KR100725940B1 - Polymethyl methacrylate resin composition - Google Patents

Polymethyl methacrylate resin composition Download PDF

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KR100725940B1
KR100725940B1 KR1020050117815A KR20050117815A KR100725940B1 KR 100725940 B1 KR100725940 B1 KR 100725940B1 KR 1020050117815 A KR1020050117815 A KR 1020050117815A KR 20050117815 A KR20050117815 A KR 20050117815A KR 100725940 B1 KR100725940 B1 KR 100725940B1
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acrylate
weight
parts
resin composition
pmma
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KR1020050117815A
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Korean (ko)
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전은진
서효정
유연옥
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엘지엠엠에이 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • 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
    • C08L2207/53—Core-shell polymer

Abstract

Provided is a polymethyl methacrylate resin composition, which has excellent brittleness, gloss and scratch resistance, and is useful as a material for producing exterior materials of household electronic appliances, or the like. The polymethyl methacrylate resin composition comprises: 100 parts by weight of a polymethyl methacrylate(PMMA) resin; 1-20 parts by weight of organic crosslinking beads obtained by polymerizing 80-99 parts by weight of at least one of methyl methacrylate, methyl acrylate, ethyl (meth)acrylate, butyl (meth)acrylate and styrene by using 1-20 parts by weight of at least one crosslinking agent selected from divinyl benzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate and diethylene glycol dimethacrylate; and 5-30 parts by weight of an impact reinforcing agent having a core or a multi-layer structure with a core and an intermediate layer obtained through polymerization of butadiene and at least one of methyl methacrylate, methyl acrylate, ethyl (meth)acrylate, butyl (meth)acrylate and styrene.

Description

폴리메틸메타크릴레이트 수지 조성물{Polymethyl methacrylate Resin Composition}Polymethyl methacrylate resin composition {Polymethyl methacrylate Resin Composition}

본 발명은 광택, 내스크래치성 및 취성이 우수하여, 도장공정을 거치지 않고도 가전제품 등의 외장 소재로 사용할 수 있는 폴리메틸메타크릴레이트(PMMA) 무도장 외장용 수지 조성물에 관한 것이다.The present invention relates to a polymethyl methacrylate (PMMA) unpainted exterior resin composition that is excellent in gloss, scratch resistance and brittleness and can be used as exterior materials such as home appliances without a coating process.

종래 가전제품 등의 외장용으로 사용되는 일반적인 수지 조성물은 폴리스티렌, 아크릴로니트릴-부타디엔-스티렌 공중합체, 폴리카보네이트 및 이들의 혼합물을 사용하여 왔다. 이러한 종래의 수지 조성물은 가전제품의 외장용으로 사용될 때 원하는 색상에 따라 도장 공정을 거치게 된다. 도장공정은 잘 알려져 있는 바와 같이 스프레이 코팅 공정으로 시행된다. 가전제품의 외장용으로 사용되는 수지 조성물에 도장을 하는 이유는 원하는 색상(광택이나 착색정도), 내스크래치성 증대 등을 부여하여 외장재로서의 물성과 심미감 등을 부여하기 위해서이다. 통상 외장 도장은 스프레이코팅 방법으로 도장하는 것이 일반적인데, 일반 외장용 수지 성형물을 도장하지 않고도 충분한 내스크래치성이나 취성을 부여할 수 있다면 별도의 도장이라는 공정을 거치지 않고 생산하여 사용할 수 있으므로 생산라인을 단축하여 공간 및 원가절감을 이룰 수 있을 뿐만 아니라 경제적으로 제조할 수 있다.Conventional resin compositions used for exteriors such as home appliances have used polystyrene, acrylonitrile-butadiene-styrene copolymers, polycarbonates, and mixtures thereof. This conventional resin composition is subjected to a coating process according to the desired color when used for the exterior of home appliances. The painting process, as is well known, is carried out by a spray coating process. The reason for coating the resin composition used for exterior of home appliances is to impart desired color (gloss or degree of coloring), increase scratch resistance, and the like to impart physical properties and aesthetics as exterior materials. In general, exterior coating is generally applied by spray coating method.If sufficient scratch resistance or brittleness can be given without coating general resin molding, shorten production line because it can be produced and used without a separate coating process. In this way, not only space and cost reduction can be achieved but also economically manufactured.

