WO2016080758A1 - 폴리메틸메타크릴레이트 아크릴계 공중합체 얼로이 고광택 조성물 및 성형품 - Google Patents
폴리메틸메타크릴레이트 아크릴계 공중합체 얼로이 고광택 조성물 및 성형품 Download PDFInfo
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- WO2016080758A1 WO2016080758A1 PCT/KR2015/012414 KR2015012414W WO2016080758A1 WO 2016080758 A1 WO2016080758 A1 WO 2016080758A1 KR 2015012414 W KR2015012414 W KR 2015012414W WO 2016080758 A1 WO2016080758 A1 WO 2016080758A1
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- acrylic
- weight
- acrylic copolymer
- high gloss
- polymethylmethacrylate
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- 0 CC(*)(*)ON=O Chemical compound CC(*)(*)ON=O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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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
- 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
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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
- 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
- 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
Definitions
- the present invention relates to a polymethyl methacrylate-acrylic copolymer alloy high gloss composition and a molded article, and more specifically, to an impact modifier of a polymethyl methacrylate resin and an acrylic copolymer alloy, a specific amount of an acrylic impact modifier is a scratch reinforcement agent.
- Polymethylmethacrylate-acrylic copolymer alloy in combination with polymethylmethacrylate can provide improved surface gloss and transparency (color) while providing the mechanical strength, processability and scratch resistance required for alloy high gloss compositions. It relates to an acrylic copolymer alloy high gloss composition and a molded article obtained therefrom.
- Polymethyl methacrylate is a synthetic resin containing MMA monomer as its main raw material. It has the highest transparency among all plastics and has a high surface hardness and excellent scratch resistance. In addition, it is excellent in weather resistance and excellent in chemicals, surface gloss, and adhesion. Due to the above characteristics, it is widely used as a material for automobiles and electric and electronic parts, but it is used only for limited uses or to increase the thickness of the product due to its impact resistance. In order to improve the impact resistance of the PMMA resin, there is a method of modifying using acrylonitrile-butadiene-styrene (ABS) resin, but there is a disadvantage in that weather resistance is weak due to the double bond of butadiene.
- ABS acrylonitrile-butadiene-styrene
- the impact resistance was improved by modifying PMMA resin with acrylonitrile-styrene-butylacrylate (ASA) and silicone-based impact modifier instead of ABS resin.
- ASA acrylonitrile-styrene-butylacrylate
- silicone-based impact modifier instead of ABS resin.
- the modified PMMA resin has a problem in that scratch resistance is lowered and glossiness and transparency are reduced as compared with the conventional PMMA resin (related prior art information: Korean Patent Publication No. 2002-0022351).
- the present invention is a polymethyl methacrylate-acrylic copolymer by using a specific amount of the acrylic impact modifier with a scratch enhancer as the impact modifier of the polymethyl methacrylate resin and the acrylic copolymer alloy
- the polymethylmethacrylate-acrylic copolymer alloy high gloss composition and the molded article obtained therefrom which can provide the mechanical strength, processability and scratch resistance required for the alloy high gloss composition while at the same time providing improved surface gloss and color
- the purpose is to provide.
- Polymethyl methacrylate-acrylic characterized in that 100 parts by weight of polymethyl methacrylate resin, 12 to 50 parts by weight of acrylic copolymer, 6 to 25 parts by weight of acrylic impact modifier, and 0.5 to 5 parts by weight of scratch enhancer A copolymer alloy high gloss composition is provided.
- the present invention also provides a molded article comprising the polymethyl methacrylate-acrylic copolymer alloy high-gloss composition described above.
- the mechanical strength required for the polymethylmethacrylate-acrylic copolymer alloy high gloss composition by using a specific amount of the acrylic impact modifier as a impact modifier of the polymethyl methacrylate resin and the acrylic copolymer alloy together with a scratch enhancer It is possible to provide improved surface gloss and color while providing strength, processability and scratch resistance, and to eliminate post-injection (painting process) economical polymethylmethacrylate-acrylic copolymer alloy high gloss composition and There is an effect of providing a molded article obtained therefrom.
- Polymethyl methacrylate-acrylic copolymer alloy high-gloss composition of the present invention is 100 parts by weight of polymethyl methacrylate resin, 12 to 50 parts by weight of acrylic copolymer, 6 to 25 parts by weight of acrylic impact modifier, and scratch enhancer 0.5 To 5 parts by weight.
