KR20090065697A - Acrylic impact modifier, a method of manufacturing the same and a vinyl chloride resin composition comprising the same - Google Patents
Acrylic impact modifier, a method of manufacturing the same and a vinyl chloride resin composition comprising the same Download PDFInfo
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Abstract
본 발명은 아크릴계 충격 보강제, 이의 제조방법 및 이를 포함하는 염화비닐 수지 조성물에 관한 것으로, 보다 상세하게는 (a) 시드를 형성하는 총 단량체 100 중량%에 대하여 비닐계 단량체 0.5 내지 40 중량%, 친수성 단량체 55 내지 99 중량% 및 가교제 단량체 0.5 내지 5 중량%가 중합되어 형성되는 시드 1 내지 10 중량부; (b) 상기 시드를 감싸며, 코어를 형성하는 총 단량체 100 중량%에 대하여 알킬기의 탄소수가 1 내지 8인 알킬 아크릴레이트 80 내지 99.9 중량%, 가교제 단량체 0.1 내지 3 중량% 및 비닐계 단량체 0.1 내지 20 중량%가 중합되어 형성되는 코어 70 내지 90 중량부; 및 (c) 상기 코어를 감싸며, 쉘을 형성하는 총 단량체 100 중량%에 대하여 알킬기의 탄소수가 1 내지 4인 알킬 메타크릴레이트 97 내지 99 중량%, (메타)아크릴산 유도체 또는 말레산 무수물 1 내지 3 중량%가 중합되어 형성되는 쉘 10 내지 30 중량부를 포함하는 아크릴계 충격 보강제, 이의 제조방법 및 이를 포함하는 염화비닐 수지 조성물에 관한 것이다.The present invention relates to an acrylic impact modifier, a method for preparing the same, and a vinyl chloride resin composition including the same. More specifically, (a) 0.5 to 40% by weight of a vinyl monomer, and hydrophilicity, based on 100% by weight of the total monomers forming a seed. 1 to 10 parts by weight of the seed formed by polymerization of 55 to 99% by weight of the monomer and 0.5 to 5% by weight of the crosslinker monomer; (b) 80 to 99.9% by weight of alkyl acrylate having 1 to 8 carbon atoms of alkyl group, 0.1 to 3% by weight of crosslinker monomer and 0.1 to 20 of vinyl monomer, based on 100% by weight of the total monomer forming the core, surrounding the seed. 70 to 90 parts by weight of the core is formed by polymerizing by weight; And (c) 97 to 99% by weight of alkyl methacrylate having 1 to 4 carbon atoms of alkyl group, 1 to 3 of (meth) acrylic acid derivative or maleic anhydride, with respect to 100% by weight of the total monomer forming the shell, surrounding the core. It relates to an acrylic impact modifier comprising 10 to 30 parts by weight of a shell formed by polymerization by weight%, a preparation method thereof, and a vinyl chloride resin composition comprising the same.
본 발명에 따른 아크릴계 충격 보강제 및 이를 포함하는 염화비닐 수지 조성물은 내충격성 및 내후성이 우수할 뿐만 아니라 우수한 내열성 및 높은 경도를 함께 가진다. The acrylic impact modifier according to the present invention and the vinyl chloride resin composition including the same have excellent impact resistance and weather resistance, as well as excellent heat resistance and high hardness.
Description
본 발명은 우수한 내충격성 및 내후성뿐만 아니라 특히 우수한 내열성 및 높은 경도를 가지는 아크릴계 충격 보강제, 이의 제조방법 및 이를 포함하는 염화비닐 수지 조성물에 관한 것이다. The present invention relates to an acrylic impact modifier having excellent impact resistance and weather resistance as well as excellent heat resistance and high hardness, a method for preparing the same, and a vinyl chloride resin composition comprising the same.
일반적으로 염화비닐 수지의 내충격성을 향상시키기 위하여 사용되는 충격보강제는 메틸 메타크릴레이트-부타디엔-스티렌(MBS)계 수지, 염화 에틸렌(CPE)계 수지, 아크릴계 수지 등이 있다. 이들 중 상기 아크릴계 수지는 내후성이 우수하여 일광 노출 시간이 많은 옥외용 플라스틱 제품의 충격보강제로 널리 사용되고 있다. 예를 들면, 창틀과 같이 내충격성과 내후성이 동시에 요구되는 제품에는 알킬 아크릴레이트로 구성된 고무성 코어에 염화비닐 수지와 상용성이 우수한 메타크릴계 고분자를 그라프트 시킨 코어-쉘 구조의 고분자가 주로 사용된다. (KR 10-2006-0105149). 그러나 종래의 아크릴계 충격보강제에서 옥외용 사이딩이나 울타리 용으 로 사용되기 위한 경도 및 강도 측면에서 취약하며, 또한 계절에 따른 온도차에 의해 염화비닐 수지의 뒤틀림 현상이 발생하였다. Generally, impact modifiers used to improve the impact resistance of vinyl chloride resins include methyl methacrylate-butadiene-styrene (MBS) resins, ethylene chloride (CPE) resins, and acrylic resins. Among these, the acrylic resin has excellent weather resistance and is widely used as an impact modifier for outdoor plastic products having a lot of daylight exposure time. For example, a core-shell structured polymer is obtained by grafting a methacryl-based polymer having excellent compatibility with vinyl chloride resin on a rubbery core made of alkyl acrylate. do. (KR 10-2006-0105149). However, the conventional acrylic impact modifiers are vulnerable in terms of hardness and strength to be used for outdoor siding or fences, and warping of vinyl chloride resin occurs due to seasonal temperature differences.
이와 같은 현상을 방지하고자 US 5,008,145 에서는 알파 메틸 스티렌기를 갖는 SAN을 염화 비닐 수지에 블렌드 하여 열변형 온도 및 인장 강도를 증가시키려는 방법이 소개 되었다. 고경도 및 강도를 갖는 외관특성이 우수한 스티렌계 충격 보강제는 상기에서 제시한 아크릴계 충격보강제가 갖는 문제점을 보완 할 만한 물성을 지니고 있지만, 스티렌계 및 부타디엔계의 이중결합으로 인해 쉽게 변색 되는 단점이 있어 옥외용 가공물에는 적합하지 않는 것으로 알려져 있다. (US 20020028878, KR 2007-0027772)In order to prevent such a phenomenon, US 5,008,145 introduces a method for increasing the thermal deformation temperature and the tensile strength by blending SAN having an alpha methyl styrene group with a vinyl chloride resin. Styrene-based impact modifiers with high hardness and strength have excellent physical properties to compensate for the problems of the above-described acrylic impact modifiers, but have the disadvantage of easily discoloring due to double bonds of styrene-based and butadiene-based ones. It is not known to be suitable for outdoor workpieces . (US 20020028878, KR 2007-0027772)
상기와 같은 종래기술의 문제점을 해결하고자, 본 발명은 우수한 내충격성, 내후성, 내열성 및 높은 경도를 가지는 아크릴계 충격 보강제를 제공하는 것을 목적으로 한다. In order to solve the problems of the prior art as described above, an object of the present invention is to provide an acrylic impact modifier having excellent impact resistance, weather resistance, heat resistance and high hardness.