미국특허 6,075,094 및 4,698,373등에 의하면 PMMA와 가교제, 개시제를 사용하여 내스크래치성이 높은 수지를 제조하는 방법이 기재되어 있으나, 이 경우 얻어진 물질이 가교되어 유동성이 없어 압출이나 사출 등 후가공으로 원하는 형태로 성형을 할 수 없는 단점이 있었다. U.S. Pat.Nos. 6,075,094 and 4,698,373 describe a method for producing a high scratch resistance resin using PMMA, a crosslinking agent, and an initiator, but in this case, the obtained material is crosslinked and formed into a desired shape by post-processing such as extrusion or injection because it has no fluidity. There was a disadvantage that can not.

따라서, 충분한 내마모성과 취성을 가지면서 압출이나 사출 등 후 가공에 의해 원하는 모양으로 성형이 가능할 정도로 유동성을 가지며, 조립 등에 적합한 취성(충격강도)을 가지고, 특히 광택, 내스크래치성이 우수한 수지를 개발할 필요성이 대두되었다.Therefore, it has sufficient abrasion resistance and brittleness, is fluid enough to be molded into a desired shape by post-processing such as extrusion or injection, and has a brittleness (impact strength) suitable for assembling, in particular, to develop a resin having excellent gloss and scratch resistance. Necessity arose.

본 발명의 목적은 가전제품 등의 외장 소재로 사용될 수 있는 내마모성과, 조립 등에서 파괴되지 않는 충분한 정도의 취성을 가지는 폴리메틸메타크릴레이트(이하 PMMA)계 수지 조성물을 제공하는 데 있다.An object of the present invention is to provide a polymethyl methacrylate (hereinafter referred to as PMMA) -based resin composition having abrasion resistance that can be used as an exterior material such as home appliances, and brittleness of a sufficient degree not to be destroyed in assembly.

상기와 같은 목적을 달성하기 위해 노력한 결과, 본 발명자들은 PMMA수지에 유기가교비드, 충격보강제를 혼합함으로써, ABS(아크릴로니트릴-부타디엔-스티렌공중합체), 폴리카보네이트, 폴리스티렌 또는 그들의 혼합물 등으로 구성된 수지 조성물에 비하여 도장 공정을 거치지 않고, 특히 착색 후에도 광택이 현저하게 상승하고 색상이 유려하며, 내스크래치성이 우수한 PMMA계 수지 조성물을 수득할 수 있음을 발견하고 본 발명을 완성하였다.As a result of efforts to achieve the above object, the present inventors, by mixing the organic cross-linked beads, impact modifier in PMMA resin, ABS (acrylonitrile-butadiene-styrene copolymer), polycarbonate, polystyrene or a mixture thereof The present invention was completed by discovering that a PMMA-based resin composition can be obtained that does not undergo a coating process as compared with the resin composition, in particular, even after coloring, the gloss is remarkably increased, the color is beautiful, and the scratch resistance is excellent.

상기의 목적을 달성하기 위하여 본 발명자들은 A) PMMA계 수지 100중량부에 대하여 B) 유기 가교 비드 1~20중량부 C) 충격보강제 5~30 중량부를 혼합함으로써, 내마모성과 취성 및 착색후 광택이 현저하게 상승하고 색상이 유려한 PMMA계 수지 조성물을 제조하였다.In order to achieve the above object, the present inventors mix A) 1 to 20 parts by weight of organic crosslinked beads C) 5 to 30 parts by weight of impact modifier with respect to 100 parts by weight of PMMA resin, thereby improving wear resistance, brittleness and gloss after coloring. PMMA-based resin composition was prepared which was markedly elevated and beautiful in color.