- the polymethyl methacrylate resin is not particularly limited in the case of a polymer commonly referred to as polymethyl methacrylate resin or PMMA resin in the technical field to which the present invention belongs, for example, homopolymer of methyl methacrylate, methyl methacrylate Copolymers of rates and acrylates, or mixtures thereof.
- the acrylic copolymer may be, for example, an acrylic rubber core-graft shell copolymer, or an alkyl acrylate-vinylaromatic compound-vinylcyan compound graft copolymer, and specific examples of styrene in 40 to 50% by weight of the acrylic rubber 50 to 60% by weight of the sum of the monomer and acrylonitrile monomer may be a grafted copolymer.
- the content of acrylonitrile monomer in the shell is 20 to 35% by weight of 100% by weight of the total rubber and monomer constituting the copolymer Can be in range.
- Alkyl in the alkyl acrylate may be, for example, alkyl having 1 to 20, or 1 to 10 carbon atoms.
- the acrylic rubber may be, for example, an alkyl acrylate rubber
- the styrene monomer may be a vinylaromatic compound including styrene
- the acrylonitrile monomer may be a vinyl cyan compound including acrylonitrile
- the acrylic copolymer is, for example, included in the range of 12 to 50 parts by weight, 18 to 35 parts by weight, or 18 to 32 parts by weight based on 100 parts by weight of the polymethyl methacrylate resin, within this range impact resistance and color It can provide an improvement effect on, scratch resistance, and surface gloss.
- the acrylic impact modifier may be, for example, a resin in which an acrylonitrile-styrene copolymer and an acrylic monomer are crosslinked.
- the acrylonitrile-styrene copolymer may be a vinyl cyan compound-vinylaromatic compound copolymer including an acrylonitrile-styrene copolymer.
- the acrylic impact modifier may cover the acrylic rubber such as butyl acrylate rubber that has the greatest influence on colorability as well as improve colorability and glossiness.
- the gloss and color it is used to form a structure of 5 to 10% by weight of the styrene seed, 50 to 60% by weight of the acrylic core surrounding the seed, and 30 to 40% by weight of the styrene shell surrounding the core, the gloss and color It is preferable because there is an effect of improving (transparency).
- the styrene seed and the styrene shell may be each independently selected from a styrene homopolymer and a styrene-acrylonitrile copolymer.
- the styrene seed and / or the acrylic core may each independently include a crosslinkable monomer within a range of 0.1 to 5% by weight, or 0.5 to 3% by weight, based on 100% by weight of the total components of the acrylic impact modifier. And a crosslinked structure between the acrylic core and the acrylic core, or a crosslinked structure between the acrylic core and the styrene shell.
- the styrene seed and the styrene shell may refer to a polymer seed or a polymer shell including a vinylaromatic compound, respectively.
- the acrylic core may be a polymer polymerized including alkyl acrylate.
- the crosslinkable monomer is, for example, divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, arylmetha Acrylate and 1,3-butylene glycol diacrylate It may be one or more selected from.
- the acrylic impact modifier is included in the range of 6 to 25 parts by weight, 6 to 15 parts by weight, or 6 to 11 parts by weight based on 100 parts by weight of the polymethyl methacrylate resin, and the color and the surface within this range. It can provide an improvement effect on impact resistance without affecting gloss.
- the scratch reinforcing agent may be, for example, a siloxane polymer or an organic modified siloxane polymer.
- the siloxane-based polymer may be an organosiloxane-based polymer, and the organosiloxane-based polymer may be a polydialkylsiloxane polymer having alkyl of 1 to 10 carbon atoms.
- the organic modified siloxane-based polymer may be an alkyl group, an aryl group, an allyl group, an alkenyl group, an amino group, a halogenated alkyl group, an epoxy group, a carboxyl group, a hydroxy group, an alkoxy group, or a methylhydrogen group in the main chain of the siloxane polymer.
- This substituted polymer can be used.
- the organic modified siloxane-based polymer may be a polymer in which the functional group of the formula (2) or the functional group of the formula (3) is substituted at the terminal position (X position) of the polydimethylsiloxane of the formula (1),
- the polymer in which the functional group of is substituted can be used preferably.
- the scratch adjuvant may be used in the form of oil or gum (gum).
- X is represented by the following Formula 2 or 3, n is an integer of 1 or more.
- N may be, for example, 1 to 1,000, or 10 to 500.
- the o and p may be 1 to 100, or 1 to 50, respectively.