또한, 본 발명은 상기 아크릴계 충격 보강제의 제조방법을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a method for producing the acrylic impact modifier.
또한, 본 발명은 상기 아크릴계 충격 보강제를 포함하는 염화비닐 수지 조성물을 제공하는 것을 목적으로 한다. Moreover, an object of this invention is to provide the vinyl chloride resin composition containing the said acrylic impact modifier.
본 발명의 상기 목적 및 기타 목적들은 하기 설명된 본 발명에 의하여 모두 달성될 수 있다.The above and other objects of the present invention can be achieved by the present invention described below.
상기의 목적을 달성하기 위하여, In order to achieve the above object,
(a) 시드를 형성하는 총 단량체 100 중량%에 대하여 비닐계 단량체 0.5 내지 40 중량%, 친수성 단량체 55 내지 99 중량% 및 가교제 단량체 0.5 내지 5 중량%가 중합되어 형성되는 시드 1 내지 10 중량부;(a) 1 to 10 parts by weight of a monomer formed by polymerizing 0.5 to 40% by weight of vinyl monomer, 55 to 99% by weight of hydrophilic monomer and 0.5 to 5% by weight of crosslinking monomer based on 100% by weight of the total monomers forming the seed;
(b) 상기 시드를 감싸며, 코어를 형성하는 총 단량체 100 중량%에 대하여 알킬기의 탄소수가 1 내지 8인 알킬 아크릴레이트 80 내지 99.9 중량%, 가교제 단량체 0.1 내지 3 중량% 및 비닐계 단량체 0.1 내지 20 중량%가 중합되어 형성되는 코어 70 내지 90 중량부; 및(b) 80 to 99.9% by weight of alkyl acrylate having 1 to 8 carbon atoms of alkyl group, 0.1 to 3% by weight of crosslinker monomer and 0.1 to 20 of vinyl monomer, based on 100% by weight of the total monomer forming the core, surrounding the seed. 70 to 90 parts by weight of the core is formed by polymerizing by weight; And
(c) 상기 코어를 감싸며, 쉘을 형성하는 총 단량체 100 중량%에 대하여 알킬기의 탄소수가 1 내지 4인 알킬 메타크릴레이트 97 내지 99 중량%, (메타)아크릴산 유도체 또는 말레산 무수물 1 내지 3 중량%가 중합되어 형성되는 쉘 10 내지 30 중량부(c) 97 to 99% by weight of alkyl methacrylate having 1 to 4 carbon atoms of alkyl group, 1 to 3% by weight of (meth) acrylic acid derivative or maleic anhydride, based on 100% by weight of the total monomer forming the shell, surrounding the core 10 to 30 parts by weight of a shell formed by polymerization of%
를 포함하는 아크릴계 충격 보강제를 제공한다.It provides an acrylic impact modifier comprising a.
또한, Also,
(a) 시드의 제조에 사용되는 총 단량체 100 중량%에 대하여 비닐계 단량체 0.5 내지 40 중량%, 친수성 단량체 55 내지 99 중량% 및 가교제 단량체 0.5 내지 5 중량%를 유화 중합에 의해 시드 1 내지 10 중량부를 제조하는 단계;(a) 0.5 to 40% by weight of the vinyl monomer, 55 to 99% by weight of the hydrophilic monomer and 0.5 to 5% by weight of the crosslinker monomer with respect to 100% by weight of the total monomers used in the preparation of the seeds 1 to 10% by emulsion polymerization Preparing a part;
(b) 상기 시드의 존재 하에, 코어의 제조에 사용되는 총 단량체 100 중량%에 대하여 알킬기의 탄소수가 1 내지 8인 알킬 아크릴레이트 80 내지 99.9 중량%, 가교제 단량체 0.1 내지 3 중량% 및 비닐계 단량체 0.1 내지 20 중량%를 유화 중합에 의해 코어 70 내지 90 중량부를 제조하는 단계; 및(b) 80 to 99.9% by weight of alkyl acrylate having 1 to 8 carbon atoms of alkyl group, 0.1 to 3% by weight of crosslinker monomer and vinylic monomer based on 100% by weight of the total monomers used for preparing the core in the presence of the seed. Preparing from 0.1 to 20% by weight of 70 to 90 parts by weight of the core by emulsion polymerization; And
(c) 상기 코어의 존재 하에, 쉘의 제조에 사용되는 총 단량체 100 중량%에 대하여 대하여 알킬기의 탄소수가 1 내지 4인 알킬 메타크릴레이트 97 내지 99 중량%, (메타)아크릴산 유도체 또는 말레산 무수물 1 내지 3 중량%를 그라프트 중합시켜 쉘 10 내지 30 중량부를 제조하는 단계(c) 97 to 99% by weight of alkyl methacrylate having 1 to 4 carbon atoms of alkyl group, (meth) acrylic acid derivative or maleic anhydride with respect to 100% by weight of the total monomers used in the preparation of the shell in the presence of the core; Graft polymerization of 1 to 3% by weight to prepare 10 to 30 parts by weight of the shell
를 포함하는 아크릴계 충격 보강제의 제조방법을 제공한다.It provides a method of manufacturing an acrylic impact modifier comprising a.
또한,Also,
염화비닐 수지 100 중량부 및 상기 아크릴계 충격 보강제 1 내지 30 중량부 를 포함하는 염화비닐 수지 조성물을 제공한다. It provides a vinyl chloride resin composition comprising 100 parts by weight of vinyl chloride resin and 1 to 30 parts by weight of the acrylic impact modifier.
본 발명에 따른 아크릴계 충격 보강제 및 이를 포함하는 염화비닐 수지 조성물은 내충격성 및 내후성이 우수할 뿐만 아니라 우수한 내열성 및 높은 경도를 함께 가지는 효과가 있다. Acrylic impact reinforcing agent according to the present invention and the vinyl chloride resin composition comprising the same as well as excellent impact resistance and weather resistance has the effect of having both excellent heat resistance and high hardness.
이하 본 발명을 상세하게 설명한다. Hereinafter, the present invention will be described in detail.
본 발명은 염화비닐 수지에 첨가되어 내충격성 및 내후성뿐만 아니라 내열성 및 고경도를 부여하는 아크릴계 충격 보강제 및 이의 제조방법을 제공하는 것으로, 이하에서 구체적으로 살펴본다. The present invention provides an acrylic impact modifier and a method for producing the same, which are added to a vinyl chloride resin to impart heat resistance and high hardness as well as impact resistance and weather resistance, and will be described in detail below.