본 발명에 사용되는 상기 (A) 수지는 메틸메타크릴레이트 단독중합체 혹은 공중합체로서, 공중합체는 메틸메타크릴레이트와 메틸아크릴레이트, 에틸 (메타)아크릴레이트, 부틸 (메타)아크릴레이트, 스티렌에서 선택되는 어느 한 성분 이상의 것과 중합한 공중합체인 것을 특징으로 하는 수지로 이루어진다. 본 발명에서 사용되는 공단량체들의 조성비는 메틸메타크릴레이트를 주요성분으로 사용하는 한에는 크게 제한을 받지 않지만 좋게는 메틸메타크릴레이트 80~100중량%와 공단량체 20~0중량%의 비로 중합하여 사용하는 것이 좋다. 더욱 좋게는 MMA 85~97중량%, 공단량체 15~3 중량부를 사용하는 것이 내마모성을 상실하지 않으므로 좋다.The resin (A) used in the present invention is a methyl methacrylate homopolymer or copolymer, and the copolymer is methyl methacrylate and methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, styrene. It is made of a resin characterized in that the copolymer is polymerized with at least one component selected. The composition ratio of the comonomers used in the present invention is not particularly limited as long as methyl methacrylate is used as the main component, but is preferably polymerized in a ratio of 80 to 100% by weight of methyl methacrylate and 20 to 0% by weight of comonomer. It is good to use. More preferably, using 85 to 97% by weight of MMA and 15 to 3 parts by weight of comonomer does not lose wear resistance.

본 발명에 사용되는 상기 (A) 수지의 중량 평균 분자량은 바람직하게는 약 6만 이상 15만 이하이며 보다 바람직하게는 7만 이상 13만 이하이다. 상기 (A) 수지의 분자량이 15만이상일 경우는 충격강도와 조성물의 분산효과를 좋게 하나, 조성물의 유동성이 저하하여 후가공성이 저하하고, 반대로 분자량이 6만 이하일 경우는 조성물의 유동성이 양호하나 충격강도나 분산성이 부족하여 좋지 않다. The weight average molecular weight of the above-mentioned (A) resin used for this invention becomes like this. Preferably it is about 60,000 or more and 150,000 or less, More preferably, it is 70,000 or more and 130,000 or less. When the molecular weight of the resin (A) is 150,000 or more, the impact strength and the effect of dispersing the composition are improved, but the fluidity of the composition is lowered, and the post-processing property is lowered. It is not good due to lack of impact strength and dispersibility.

본 발명에서 사용하는 상기 (B) 유기 가교 비드는 투명성과 내마모성이 우수 한 메틸메타크릴레이트와 메틸아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 스티렌에서 선택되는 어느 한 성분 이상을 80~99중량% 및 가교제로서 디비닐벤젠, 에틸렌 글리콜 디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트에서 1종 이상을 1~20중량%를 사용하여 중합한 평균입경 1~10μm의 입자이다. 가교되지 않은 입자를 사용하는 경우 가공 시 입자의 형태가 변하여, 광택과 내스크래치성이 저하한다. 상기 (B)수지의 크기가 1미크론 이하이면 고른 분산을 얻기 어렵고, 내스크래치성의 개선효과를 충분히 얻을 수 없으며, 10μm이상이면 충격강도나 광택이 저하하거나 가공 후 표면에 핀홀 등 품질 문제를 일으킬 수 있다. 본 발명에서 사용하는 상기 유기가교비드로서 아크릴계를 사용하는 경우 투명성과 내마모성을 충분히 확보할 수 있지만, 아크릴계 이외의 가교중합체 입자를 사용하는 경우에는 본 발명이 원하는 정도의 내마모성과 표면광택이나 투명성을 충분히 확보할 수 없어서 좋지 않다.The (B) organic crosslinked beads used in the present invention are at least one component selected from methyl methacrylate, methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and styrene having excellent transparency and wear resistance. 80 to 99% by weight and at least one polymerized in divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol dimethacrylate as 1 to 20% by weight as a crosslinking agent It is a particle having an average particle diameter of 1 to 10 µm. In the case of using uncrosslinked particles, the shape of the particles changes during processing, thereby decreasing gloss and scratch resistance. If the size of the resin (B) is less than 1 micron, it is difficult to obtain even dispersion, and the effect of improving scratch resistance cannot be sufficiently obtained. If the size of the resin is greater than 10 μm, impact strength or gloss may be degraded, or quality problems such as pinholes may occur on the surface after processing. have. When acrylic is used as the organic crosslinked beads used in the present invention, transparency and wear resistance can be sufficiently secured. However, when crosslinked polymer particles other than acrylic are used, the wear resistance and surface gloss or transparency of the present invention are sufficiently high. Not good because you can't secure it.