- the scratch reinforcing agent for example, based on 100 parts by weight of polymethyl methacrylate resin, 0.5 to 5 parts by weight, or It is included in the range of 0.6 to 4.5 parts by weight, and within this range, it is possible to provide an improvement effect on scratch resistance without affecting color and surface gloss.
- the alloy composition may include one or more additives selected from impact modifiers, lubricants, heat stabilizers, ultraviolet light stabilizers, anti-drip agents, pigments, dyes, and inorganic fillers, as necessary.
- the alloy composition may have a scratch resistance ( ⁇ L ) of, for example, more than 0.5 to less than 1.5, more than 0.5 to less than 1.1, less than 0.6 to less than 1.5, or 0.6 to 1.1, as measured by the Ericshen test method.
- the alloy composition may have a glossiness (45 °) measured by the ASTM D2457 method, for example, in the range of more than 87.0, 89.0 or more, more than 87.0 to 92.0 or less, or 89.0 to 92.0.
- the alloy composition is measured by COLOR-EYE 7000 Series (CE 7000A), the color value represented by L * is for example greater than 2.9, less than 5.5, 3.5 or more to less than 5.5, more than 2.9 to 4.0, or It may be in the range of 3.5 to 4.0.
- the alloy composition has an Izod impact strength of greater than 3.5 kg.cm/cm, less than 6.5 kg.cm/cm, greater than 3.5 kg.cm/cm to 5.5 kg.cm/cm, 3.8 kg as determined by ASTM D256 method. cm / cm to less than 6.5 kg.cm/cm, or from 3.8 kg.cm/cm to 5.5 kg.cm/cm.
- the alloy composition has a melt index (g / 10 min) measured at 220 ° C. and 10.0 kg load by ASTM D1228 method, for example, greater than 3.8 g / 10 min, less than 7.6 g / 10 min, greater than 3.8 g / 10 min to 5.0 g. / 10min, 4.0 g / 10min to 7.6 g / 10min, or 4.0 g / 10min to 5.0 g / 10min.
- a melt index g / 10 min measured at 220 ° C. and 10.0 kg load by ASTM D1228 method
- the molded article may be, for example, an injection molded article.
- the molded article may be, for example, an automotive exterior material such as a side miller or a pillar garnish, and may be applied as an unpainted product because it has excellent surface resistance as well as scratch resistance. It can provide enhanced black feeling and slip feeling.
- ASA 40 to 50% by weight of styrene / acrylonitrile is grafted to 40 to 50% by weight of acrylic rubber with poly (acrylonitrile-styrene-butylacrylate; coalescence.
- Silicone-based impact modifier manufactured by MITSUBISHI RAYON, which has a silicone / acryl core and a methyl methacrylate copolymer shell.
- Acrylic impact modifier 5 to 10% by weight of a styrene seed (styrene homopolymer), 50 to 60% by weight of the acrylic core surrounding the seed, and 30 to 40% by weight of the styrene shell surrounding the core, the styrene Copolymer comprising, based on the seed and the acrylic core, divinylbenzene in an amount of 1% by weight of the total 100% by weight of the total components constituting the acrylic impact modifier (from GANZ CHEMICAL)
- the black pigment was added together and then melt-extruded at a temperature range of 250 ⁇ 280 °C using a twin-screw extruder. After extrusion, pelletized and dried at 80 ° C. for at least 4 hours, followed by injection molding, and left at room temperature for at least 48 hours to prepare injection specimens.
- Example Control Comparative example One 2 3 4 5 One 2 One 2 3 4 5 PMMA 100 100 100 100 100 100 - 100 100 100 100 100 ASA * 18.87 19.48 20.27 24.32 31.43 - 100 11.76 54.55 18.87 19.79 49.09 Silicone Shock Reinforcement * - - - - - - - - 6.29 - - Acrylic impact modifier * 6.29 6.49 10.81 6.76 7.14 - - 5.88 27.27 - 6.60 27.27 Scratch Reinforcement * 0.63 3.90 4.05 4.05 4.29 - - - - 0.63 6.0 5.46
- Izod impact strength (kg.cm / cm) was measured by the ASTM D256 method.
- Example 2 As shown in Table 2, the scratch resistance, glossiness, color (black) of Examples 1 to 5 including the acrylic impact modifier and the scratch reinforcement in the alloy of the polymethyl methacrylate resin and the acrylic copolymer within an appropriate amount range, respectively. Persimmon, transparency), impact strength, melt index was found to be improved.
- Comparative Example 1 using neat PMMA resin, the impact strength and melt index was poor, while in Comparative Example 2 using neat ASA resin, scratch resistance, glossiness, color was poor.