본 발명의 아크릴계 충격 보강제는 (a) 시드를 형성하는 총 단량체 100 중량%에 대하여 비닐계 단량체 0.5 내지 40 중량%, 친수성 단량체 55 내지 99 중량% 및 가교제 단량체 0.5 내지 5 중량%가 중합되어 형성되는 시드 1 내지 10 중량부; (b) 상기 시드를 감싸며, 코어를 형성하는 총 단량체 100 중량%에 대하여 알킬기의 탄소수가 1 내지 8인 알킬 아크릴레이트 80 내지 99.9 중량%, 가교제 단량체 0.1 내지 3 중량% 및 비닐계 단량체 0.1 내지 20 중량%가 중합되어 형성되는 코어 70 내지 90 중량부; 및 (c) 상기 코어를 감싸며, 쉘을 형성하는 총 단량체 100 중량%에 대하여 알킬기의 탄소수가 1 내지 4인 알킬 메타크릴레이트 97 내지 99 중량%, (메타)아크릴산 유도체 또는 말레산 무수물 1 내지 3 중량%가 중합되어 형성되는 쉘 10 내지 30 중량부를 포함하여 이루어진다.Acrylic impact modifier of the present invention (a) is formed by polymerizing 0.5 to 40% by weight of the vinyl monomer, 55 to 99% by weight hydrophilic monomer and 0.5 to 5% by weight of the crosslinker monomer relative to 100% by weight of the total monomer forming the seed 1 to 10 parts seed; (b) 80 to 99.9% by weight of alkyl acrylate having 1 to 8 carbon atoms of alkyl group, 0.1 to 3% by weight of crosslinker monomer and 0.1 to 20 of vinyl monomer, based on 100% by weight of the total monomer forming the core, surrounding the seed. 70 to 90 parts by weight of the core is formed by polymerizing by weight; And (c) 97 to 99% by weight of alkyl methacrylate having 1 to 4 carbon atoms of alkyl group, 1 to 3 of (meth) acrylic acid derivative or maleic anhydride, with respect to 100% by weight of the total monomer forming the shell, surrounding the core. The wt% comprises 10 to 30 parts by weight of the shell formed by polymerization.
본 발명에 따른 (a)시드를 형성하기 위하여 사용되는 비닐계 단량체는 스티렌, 알파 메틸 스티렌, 비닐 톨루엔, 4-클로로스티렌 및 3,4-디클로로 스티렌으로 이루어진 군으로부터 1종 이상 선택되는 것을 사용할 수 있다.The vinyl monomer used to form the seed (a) according to the present invention may be one or more selected from the group consisting of styrene, alpha methyl styrene, vinyl toluene, 4-chlorostyrene and 3,4-dichloro styrene. have.
상기 비닐계 단량체는 시드를 형성하는 총 단량체 100 중량%에 대하여 0.5 내지 40 중량%으로 포함되는 것이 바람직하다. 상기 함량이 40 중량%를 초과할 경우 충격강도가 저하될 수 있으며, 0.5 중량% 미만일 경우 낮은 유리전이 온도를 갖는 다른 단량체의 상대적인 과량으로 인해 열적 특성을 나타내지 못하는 문제점이 있다. The vinyl monomer is preferably included in 0.5 to 40% by weight relative to 100% by weight of the total monomer forming the seed. If the content exceeds 40% by weight, the impact strength may be lowered. If the content is less than 0.5% by weight, the thermal properties may not be exhibited due to the relative excess of other monomers having a low glass transition temperature.
또한, 본 발명에 따른 (a)시드의 형성에 사용되는 친수성 단량체는 메틸 아크릴레이트, 에틸 아크릴레이트, 부틸 아크릴레이트, 2-에틸헥실 아크릴레이트의 알킬 아크릴레이트; 메틸 메타크릴레이트, 벤질 메타크릴레이트의 알킬 메타크릴레이트; 및 아크릴로니트릴로 이루어진 군으로부터 1종 이상 선택되는 것을 사용할 수 있다.In addition, the hydrophilic monomers used for the formation of the seed (a) according to the present invention include alkyl acrylates of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate; Alkyl methacrylates of methyl methacrylate, benzyl methacrylate; And acrylonitrile can be used at least one selected from the group consisting of.
상기 친수성 단량체는 시드를 형성하는 총 단량체 100 중량%에 대하여 55 내지 99 중량%으로 포함되는 것이 바람직하다. 상기 함량이 55 중량% 미만일 경우 고무적인 특성의 감소로 인한 충격이 저하되는 문제점이 있으며, 99 중량%를 초과할 경우 내열성이 발현되지 않는 문제점이 있다. The hydrophilic monomer is preferably included in the 55 to 99% by weight relative to 100% by weight of the total monomer forming the seed. If the content is less than 55% by weight, there is a problem that the impact due to the reduction of the rubber properties is lowered, when the content exceeds 99% by weight there is a problem that the heat resistance is not expressed.
또한, 본 발명에 따른 (a)시드의 형성에 사용되는 가교제 단량체는 디비닐벤젠, 3-부탄디올 디아크릴레이트, 1,3-부탄디올 디메타크릴레이트, 1,4-부탄디올 디아크릴레이트, 1,4-부탄디올 디메타크릴레이트, 알릴 아크릴레이트, 알릴 메타크릴 레이트, 트리메틸올프로판 트리아크릴레이트, 테트라에틸렌글리콜 디아크릴레이트 및 테트라에틸렌글리콜 디메타크릴레이트로 이루어진 군으로부터 1종 이상 선택되는 것을 사용할 수 있다. In addition, the crosslinker monomers used in the formation of the seed (a) according to the present invention are divinylbenzene, 3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1, One or more selected from the group consisting of 4-butanediol dimethacrylate, allyl acrylate, allyl methacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate and tetraethylene glycol dimethacrylate can be used. have.
상기 가교제 단량체는 시드를 형성하는 총 단량체 100 중량%에 대하여 0.5 내지 5 중량%으로 포함되는 것이 바람직하다. 상기 함량이 0.5 중량% 미만일 경우 시드 라텍스 입자안정성이 나빠지게 되는 문제점이 있으며, 5 중량% 초과할 경우 충격강도가 저하되는 문제점이 있다. The crosslinker monomer is preferably included in 0.5 to 5% by weight relative to 100% by weight of the total monomer forming the seed. If the content is less than 0.5% by weight, there is a problem that the seed latex particle stability worsens, when it exceeds 5% by weight there is a problem that the impact strength is lowered.
상기에서 살펴본 바와 같은 비닐계 단량체, 친수성 단량체 및 가교제 단량체를 유화중합으로 가교 반응시켜 시드 라텍스를 제조하게 된다. As described above, the vinyl-based monomer, the hydrophilic monomer, and the crosslinking agent monomer are cross-linked by emulsion polymerization to prepare seed latex.