본 발명에서 사용하는 상기 (C) 내충격 보강제로는 메틸메타크릴레이트와 메틸아크릴레이트, 에틸(메타)아크릴레이트, 부틸(메타)아크릴레이트, 스티렌에서 선택된 어느 한 성분 이상과 부타디엔의 공중합체 및 가교제로서 디비닐벤젠, 에틸렌 글리콜 디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트에서 1종 이상을 사용하는 고무중합체를 코어물질로 하는 다층구조를 가지는 수지 입자로서 그 크기는 0.1~0.3마이크로미터이다. 고무입자가 너무 작으면 충격강도의 개선효과가 미미하고, 너무 크면 표면에 위치한 고무입자로 인하여 내스크래치성 및 광택이 저하한다. 상기 (C) 수지는 3층 또는 2층으로 된 입자로 내 부 또는 내부와 중간층이 상기에서 기재한 바와 같이 고무층으로 되어 있어 우수한 충격강도를 발현하고, 최 외부층은 메틸메타크릴레이트로 그라프팅 되어 있어 PMMA와의 상용성을 높여 분산을 좋게 한다. 상기 (C) 수지의 함량이 너무 적으면 충격강도의 개선효과가 미비하고, 너무 많으면 경도가 낮아 내스크래치성 및 광택이 저하한다.The impact modifier (C) used in the present invention is a copolymer and a crosslinking agent of at least one component selected from methyl methacrylate, methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, styrene, and butadiene. As resin particles having a multi-layered structure comprising a rubber polymer using at least one of divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate and diethylene glycol dimethacrylate as core materials. Is 0.1 to 0.3 micrometers. If the rubber particles are too small, the effect of improving the impact strength is insignificant, and if the rubber particles are too large, scratch resistance and gloss decrease due to the rubber particles located on the surface. The resin (C) is a three- or two-layered particle, and the inner or inner and middle layers are rubber layers as described above, and thus exhibit excellent impact strength, and the outermost layer is grafted with methyl methacrylate. This improves the compatibility with PMMA and improves dispersion. If the content of the resin (C) is too small, the effect of improving the impact strength is insignificant, and if too large, the hardness is low, so that scratch resistance and gloss are reduced.

본 발명의 PMMA 수지 조성물의 블랜딩 온도는 섭씨 180도 내지 250도 사이가 적합하다. 융합의 순서는 중요하지 않다. 예컨대 모든 성분이 1단계에서 블랜딩 되거나 혹은 유기 가교 입자를 PMMA와 우선 블랜딩한 다음 나머지 성분을 블랜딩하는 방법이 사용될 수 있다. The blending temperature of the PMMA resin composition of the present invention is suitably between 180 degrees Celsius and 250 degrees Celsius. The order of fusion is not important. For example, all components may be blended in one step, or a method of first blending organic crosslinked particles with PMMA and then blending the remaining components.