- Comparative Example 1 containing an acrylic copolymer and an acrylic impact modifier less than an appropriate lower limit and not including a scratch reinforcement, scratch resistance, impact strength and melt index were somewhat poorer than those of Examples 1 to 5,
- Comparative Example 2 including the acrylic copolymer and the acrylic impact modifier in an amount exceeding the upper limit of the appropriate amount and did not include a scratch reinforcing agent, it was confirmed that the scratch resistance, glossiness, and color were significantly poorer than those of Examples 1 to 5.
- Comparative Example 5 including the acrylic impact modifier and the scratch reinforcement in an amount exceeding the upper limit of the appropriate amount, it was confirmed that the scratch resistance, glossiness, color is significantly poor compared to Examples 1 to 5.
- a polymethylmethacrylate-acrylic air prepared by using a specific amount of an acrylic impact modifier as a shock modifier of a polymethyl methacrylate resin and an acrylic copolymer alloy together with a specific scratch enhancer together
- the alloy alloy high gloss composition it was confirmed that a molded article having improved high gloss, scratch resistance, color (transparency, black feeling), etc. was produced, and as a result, it was possible to provide economic efficiency by reducing the cost of additional coating after injection. have.
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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- Manufacture Of Macromolecular Shaped Articles (AREA)
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Abstract
Description
구분(중량부) | 실시예 | 대조예 | 비교예 | |||||||||
1 | 2 | 3 | 4 | 5 | 1 | 2 | 1 | 2 | 3 | 4 | 5 | |
PMMA | 100 | 100 | 100 | 100 | 100 | 100 | - | 100 | 100 | 100 | 100 | 100 |
ASA* | 18.87 | 19.48 | 20.27 | 24.32 | 31.43 | - | 100 | 11.76 | 54.55 | 18.87 | 19.79 | 49.09 |
실리콘계 충격보강제* | - | - | - | - | - | - | - | - | 6.29 | - | - | |
아크릴계 충격보강제* | 6.29 | 6.49 | 10.81 | 6.76 | 7.14 | - | - | 5.88 | 27.27 | - | 6.60 | 27.27 |
스크래치 보강제* | 0.63 | 3.90 | 4.05 | 4.05 | 4.29 | - | - | - | - | 0.63 | 6.0 | 5.46 |
구분 | 실시예 | 대조예 | 비교예 | |||||||||
1 | 2 | 3 | 4 | 5 | 1 | 2 | 1 | 2 | 3 | 4 | 5 | |
내스크래치성(△L) | 1.1 | 0.6 | 0.7 | 0.8 | 1.0 | 0.3 | 11.6 | 1.5 | 3.0 | 0.9 | 0.5 | 2.5 |
광택도(45°) | 92.0 | 91.0 | 91.0 | 90.0 | 89.0 | 95.0 | 85.0 | 93.0 | 85.0 | 87.0 | 87 | 83.5 |
Color(L*) | 3.5 | 3.7 | 3.7 | 3.8 | 4.0 | 2.9 | 9.3 | 3.2 | 7.1 | 5.9 | 5.5 | 7.5 |
Izod 충격강도 | 3.8 | 4.0 | 4.5 | 4.5 | 5.5 | 1.0 | 10.3 | 2.5 | 6.5 | 4.8 | 3.5 | 6.4 |
Melt Index(g/10min) | 4.0 | 4.2 | 4.2 | 4.5 | 5.0 | 2.0 | 12.0 | 3.0 | 7.6 | 4.8 | 3.8 | 7.7 |
Claims (14)
- 폴리메틸메타크릴레이트 수지 100 중량부에, 아크릴계 공중합체 12 내지 50 중량부, 아크릴계 충격보강제 6 내지 25 중량부, 및 스크래치 보강제 0.5 내지 5 중량부를 포함하는 것을 특징으로 하는폴리메틸메타크릴레이트-아크릴계 공중합체 얼로이 고광택 조성물.
- 제1항에 있어서,상기 폴리메틸메타크릴레이트 수지는 메틸메타크릴레이트의 단독 중합체, 메틸메타크릴레이트-아크릴레이트 공중합체, 또는 이들의 혼합인 것을 특징으로 하는폴리메틸메타크릴레이트-아크릴계 공중합체 얼로이 고광택 조성물.