상기와 같이 형성된 시드는 본 발명의 시드, 코어 및 쉘로 이루어진 아크릴계 충격 보강제 100 중량부에 대하여 1 내지 10 중량부로 포함되는 것이 바람직하다. 상기 함량이 1 중량부 미만일 경우 라텍스내 입자수가 줄어들어 입자간의 간격이 커져 충격강도가 저하되는 문제점이 있을 수 있으며, 10 중량부를 초과할 경우 라텍스내 소구경 입자가 과량으로 존재하여 그만큼 쉘 두께가 감소하고 고무성 코어가 충분히 감싸주지 못하므로 응집특성이 불량해지는 문제점이 있다.The seed formed as described above is preferably included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the acrylic impact modifier composed of the seed, core and shell of the present invention. If the content is less than 1 part by weight, the number of particles in the latex is reduced to increase the spacing between the particles, there is a problem that the impact strength is lowered. When the content exceeds 10 parts by weight, the small thickness particles in the latex is present in excess, reducing the shell thickness by that amount And since the rubber core is not sufficiently wrapped there is a problem that the cohesive properties are poor.
본 발명에 따른 (b)코어를 형성하기 위하여 사용되는 알킬 아크릴레이트는 알킬기의 탄소수가 1 내지 8인 것이 바람직하며, 예를 들어 메틸 아크릴레이트, 에틸 아크릴레이트, 프로필 아크릴레이트, 이소프로필 아크릴레이트, 부틸 아크릴레이트, 헥실 아크릴레이트, 옥틸 아크릴레이트 및 2-에틸헥실 아크릴레이트로 이루어진 군으로부터 1종 이상 선택되는 것을 사용할 수 있다. The alkyl acrylate used to form the core (b) according to the present invention preferably has 1 to 8 carbon atoms in the alkyl group, for example methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, One or more selected from the group consisting of butyl acrylate, hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate can be used.
상기 알킬 아크릴레이트는 코어를 형성하는 총 단량체 100 중량%에 대하여 80 내지 99.9 중량%로 포함되는 것이 바람직하다. 상기 함량이 80 중량% 미만일 경우 고무 성질의 저하로 내충격성이 저하되는 문제점이 있으며, 99.9 중량%를 초과할 경우 코어의 고무성질이 매우 높아 내충격성은 향상되나 경도 및 강도는 저하되는 문제점이 있다.The alkyl acrylate is preferably included in 80 to 99.9% by weight relative to 100% by weight of the total monomer forming the core. If the content is less than 80% by weight, there is a problem that the impact resistance is lowered due to the deterioration of the rubber properties, when the content exceeds 99.9% by weight, the rubber properties of the core is very high, the impact resistance is improved, but the hardness and strength is lowered.
또한, 본 발명에 따른 (b)코어의 형성에 사용되는 가교제 단량체는 앞에서 살펴본 (a)시드의 형성에 사용되는 가교제 단량체와 동일한 성분을 사용할 수 있다. In addition, the crosslinking monomer used in the formation of the core (b) according to the present invention may use the same components as the crosslinking monomer used in the formation of the seed (a).
상기 가교제 단량체는 코어를 형성하는 총 단량체 100 중량%에 대하여 0.1 내지 3 중량%로 포함되는 것이 바람직하다. 상기 함량이 0.1 중량% 미만일 경우 가공 중에 매트릭스와 구형의 입자가 변형될 수 있는 문제점이 있으며, 3 중량%를 초과할 경우 코어가 취성(brittle)의 특성을 나타내어 충격보강효과가 저하된다는 문제점이 있다. The crosslinker monomer is preferably included in 0.1 to 3% by weight relative to 100% by weight of the total monomer forming the core. If the content is less than 0.1% by weight, there is a problem that the matrix and spherical particles may be deformed during processing. If the content is more than 3% by weight, the core exhibits brittle characteristics and thus the impact reinforcing effect is lowered. .
또한, 본 발명에 따른 (b)코어의 형성에 사용되는 비닐계 단량체는 앞에서 살펴본 (a)시드의 형성에 사용되는 비닐계 단량체와 동일한 성분을 사용할 수 있다. In addition, the vinyl monomer used in the formation of the core (b) according to the present invention may use the same components as the vinyl monomer used in the formation of the seed (a).
상기 비닐계 단량체는 코어를 형성하는 총 단량체 100 중량%에 대하여 0.1 내지 20 중량%로 포함되는 것이 바람직하다. 상기 함량이 0.1 중량% 미만일 경우 경도, 강도 및 내열성이 저하되는 문제점이 있으며, 20 중량%를 초과할 경우 내충격성이 저하되는 문제점이 있다. The vinyl monomer is preferably included in 0.1 to 20% by weight based on 100% by weight of the total monomers forming the core. If the content is less than 0.1% by weight, there is a problem in that hardness, strength and heat resistance are lowered, and when it exceeds 20% by weight, impact resistance is lowered.
앞에서 제조된 시드 라텍스에 상기에서 살펴본 바와 같은 알킬 아크릴레이트, 가교제 단량체 및 비닐계 단량체를 유화중합하여 고무성 코어 라텍스를 제조하게 된다. The rubber latex is prepared by emulsion polymerization of the alkyl acrylate, the crosslinker monomer, and the vinyl monomer as described above in the seed latex prepared above.
상기와 같이 형성된 코어는 본 발명의 시드, 코어 및 쉘로 이루어진 아크릴계 충격 보강제 100 중량부에 대하여 70 내지 90 중량부로 포함되는 것이 바람직하다. 상기 함량이 70 중량부 미만일 경우 충격을 흡수 할 수 있는 고무적 성질이 적어 충격이 저하되는 문제점이 발생할 수 있으며, 90 중량부를 초과할 경우 상대적으로 쉘 함량이 적어져 매트릭스 수지와의 상용성과 분산성이 떨어져 결과적으로 가공의 문제점이 발생할 수 있다.The core formed as described above is preferably included in 70 to 90 parts by weight based on 100 parts by weight of the acrylic impact modifier consisting of the seed, core and shell of the present invention. If the content is less than 70 parts by weight, there is a problem in that the impact is reduced due to the less rubbery properties that can absorb the shock, and when the content exceeds 90 parts by weight, the shell content is relatively small, so that the compatibility and dispersibility with the matrix resin As a result, processing problems may occur.
본 발명에 따른 (c)쉘을 형성하기 위하여 사용되는 알킬 메타크릴레이트는 알킬기의 탄소수가 1 내지 4인 것이 바람직하며, 예를 들어 메틸 메타크릴레이트, 에틸 메타크릴레이트, 부틸 메타크릴레이트, 아크릴로니트릴 및 메타크릴로니트릴로 이루어진 군으로부터 1종 이상 선택되는 것을 사용할 수 있다. The alkyl methacrylate used to form the (c) shell according to the present invention preferably has 1 to 4 carbon atoms in the alkyl group, for example methyl methacrylate, ethyl methacrylate, butyl methacrylate, acryl One or more selected from the group consisting of ronitrile and methacrylonitrile can be used.
상기 알킬 메타크릴레이트는 쉘을 형성하는 총 단량체 100 중량%에 대하여 97 내지 99 중량%로 포함되는 것이 바람직하다.The alkyl methacrylate is preferably included in 97 to 99% by weight relative to 100% by weight of the total monomers forming the shell.