본 발명에 따르는 PMMA계 수지 조성물은 충진제, 보강제, 착색제, 활제, 안정제, 산화방지제, 내열제 및 자외선 안정제 및 다른 화합물 성분과 같은 일반적인 열가소성 첨가물을 포함할 수 있다.PMMA-based resin compositions according to the present invention may include common thermoplastic additives such as fillers, reinforcing agents, colorants, lubricants, stabilizers, antioxidants, heat resistant and ultraviolet stabilizers, and other compound components.

상술한 설명들에 의하여, 기술 분야의 당 업자는 본 발명의 필수적인 특징들을 쉽게 이해할 수 있을 것이며, 이 발명의 요지 및 범주를 벗어나지 않는 범위 내에서 다양한 용도, 조건 및 구체적인 예에 적합한 변경 및 수정이 가해질 수 있음에 주목하여야 한다. 이하에서 본 발명의 범주를 제한하지 않는 실시예에 의하여 본 발명에 따른 PMMA계 수지 조성물을 설명한다.Based on the above description, those skilled in the art will be able to easily understand the essential features of the present invention, and changes and modifications suitable for various uses, conditions, and specific examples can be made without departing from the spirit and scope of the present invention. It should be noted that this may be done. Hereinafter, the PMMA resin composition according to the present invention will be described by examples which do not limit the scope of the present invention.

본 발명의 가공성은 ASTM D1238에 의거 멜트 플로우 인덱스(Melt Flow Index)를 측정하였다. Melt Flow Index가 0.5이상인 경우 사출 및 압출 등 후가공이 가능하다.The processability of the present invention measured the melt flow index in accordance with ASTM D1238. If the Melt Flow Index is 0.5 or higher, post-processing such as injection and extrusion is possible.

광택은 ASTM D523에 의거 글로스미터(glossmeter)를 사용하여 45도 광택도를 측정하였다. 광택도가 90% 이상의 경우 외관이 양호하다. Gloss was measured at 45 degree glossiness using a glossmeter according to ASTM D523. If the glossiness is 90% or more, the appearance is good.

취성은 ASTM D256에 따라 아이조드 충격강도를 측정하였다. 충격강도가 3kJ/m2이하이면 조립시 깨짐 등의 문제가 발생할 위험이 있다. Brittleness was measured for Izod impact strength according to ASTM D256. If the impact strength is 3kJ / m 2 or less, there is a risk of problems such as cracking during assembly.

내스크래치성은 ASTM D3363에 따라 연필경도를 측정하였다. 외장용으로 사용되기 위하여는 연필경도 HB이상이 요구된다.Scratch resistance was measured by pencil hardness according to ASTM D3363. To be used for exterior, pencil hardness more than HB is required.

분자량은 Gel Permeation Chromatography (Waters사 제)를 이용하여 측정하였다.Molecular weight was measured using Gel Permeation Chromatography (manufactured by Waters).

실시예1Example 1 ~3 및 ~ 3 and 비교예Comparative example 1~4 1 ~ 4

표1에 기재된 수지와 첨가성분, 조성비 함량으로, PMMA 수지 조성물을 제조 하였으며, 그 결과를 표2에 나타냈다. PMMA resin composition was prepared with the resins, additive components, and composition ratio contents shown in Table 1, and the results are shown in Table 2.

먼저, 표1의 물성을 가지는 수시성분을 혼합하고, 수지 조성물은 32파이 이축 스크류 압출기(L/D:30) (제조사 SM플라텍)을 사용하여 200rpm으로 스큐류를 교반하면서 호퍼로부터 상기 조성물을 투입하였다. 호퍼는 냉각수를 순환시켜 냉각하였다. 스크류은 전단부(1~2존)을 180도로 유지하고 후단부(3~7존)을 210도~220도 유지하여 용융 혼련하였으며, 압출다이의 온도는 235도로 유지하고 20kg/hr로 압출하고 냉각하고 컷팅하여 펠렛화하였다.First, the occasional components having the physical properties shown in Table 1 were mixed, and the resin composition was prepared from the hopper while stirring the skew at 200 rpm using a 32 pi twin screw extruder (L / D: 30) (manufactured by SM Platec). Input. The hopper was cooled by circulating cooling water. The screw was melt kneaded by maintaining the front end (zones 1-2) and the rear end (zones 3-7) by 210-220 degrees, and the extrusion die temperature was maintained at 235 degrees and extruded at 20 kg / hr and cooled. And cut and pelletized.