- 제1항에 있어서,상기 아크릴계 공중합체는 아크릴계 고무 40 내지 50 중량%에 스티렌계 단량체와 아크릴로니트릴계 단량체 50 내지 60 중량%가 그라프트된 공중합체로서, 쉘내 아크릴로니트릴 단량체가 상기 공중합체를 구성하는 아크릴 고무 및 단량체 총 100 중량% 중 20 내지 35 중량% 범위 내로 포함된 것을 특징으로 하는폴리메틸메타크릴레이트-아크릴계 공중합체 얼로이 고광택 조성물.
- 제1항에 있어서,상기 아크릴계 충격보강제는 아크릴로니트릴-스티렌 공중합체와 아크릴계 단량체가 가교된 수지인 것을 특징으로 하는폴리메틸메타크릴레이트-아크릴계 공중합체 얼로이 고광택 조성물.
- 제1항에 있어서,상기 아크릴계 충격보강제는 스티렌계 시드 5 내지 10 중량%, 상기 시드를 감싸는 아크릴계 코어 50 내지 6 중량%, 및 상기 코어를 감싸는 스티렌계 쉘 30 내지 40 중량%를 포함하는 공중합체인 것을 특징으로 하는폴리메틸메타크릴레이트-아크릴계 공중합체 얼로이 고광택 조성물.
- 제5항에 있어서,상기 스티렌계 시드와 스티렌계 쉘은 각각 독립적으로 스티렌계 호모중합체 및 스티렌-아크릴로니트릴계 공중합체 중에서 선택된 것을 특징으로 하는폴리메틸메타크릴레이트-아크릴계 공중합체 얼로이 고광택 조성물.
- 제5항에 있어서,상기 스티렌계 시드 및 아크릴계 코어는 각각 독립적으로 가교성 단량체를 아크릴계 충격보강제를 구성하는 전체 성분의 총 100 중량% 중 0.1 내지 5 중량% 범위 내로 포함하는 것을 특징으로 하는폴리메틸메타크릴레이트-아크릴계 공중합체 얼로이 고광택 조성물.
- 제7항에 있어서,상기 가교성 단량체는 디비닐벤젠, 에틸렌글리콜 디메타크릴레이트, 디에틸렌글리콜 디메타크릴레이트, 트리에틸렌글리콜 디메타크릴레이트, 1,3-부틸렌글리콜 디메타클릴레이트, 아릴메타크릴레이트 및 1,3-부틸렌글리콜 디아크릴레이트 중에서 선택된 1종 이상인 것을 특징으로 하는폴리메틸메타크릴레이트-아크릴계 공중합체 얼로이 고광택 조성물.
- 제1항에 있어서,상기 스크래치 보강제는 실록세인계 중합체 혹은 유기변성 실록세인계 중합체인 것을 특징으로 하는폴리메틸메타크릴레이트-아크릴계 공중합체 얼로이 고광택 조성물.
- 제9항에 있어서,상기 실록세인계 중합체는 탄소수 1 내지 10의 알킬이 결합된 폴리디알킬실록세인 중합체인 것을 특징으로 하는폴리메틸메타크릴레이트-아크릴계 공중합체 얼로이 고광택 조성물.
- 제1항에 있어서,상기 얼로이 조성물은 충격보강제, 활제, 열안정제, 자외선 안정제, 적하 방지제, 안료, 염료, 및 무기 충진제 중에서 선택된 1종 이상의 첨가제를 포함하는 것을 특징으로 하는폴리메틸메타크릴레이트-아크릴계 공중합체 얼로이 고광택 조성물.
- 제1항의 폴리메틸메타크릴레이트-아크릴계 공중합체 얼로이 고광택 조성물을 포함하는 성형품.
- 제13항에 있어서,상기 성형품은 무도장 자동차 외장재인 것을 특징으로 하는 성형품.
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CN201580002928.6A CN106068305B (zh) | 2014-11-21 | 2015-11-19 | 高光泽度聚甲基丙烯酸甲酯-丙烯酸共聚物复合组合物及模塑制品 |
EP15853635.9A EP3053962B1 (en) | 2014-11-21 | 2015-11-19 | High gloss polymethyl methacrylate-acrylic copolymer alloy composition, and molded product |
US15/035,185 US9663651B2 (en) | 2014-11-21 | 2015-11-19 | High-gloss polymethylmethacrylate acrylic copolymer alloy composition and molded article |
JP2016528856A JP6284249B2 (ja) | 2014-11-21 | 2015-11-19 | ポリメチルメタクリレートアクリル系共重合体アロイ高光沢組成物及び成形品 |
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