또한, 본 발명에 따른 (c)쉘의 형성에 사용되는 (메타)아크릴산 유도체는 페닐 메타크릴레이트, 아크릴릭산, 메타크릴릭산, 이타코닉산, 히드록실 메틸 메타크릴레이트 및 글리시딜 메타크릴레이트로 이루어진 군으로부터 1종 이상 선택되는 것을 사용할 수 있다. In addition, the (meth) acrylic acid derivatives used for the formation of the (c) shell according to the present invention are phenyl methacrylate, acrylic acid, methacrylic acid, itaconic acid, hydroxyl methyl methacrylate and glycidyl methacrylate. One or more selected from the group consisting of can be used.
상기 (메타)아크릴산 유도체 또는 말레산 무수물은 쉘을 형성하는 총 단량체 100 중량%에 대하여 1 내지 3 중량%로 포함되는 것이 바람직하다. 상기 함량이 1 중량% 미만일 경우 내열성 및 내후성이 취약한 문제점이 있으며, 3 중량%를 초과할 경우 염화비닐 수지에서의 분산성 악화로 인해 충격강도가 저하되는 문제점이 있다. The (meth) acrylic acid derivative or maleic anhydride is preferably included in an amount of 1 to 3% by weight based on 100% by weight of the total monomers forming the shell. When the content is less than 1% by weight, there is a problem in that heat resistance and weather resistance are weak, and when it exceeds 3% by weight, the impact strength is lowered due to deterioration in dispersibility in the vinyl chloride resin.
앞에서 제조된 고무 코어 라텍스에 상기에서 살펴본 바와 같은 알킬 메타크릴레이트, (메타)아크릴산 유도체 또는 말레산 무수물과 같은 높은 유리전이온도를 가지는 단량체를 그라프트 중합하여 쉘을 형성시켜 본 발명의 아크릴계 충격 보강제를 제조하게 된다. The acrylic impact modifier of the present invention is formed by graft polymerizing a monomer having a high glass transition temperature such as alkyl methacrylate, (meth) acrylic acid derivative or maleic anhydride as described above in the rubber core latex prepared above. It will be prepared.
상기와 같이 형성된 쉘은 본 발명의 시드, 코어 및 쉘로 이루어진 아크릴계 충격 보강제 100 중량부에 대하여 10 내지 30 중량부로 포함되는 것이 바람직하다. 상기 함량이 10 중량부 미만일 경우 쉘의 두께가 얇아 응집 특성 및 라텍스의 기계적 안정성이 취약해지는 문제점이 있으며, 30중량부를 초과할 경우 두꺼운 쉘 두께로 인해 응집 온도가 높아지는 단점이 있고 상대적인 고무성 코어의 감소로 인해 충격이 저하되는 문제가 생길 수 있다. The shell formed as described above is preferably included in 10 to 30 parts by weight based on 100 parts by weight of the acrylic impact modifier consisting of the seed, core and shell of the present invention. If the content is less than 10 parts by weight, the shell thickness is thin, there is a problem that the cohesive properties and mechanical stability of the latex is weak, if the content exceeds 30 parts by weight due to the thick shell thickness has a disadvantage of increasing the coagulation temperature of the relative rubber core The reduction can lead to the problem of lowering the impact.
본 발명의 염화비닐 수지 조성물은 염화비닐 수지 100 중량부와 상기 본 발명에 따라 제조된 아크릴계 충격 보강제 1 내지 30 중량부를 포함하여 이루어지며, 이러한 염화비닐 수지 조성물은 내충격성 및 내후성이 우수할 뿐만 아니라, 우수한 내열성 및 높은 경도를 가지게 된다. The vinyl chloride resin composition of the present invention comprises 100 parts by weight of the vinyl chloride resin and 1 to 30 parts by weight of the acrylic impact modifier prepared according to the present invention. Such a vinyl chloride resin composition is not only excellent in impact resistance and weather resistance. It has excellent heat resistance and high hardness.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실 시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예 에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
[실시예]EXAMPLE
<아크릴계 충격 보강제 제조><Acryl-based impact reinforcing agent manufacturing>
실시예Example 1 One
1) 시이드 중합1) Seed polymerization
먼저 교반기와 온도계, 질소 투입구와 순환 콘덴서를 장착한 4구 플라스크의 반응기를 준비하고 탈이온수(deionized water; DDI water) 4.33중량부와 소디움라우릴설페이트 (Sodium lauryl sulfate; SLS) 0.04중량부, 소디움포름알데히드설폭실레이트 (Sodium formaldehyde sulfoxylate; SFS)0.01중량부, 디소디움에틸렌디아민테드라아세테이트 (dixodium ethylendiaminetetraacetate; EDTA) 0.0014중량부, 페로스 설페이트(Ferrous sulfate; FES) 0.0001중량부으로 이루어진 미리 제조한 4 wt% 활성화 용액 0.3중량부를 반응기 내부에 투입하고 온도를 60℃까지 상승시킨다. 이온교환수의 온도가 60℃에 도달하면 탈이온수 2.96중량부, 부틸 아크릴레이트(Butylacrylate; BA) 2.98중량부, 스타이렌(Styrene; ST) 2중량부, 아릴메타크릴레이트(Allylmethacrylate; AMA) 0.02중량부, 소디움라우릴설페이트 (Sodium lauryl sulfate; SLS) 0.025중량부 및 큐멘하이드로퍼옥사이드 (Cumenehydroperoxide: CHP) 0.013중량부를 혼합하여 미리 제조한 단량체 프리 에멀젼을 4시간동안 투입하여 반응을 진행시켰다. 반응기내 온도를 60℃로 유지하면서 시이드를 중합하였다. First, prepare a reactor of a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a circulating condenser. Formaldehyde sulfoxylate (SFS) 0.01 parts by weight, disodium ethylenediaminetetraacetate (EDTA) 0.0014 parts by weight, ferro sulfate (FES) 0.0001 parts by weight prepared in advance 0.3 parts by weight of a 4 wt% activating solution was introduced into the reactor and the temperature was raised to 60 ° C. When the temperature of the ion-exchanged water reaches 60 ° C, 2.96 parts by weight of deionized water, 2.98 parts by weight of butyl acrylate (BA), 2 parts by weight of styrene (ST), and aryl methacrylate (AllMA) 0.02 By weight, 0.025 parts by weight of sodium lauryl sulfate (SLS) and 0.013 parts by weight of cumenehydroperoxide (CHP) were mixed, and the prepared monomer pre-emulsion was added for 4 hours to proceed with the reaction. The seed was polymerized while maintaining the temperature in the reactor at 60 ° C.