기본물성시험을 평가하기 위한 샘플은 사출성형기(LG전선, 100톤)을 이용하 여 노즐온도 223도에서 1차 사출압력을 100 kg/cm2, 2차 사출 압력을 60 kg/cm2, 배압 10kg/cm2 및 사출시간 15초하고 사출스크류를 100 rpm으로 하여 사출물을 제조하였다. 사출물은 물성 평가를 위하여 상온에서 48시간 체류 후에 측정하였다. 그 결과를 표 2에 기재하였다.The sample injection molding machine (LG wires, 100 ton) to take advantage over the nozzle temperature 223 is also a primary injection pressure at 100 kg / cm 2, 2 a primary injection pressure of 60 kg / cm 2, the back pressure 10kg to evaluate basic physical properties test Injection molding was carried out with / cm 2 and the injection time of 15 seconds and the injection screw at 100 rpm. The extrudate was measured after 48 hours retention at room temperature for physical properties evaluation. The results are shown in Table 2.

실시예1은 분자량이 80,000인 PMMA 100중량부에 대하여 PMMA 유기 가교비드 5중량부, UMG사의 아크릴 비드 MUX 60을 20중량부 사용하여 샘플을 제조하였다. 표2의 결과로부터 유동지수가 후가공에 적합하고, 취성, 광택도, 연필경도가 양호함을 알 수 있다. 실시예2는 충격보강제를 달리 적용한 이외에는 실시예1과 동일한데, 표2의 결과로부터 유동지수가 후가공에 적합하고, 취성, 광택도, 연필경도가 양호함을 알 수 있다. 실시예3은 PMMA의 분자량이 120,000인 것을 제외하고 실시예1과 동일한데, 표2의 결과로부터 유동지수가 후가공에 적합하고, 취성, 광택도, 연필경도가 양호함을 알 수 있다. 비교예1은 PMMA의 분자량이 200,000인 것을 제외하고 실시예1과 동일한데, 표2의 결과로부터 유동지수가 너무 낮아 후가공에 적합하지 않음을 알 수 있다. 비교예2는 유기가교비드의 크기가 20μm인 것을 제외하고 실시예1과 동일한데 큰입자가 표면에 위치하여 광택도가 저하함을 알 수 있다. 비교예3은 유기가교비드의 함량이 30중량부 인 것을 제외하고 실시예1과 동일한데 충격강도가 열세하였다. 비교예4는 충격보강제의 함량이 40중량부인 것을 제외하고 실시예1과 동일한데 연필경도가 낮아 내스크래치성이 열세하였다.Example 1 prepared a sample using 5 parts by weight of PMMA organic crosslinked beads and 20 parts by weight of acrylic beads MUX 60 from UMG, based on 100 parts by weight of PMMA having a molecular weight of 80,000. The results of Table 2 show that the flow index is suitable for post processing, and the brittleness, glossiness, and pencil hardness are good. Example 2 is the same as in Example 1 except that the impact modifier is applied differently, it can be seen from the results of Table 2 that the flow index is suitable for post-processing, and brittleness, glossiness, and pencil hardness are good. Example 3 is the same as Example 1 except that the molecular weight of PMMA is 120,000. From the results in Table 2, the flow index is suitable for post-processing, and the brittleness, glossiness, and pencil hardness are good. Comparative Example 1 is the same as Example 1 except that the molecular weight of PMMA is 200,000, it can be seen from the results of Table 2 that the flow index is too low to be suitable for post processing. Comparative Example 2 is the same as in Example 1 except that the size of the organic cross-linked beads is 20μm, it can be seen that the gloss is reduced because the large particles are located on the surface. Comparative Example 3 is the same as Example 1 except that the content of the organic cross-linked beads is 30 parts by weight, the impact strength was inferior. Comparative Example 4 is the same as Example 1 except that the content of the impact modifier is 40 parts by weight, but the pencil hardness was low, the scratch resistance was inferior.

