in impact resistance |
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| WO2011081426A3 (en) * | 2009-12-29 | 2011-12-01 | 제일모직주식회사 | Acrylic resin having excellent transparency, fluidity and scratch-resistant property |
| US8933185B2 (en) | 2009-12-29 | 2015-01-13 | Cheil Industries Inc. | Acrylic resin having excellent transparency, fluidity and scratch-resistance |
| KR101378187B1 (en) * | 2011-05-19 | 2014-03-26 | 주식회사 엘지화학 | Light diffusion resin composition with improved weatherability and surface contamination |
| KR20140147225A (en) * | 2013-06-19 | 2014-12-30 | 주식회사 엘지화학 | Light diffusing composition and light diffusing resin composition comprising thereof |
| CN104672879A (en) * | 2015-02-13 | 2015-06-03 | 厦门市天宇塑料工业有限公司 | Stress-crack-resistant light diffusion PC material for LED aluminum-coated lamp cup and preparation method of PC material |
| WO2018110938A1 (en) * | 2016-12-14 | 2018-06-21 | 롯데첨단소재(주) | Thermoplastic resin composition and molded article produced therefrom |
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