2) 코어 중합2) core polymerization
상기에서 제조한 시이드 라텍스 5.0중량부 및 탈이온수 44.4중량부를 차례로 반응기에 첨가하여, 질소 세척과 함께 온도를 75℃까지 승온시켰다. 고무성 코어를 형성시키기 위하여 탈이온수(deionized water; DDI water) 33중량부, 부틸 아크릴레이트(Butylacrylate; BA) 64.4중량부, 알파메틸스티렌(α-Methylstyenre; AMS) 10중량부, 아릴 메타크릴레이트(Allylmethacrylate; AMA) 0.6중량부, 소디움라우릴설페이트 (Sodium lauryl sulfate; SLS) 0.27중량부를 함유한 단량체 프리 에멀젼과 별도의 큐멘하이드로퍼옥사이드 (Cumenehydroperoxide: CHP) 0.015중량부, 시드 중합 시 사용한 동일한 활성화 용액 4wt% 5중량부를 온도 75℃에서 5시간동안 투입하여 반응 시켰다. 반응에서 반응기의 온도는 75℃로 일정하게 유지하였으며, 질소 세척은 반응이 종결될 때까지 연속적으로 수행하였고, 단량체 프리에멀젼과 큐멘하이드로퍼옥사이드 투입이 끝난 후 온도 80℃에서 1시간 숙성시키고 코어 부분을 완성한다. 5.0 parts by weight of the prepared latex and 44.4 parts by weight of deionized water were sequentially added to the reactor, and the temperature was raised to 75 ° C with nitrogen washing. 33 parts by weight of deionized water (DDI water), 64.4 parts by weight of butyl acrylate (BA), 10 parts by weight of α-Methylstyenre (AMS), aryl methacrylate to form a rubbery core (Allylmethacrylate; AMA) 0.65 parts by weight, monomer pre-emulsion containing 0.27 parts by weight of sodium lauryl sulfate (SLS) and 0.015 parts by weight of separate cumenehydroperoxide (CHP), the same activation used in seed polymerization 4 parts by weight of 5 parts by weight of the reaction was added at a temperature of 75 ℃ for 5 hours to react. In the reaction, the temperature of the reactor was kept constant at 75 ° C., and nitrogen washing was performed continuously until the reaction was completed. After completion of the monomer preemulsion and cumene hydroperoxide, the temperature was aged at 80 ° C. for 1 hour and the core part was removed. To complete.
3) 쉘 중합3) shell polymerization
반응기의 내부 온도를 60℃로 조절한 후 탈이온교환수 2.24 중량부, 소디움라우릴설페이트 (Sodium lauryl sulfate; SLS) 0.012중량부, 및 메틸 메타크릴레이트(Methylmethacrylate; MMA) 18중량부와 메타크릴릭산(Methacrylic acid; MAA) 2중량부를 혼합한 단량체를 첨가하여 에멀션을 만들었다. 에멀션을 만든 후 반응기의 내부 온도를 70℃로 유지하고 질소분위기로 치환한 후, 중합 개시제로 포타슘 퍼설페이트 용액 (Potassium persulfate; KPS 3wt%) 2중량부와 4wt% 활성화 용액 0.5중량부를 첨가하여 반응을 진행 시켰다. After adjusting the internal temperature of the reactor to 60 ° C., 2.24 parts by weight of deionized water, 0.012 part of sodium lauryl sulfate (SLS), and 18 parts by weight of methyl methacrylate (MMA) and methacryl An emulsion was prepared by adding monomers mixed with 2 parts by weight of methacrylic acid (MAA). After the emulsion was prepared, the reactor was maintained at 70 ° C. and replaced with a nitrogen atmosphere. Then, 2 parts by weight of potassium persulfate (KPS 3 wt%) and 0.5 parts by weight of 4 wt% activating solution were added as a polymerization initiator. Proceeded.
4) 아크릴레이트 라텍스 응집4) acrylate latex flocculation
상기에서 제조된 아크릴레이트 라텍스를 이온교환수를 투입하여 라텍스 고형분 함량을 10 중량%로 낮춘다. 온도를 60℃로 상승 시킨 후, 이 희석 라텍스에 CaCl2 수용액(22 wt% 농도의 희석 용액) 4중량부를 교반 하면서 투입하여 중합체 입자들을 응집시켜 모액 분리된 슬러리 상태를 만들었다. 이어서 입자들의 뭉치는 현상을 방지하고 입도를 향상 시키고자 유기 분산제 4중량부를 응집 직후 모액 분리 된 상태에 투입하여 교반 하였다.The acrylate latex prepared above is charged with ion-exchanged water to lower the latex solids content to 10% by weight. After the temperature was raised to 60 ° C., 4 parts by weight of CaCl 2 aqueous solution (22 wt% dilute solution) was added to the diluted latex with stirring to agglomerate the polymer particles, thereby preparing a mother liquid separated slurry. Subsequently, 4 parts by weight of the organic dispersant was added to the mother liquid separated state immediately after aggregation to prevent agglomeration of particles and to improve particle size, followed by stirring.
상기 응집 슬러리를 90℃까지 승온시키고, 60분 동안 숙성 시킨 후 냉각시켰다. 이를 이온 교환수로 2 내지 3 회 세척하여 잔류 모노머를 제거한 후, 이를 여과기를 사용하여 탈수 시켰다.The flocculation slurry was heated to 90 ° C., aged for 60 minutes and then cooled. This was washed 2-3 times with ion-exchanged water to remove residual monomer, which was then dehydrated using a filter.
상기 과정을 거쳐 탈수된 파우더 형태의 아크릴계 충격보강제를 열풍 건조기 100℃에서 2 시간 동안 건조 시킨 후, 30mesh 에 통과시켜 균일한 입자의 파우더를 회수하였다.After drying the acrylic impact modifier in the form of powder dehydrated through the above process for 2 hours at 100 ℃ hot air dryer, and passed through 30mesh to recover the powder of uniform particles.
실시예Example 2 2
실시예 1의 3)쉘 중합에 있어서, 탈이온교환수 2.24중량부, 소디움라우릴설페이트 (Sodium lauryl sulfate; SLS) 0.012중량부, 및 메틸 메타크릴레이트(Methylmethacrylate; MMA) 18중량부와 페닐메타크릴레이트(Phenyl methacrylate; PMA) 2중량부를 혼합한 단량체를 첨가하여 에멀션을 만든 것을 제외 하고는 실시예1과 같은 제조 방법으로 아크릴계 충격 보강제 파우더를 회수하였다. 3) Shell polymerization of Example 1, 2.24 parts by weight of deion-exchanged water, 0.012 parts by weight of sodium lauryl sulfate (SLS), and 18 parts by weight of methyl methacrylate (MMA) and phenylmeta An acrylic impact modifier powder was recovered by the same method as in Example 1 except that an emulsion was prepared by adding a monomer mixed with 2 parts by weight of methacrylate (Phenyl methacrylate; PMA).
실시예Example 3 3
실시예 1의 3)쉘 중합에 있어서, 탈이온교환수 2.24중량부, 소디움라우릴설페이트 (Sodium lauryl sulfate; SLS) 0.012중량부, 및 메틸 메타크릴레이트(Methylmethacrylate; MMA) 18중량부와 멜레안하이드라이드(Maleic anhydride; MAH) 2중량부를 혼합한 단량체를 첨가하여 에멀션을 만든 것을 제외하고는 실시예1과 같은 제조 방법으로 아크릴계 충격 보강제 파우더를 회수하였다. 3) Shell polymerization of Example 1, 2.24 parts by weight of deion-exchanged water, 0.012 parts by weight of sodium lauryl sulfate (SLS), and 18 parts by weight of methyl methacrylate (MMA) and melane An acrylic impact modifier powder was recovered in the same manner as in Example 1 except that an emulsion was prepared by adding a monomer mixed with 2 parts by weight of a hydride (Maleic anhydride; MAH).