표1. 실시예 및 비교예의 조성성분Table 1. Composition Components of Examples and Comparative Examples

Figure 112005071004719-pat00001
Figure 112005071004719-pat00001

(1) PMMA는 LG MMA사 제품으로 메틸메타크릴레이트 90중량부와 메틸아크릴레이트 10중량부로 구성된 중합물을 사용. (1) PMMA is manufactured by LG MMA Co., Ltd. and uses a polymer composed of 90 parts by weight of methyl methacrylate and 10 parts by weight of methyl acrylate.

(2) Ganz Chemicals사의 crossslinked PMMA사용, GM-0630H, GM2009S(2) Use of crossslinked PMMA from Ganz Chemicals, GM-0630H, GM2009S

(3) UMG사의 MUX 60 사용.(부타디엔 스티렌 메틸메타크릴레이트로 구성)(3) MUX 60 use of UMG company. (Composed of butadiene styrene methyl methacrylate)

(4) 엘지화학의 MB838 사용. (부타디엔 스티렌 메틸메타크릴레이트로 구성)(4) Use MB838 from LG Chem. (Composed of butadiene styrene methyl methacrylate)

표2. PMMA계 성형물의 물성비교Table 2. Property comparison of PMMA moldings

Figure 112005071004719-pat00002
Figure 112005071004719-pat00002

본 발명의 수지 조성물을 사용함으로써 유동성 및 충격강도 등이 바람직한 물성의 균형을 이루어 사출, 압출, 조립 등의 후가공이 가능하고, 도장하지 않은 상태로 광택 및 내스크래치 특성을 향상시켜 도장공정을 생략함으로써, 저렴하게 유려한 외관의 외장 소재를 수득할 수 있다. 또한 본 발명에 따른 조성물의 경우 가공성, 충격성, 광택도 및 내마모성이 매우 우수한 성형물을 제조할 수 있어서, 그 자체로서 외장재로 가공가능하고, 또한 도장공정을 생략하여 그대로 사용할 수 있는 새로운 PMMA계 수지 조성물을 제공할 수 있었다.By using the resin composition of the present invention, the fluidity and the impact strength are balanced to the desired physical properties, so that post-processing such as injection, extrusion, and granulation are possible, and the gloss and scratch resistance are improved without coating, thereby eliminating the coating process. It is possible to obtain an exterior material having a good appearance at low cost. In addition, in the case of the composition according to the present invention, it is possible to produce a molded article having excellent workability, impact resistance, glossiness and wear resistance, and can be processed into an exterior material as it is, and a new PMMA resin composition which can be used as it is by omitting a coating process Could provide.

Claims (9)

폴리메틸메타크릴레이트(PMMA)계 수지 100중량부에 대하여, 메틸메타크릴레이트와 메틸아크릴레이트, 에틸 (메타)아크릴레이트, 부틸 (메타)아크릴레이트, 스티렌에서 선택되는 어느 한 성분 이상 80~99중량부 및 디비닐벤젠, 에틸렌 글리콜 디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트, 디에틸렌글리콜디메타크릴레이트에서 선택되는 1종 이상의 가교제 1~20중량부 사용하여 중합한 유기 가교 비드 1~20중량부 및 메틸메타크릴레이트와 메틸아크릴레이트, 에틸 (메타)아크릴레이트, 부틸 (메타)아크릴레이트, 스티렌에서 선택되는 어느 한 성분이상과 부타디엔을 중합한 코어 또는 코어와 중간층을 형성하는 다층구조를 갖는 충격보강제 5~30중량부 사용하는 것을 특징으로 하는 내마모성 및 내충격성이 우수한 PMMA계 수지 조성물.80 to 99 or more of any component selected from methyl methacrylate, methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and styrene based on 100 parts by weight of polymethyl methacrylate (PMMA) resin 1 to 20 parts by weight of organic crosslinking beads polymerized using 1 to 20 parts by weight of at least one crosslinking agent selected from parts by weight and divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol dimethacrylate. 20 parts by weight and a multi-layered structure forming a core or an intermediate layer polymerized with at least one component selected from methyl methacrylate, methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and styrene and butadiene PMMA-based resin composition excellent in wear resistance and impact resistance, characterized in that to use 5 to 30 parts by weight of an impact modifier. 제 1항에 있어서,The method of claim 1, 상기 PMMA계 수지는 메틸메타크릴레이트 단독중합체 혹은 공중합체인 것을 특징으로 하는 내마모성 및 내충격성이 우수한 PMMA계 수지 조성물.PMMA resin composition is excellent in wear resistance and impact resistance, characterized in that the methyl methacrylate homopolymer or copolymer. 제 2항에 있어서,The method of claim 2, 상기 PMMA계 공중합체는 메틸메타크릴레이트와 메틸아크릴레이트, 에틸(메타)아크릴레이트, 부틸 (메타)아크릴레이트, 스티렌에서 선택되는 어느 한 성분 이상의 공중합체인 것을 특징으로 하는 내마모성 및 내충격성이 우수한 PMMA계 수지 조성물.The PMMA copolymer is a PMMA having excellent abrasion resistance and impact resistance, characterized in that the copolymer of at least one component selected from methyl methacrylate, methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and styrene. System resin composition. 삭제delete 제 1항 내지 제 3항에서 선택되는 어느 한 항에 있어서, The method according to any one of claims 1 to 3, 유기 가교 비드는 평균입경이 1~10㎛인 것을 특징으로 하는 내마모성 및 내충격성이 우수한 PMMA계 수지 조성물.Organic crosslinked beads are PMMA resin composition excellent in wear resistance and impact resistance, characterized in that the average particle diameter is 1 ~ 10㎛. 삭제delete 제 1항 내지 제 3항에서 선택되는 어느 한 항에 있어서,The method according to any one of claims 1 to 3, 상기 충격보강제는 최외층이 메틸메타크릴레이트로 그라프트 되는 것을 특징으로 하는 내마모성 및 내충격성이 우수한 PMMA계 수지 조성물.The impact modifier is a PMMA resin composition excellent in wear resistance and impact resistance, characterized in that the outermost layer is grafted with methyl methacrylate. 삭제delete 제 5항에 있어서,The method of claim 5, 상기 충격보강제는 최외층이 메틸메타크릴레이트로 그라프트 되는 것을 특징으로 하는 내마모성 및 내충격성이 우수한 PMMA계 수지 조성물.The impact modifier is a PMMA resin composition excellent in wear resistance and impact resistance, characterized in that the outermost layer is grafted with methyl methacrylate.
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KR20160129171A (en) 2015-04-29 2016-11-09 롯데첨단소재(주) Thermoplastic resin composition and molded article using thereof
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KR20230096404A (en) * 2021-12-23 2023-06-30 주식회사 엘엑스엠엠에이 Metallic look resin composition with improved alumina pinhole defects
KR102633041B1 (en) * 2021-12-23 2024-02-05 주식회사 엘엑스엠엠에이 Metallic look resin composition with improved alumina pinhole defects
KR20230097524A (en) * 2021-12-24 2023-07-03 주식회사 엘엑스엠엠에이 Composite laminated film and manufacturing method there of Composite laminated film
KR102628823B1 (en) * 2021-12-24 2024-01-25 주식회사 엘엑스엠엠에이 Composite laminated film and manufacturing method there of Composite laminated film

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