비교예Comparative example 1 One
실시예 1의 2)코어 중합에 있어서, 상기에서 제조한 시이드 라텍스 5.0중량부 및 탈이온수 44.4중량부를 차례로 반응기에 첨가하여, 질소 세척과 함께 온도를 55℃까지 승온시켰다. 고무성 코어를 형성시키기 위하여 탈이온수(deionized water; DDI water) 33중량부, 부틸 아크릴레이트(Butylacrylate; BA) 74.4중량부, 아릴 메타크릴레이트(Allylmethacrylate; AMA) 0.6중량부, 소디움라우릴설페이트 (Sodium lauryl sulfate; SLS) 0.27중량부를 함유한 단량체 프리 에멀젼을 제조한 것을 제외하고는 실시예1과 같은 제조 방법으로 아크릴계 충격 보강제 파우더를 회수하였다. In 2) core polymerization of Example 1, 5.0 weight part of said seed latex and 44.4 weight part of deionized water which were prepared above were sequentially added to the reactor, and the temperature was heated up to 55 degreeC with nitrogen washing. 33 parts by weight of deionized water (DDI water), 74.4 parts by weight of butyl acrylate (BA), 0.6 parts by weight of aryl methacrylate (AMA), sodium lauryl sulfate ( An acrylic impact modifier powder was recovered in the same manner as in Example 1 except that a monomer free emulsion containing 0.27 parts by weight of sodium lauryl sulfate (SLS) was prepared.
비교예Comparative example 2 2
실시예 1의 2)코어 중합에 있어서, 상기에서 제조한 시이드 라텍스 5.0중량부 및 탈이온수 44.4중량부를 차례로 반응기에 첨가하여, 질소 세척과 함께 온도를 55℃까지 승온시켰다. 고무성 코어를 형성시키기 위하여 탈이온수(deionized water; DDI water) 33중량부, 부틸 아크릴레이트(Butylacrylate; BA) 64.4중량부, 알파메틸스티렌(α-Methylstyenre; AMS) 10중량부, 아릴 메타크릴레이트(Allylmethacrylate; AMA) 0.6중량부, 소디움라우릴설페이트 (Sodium lauryl sulfate; SLS) 0.27중량부를 함유한 단량체 프리 에멀젼을 제조한다. In 2) core polymerization of Example 1, 5.0 weight part of said seed latex and 44.4 weight part of deionized water which were prepared above were sequentially added to the reactor, and the temperature was heated up to 55 degreeC with nitrogen washing. 33 parts by weight of deionized water (DDI water), 64.4 parts by weight of butyl acrylate (BA), 10 parts by weight of α-Methylstyenre (AMS), aryl methacrylate to form a rubbery core A monomer free emulsion containing 0.6 parts by weight of (Allylmethacrylate; AMA) and 0.27 parts by weight of sodium lauryl sulfate (SLS) was prepared.
또한 실시예 1의 3)쉘 중합에 있어서, 탈이온교환수 2.24중량부, 소디움라우릴설페이트 (Sodium lauryl sulfate; SLS) 0.012중량부, 및 메틸 메타크릴레이트(Methylmethacrylate; MMA) 16중량부와 메타크릴릭엑시드(Methacrylic acid; MAA) 4중량부를 혼합한 단량체를 첨가하여 에멀젼을 제조한 것을 제외하고는 실시예1과 같은 제조 방법으로 아크릴계 충격 보강제 파우더를 회수하였다. Also, in 3) Shell polymerization of Example 1, 2.24 parts by weight of deion-exchanged water, 0.012 parts by weight of sodium lauryl sulfate (SLS), and 16 parts by weight of methyl methacrylate (MMA) and meta An acrylic impact modifier powder was recovered by the same method as in Example 1 except that an emulsion was prepared by adding a monomer mixed with 4 parts by weight of methacrylic acid (MAA).
비교예Comparative example 3 3
실시예 1의 1)시드 중합에 있어서, 부틸 아크릴레이트(Butylacrylate; BA) 4.98중량부, 아릴메타크릴레이트(Allylmethacrylate; AMA) 0.02중량부, 소디움라우릴설페이트 (Sodium lauryl sulfate; SLS) 0.025중량부 t-부틸 하이드로퍼옥사이드 (t-butyl hydroperoxide: TBHP 1wt%) 0.13중량부를 혼합하여 단량체 프리 에멀젼을 제조한다.In 1) seed polymerization of Example 1, 4.98 parts by weight of butyl acrylate (BA), 0.02 part by weight of aryl methacrylate (AMA), 0.025 part by weight of sodium lauryl sulfate (SLS) 0.13 parts by weight of t-butyl hydroperoxide (TBHP 1wt%) was mixed to prepare a monomer free emulsion.
또한, 실시예 1의 2)코어 중합에 있어서, 상기 제조된 시드 5.0중량부 및 탈이온수 44.4중량부를 차례로 반응기에 첨가하여, 질소 세척과 함께 온도를 55℃까지 승온시켰다. 고무성 코어를 형성시키기 위하여 탈이온수(deionized water; DDI water) 33중량부, 부틸 아크릴레이트(Butylacrylate; BA) 74.4중량부, 아릴 메타크릴레이트(Allylmethacrylate; AMA) 0.6중량부, 소디움라우릴설페이트 (Sodium lauryl sulfate; SLS) 0.27중량부를 함유한 단량체 프리 에멀젼을 제조한 것을 제외하고는 실시예1과 같은 제조 방법으로 아크릴계 충격 보강제 파우더를 회수하였다. In addition, in 2) core polymerization of Example 1, 5.0 weight part of said seeds and 44.4 weight part of deionized water were added one by one to the reactor, and the temperature was heated up to 55 degreeC with nitrogen washing. 33 parts by weight of deionized water (DDI water), 74.4 parts by weight of butyl acrylate (BA), 0.6 parts by weight of aryl methacrylate (AMA), sodium lauryl sulfate ( An acrylic impact modifier powder was recovered in the same manner as in Example 1 except that a monomer free emulsion containing 0.27 parts by weight of sodium lauryl sulfate (SLS) was prepared.
비교예Comparative example 4 4
비교예 3의 2)코어 중합에 있어서, 고무성 코어를 형성시키기 위하여 탈이온수(deionized water; DDI water) 33중량부, 부틸 아크릴레이트(Butylacrylate; BA) 64.4중량부, 알파메틸스티렌(α-Methylstyenre; AMS) 10중량부, 아릴메타크릴레이트(Allylmethacrylate; AMA) 0.6중량부, 소디움라우릴설페이트 (Sodium lauryl sulfate; SLS) 0.27중량부를 함유한 단량체 프리 에멀젼을 제조한 것을 제외하고는 비교예 3과 같은 제조 방법으로 아크릴계 충격 보강제 파우더를 회수하였다. 2) In the core polymerization of Comparative Example 3, 33 parts by weight of deionized water (DDI water), 64.4 parts by weight of butyl acrylate (BA) and alphamethylstyrene (α-Methylstyenre) to form a rubbery core AMS), 10 parts by weight of aryl methacrylate (Allylmethacrylate; AMA) 0.6 parts by weight, sodium lauryl sulfate (SLS) 0.27 parts by weight except that a monomer pre-emulsion was prepared except that The acrylic impact modifier powder was recovered by the same manufacturing method.
비교예Comparative example 5 5
비교예 3의 3)쉘 중합에 있어서, 탈이온교환수 2.24중량부, 소디움라우릴설페이트 (Sodium lauryl sulfate; SLS) 0.012중량부, 메틸 메타크릴레이트(Methylmethacrylate; MMA) 18중량부와 메타크릴릭엑시드(Methacrylic acid; MAA) 2중량부를 혼합한 단량체를 첨가하여 에멀션을 만든 것을 제외하고는 비교예 3과 같은 제조 방법으로 아크릴계 충격 보강제 파우더를 회수하였다. 3) Shell polymerization of Comparative Example 3, 2.24 parts by weight of deion-exchanged water, 0.012 parts by weight of sodium lauryl sulfate (SLS), 18 parts by weight of methyl methacrylate (MMA) and methacrylic An acrylic impact modifier powder was recovered in the same manner as in Comparative Example 3 except that an emulsion was prepared by adding a monomer mixed with 2 parts by weight of an acid (Methacrylic acid; MAA).
상기 실시예 1 내지 3 및 비교예 1 내지 5에 따른 조성비 및 물성을 하기 표 1에 나타내었다. Composition ratios and physical properties according to Examples 1 to 3 and Comparative Examples 1 to 5 are shown in Table 1 below.
[표 1]TABLE 1
< 염화비닐 수지 조성물 제조 ><Production of vinyl chloride resin composition>
염화비닐수지(LS 100, LG화학 제조) 100중량부, 틴계 열안정제(BT-107) 2.0중량부, 칼슘스테아레이트(Ca-St) 1.2중량부, 폴리에틸렌왁스(PE-WAX) 1.0 중량부 및 충진제(CaCO3) 14중량부를 115℃까지 승온하면서 헨셀 믹서기를 이용하여 혼련시켜 염화비닐 수지를 제조하였다. 100 parts by weight of vinyl chloride resin (LS 100, manufactured by LG Chemical), 2.0 parts by weight of tin-based heat stabilizer (BT-107), 1.2 parts by weight of calcium stearate (Ca-St), 1.0 parts by weight of polyethylene wax (PE-WAX), and 14 parts by weight of the filler (CaCO 3 ) was kneaded using a Henschel mixer while heating up to 115 ° C. to produce a vinyl chloride resin.
상기 염화비닐 수지와 앞에서 제조한 아크릴계 충격보강제 파우더를 하기 표 2와 같은 배율에 따라(헨셀 믹서를 이용하여 115℃에서 20분간 혼련 시켜 염화비닐 수지 조성물을 제조하였다. The vinyl chloride resin and the acrylic impact modifier powder prepared above were kneaded for 20 minutes at 115 ° C. using a Henschel mixer to prepare a vinyl chloride resin composition.
상기 제조된 염화비닐 수지 조성물의 가공성 및 물성을 다음과 같이 측정하여 그 결과를 표 2에 나타내었다.Processability and physical properties of the vinyl chloride resin composition prepared above were measured as follows, and the results are shown in Table 2.
Haake Extruder를 이용해 일정한 가공온도 C1/C2/C3/Die = 190℃/180℃/188℃/165℃ 조건에서 압출하여, 윈도우 프로파일을 제작 하여 ISO 179 규격 Charpy 충격강도 및 ASTM D785 규격 경도 측정, ASTM D638 규격 인장강도 측정, ASTM D648 규격 열변형 온도(HDT), ASTM G-156 규격 내후성을 측정하였다.Extruded at a constant processing temperature C1 / C2 / C3 / Die = 190 ℃ / 180 ℃ / 188 ℃ / 165 ℃ using a Haake Extruder to make a window profile to measure ISO 179 Charpy impact strength and ASTM D785 hardness, ASTM D638 standard tensile strength measurement, ASTM D648 standard heat deflection temperature (HDT), ASTM G-156 standard weather resistance was measured.
[표 2]TABLE 2
상기 표 1을 통하여, 본 발명에 따른 아크릴계 충격 보강제를 제조한 실시예 1 내지 3은 성분 또는 조성비가 본 발명의 해당 범위를 벗어난 비교예 1 내지 5와 비교하여 유리전이온도가 높음을 확인할 수 있는데, 특히 비교예 1과 비교예 3 내지 5를 통하여 코어 중합시 비닐계 단량체의 부재 및 쉘 중합시 (메타)아크릴산 유도체 또는 말레산 무수물의 부재가 유리전이온도의 저하를 가져옴을 확인할 수 있었다. Through Table 1, Examples 1 to 3 prepared an acrylic impact modifier according to the present invention can be confirmed that the glass transition temperature is high compared to Comparative Examples 1 to 5 in which the component or composition ratio is outside the range of the present invention. In particular, it was confirmed through Comparative Example 1 and Comparative Examples 3 to 5 that the absence of a vinyl monomer during core polymerization and the absence of (meth) acrylic acid derivatives or maleic anhydride during shell polymerization resulted in a decrease in glass transition temperature.
또한 상기 표 2를 통하여, 코어 중합시 비닐계 단량체를 포함하지 않은 비교 예 6, 8 및 10은 경도, 강도 및 열적 특성이 저하됨을 알 수 있다. 또한, 쉘 중합시 (메타)아크릴산 유도체 또는 말레산 무수물을 다량 사용한 비교예 7은 염화비닐 수지에서의 분산성 악화로 인해 충격강도가 저하됨을 확인할 수 있다. 또한, 코어 중합시 알킬 아크릴레이트를 다량 사용한 비교예 8은 코어의 고 고무성질로 인해 충격은 향상되나 경도 및 강도의 물성이 저하됨을 확인할 수 있다. 또한, 쉘 중합시 (메타)아크릴산 유도체 또는 말레산 무수물을 포함하지 않은 비교예 9는 내후성이 취약한 단점이 있음을 확인할 수 있다. In addition, it can be seen from Table 2 that Comparative Examples 6, 8, and 10, which do not include a vinyl monomer during core polymerization, have reduced hardness, strength, and thermal characteristics. In addition, Comparative Example 7 using a large amount of (meth) acrylic acid derivative or maleic anhydride during shell polymerization can confirm that the impact strength is lowered due to deterioration of dispersibility in the vinyl chloride resin. In addition, Comparative Example 8 using a large amount of alkyl acrylate during the core polymerization can be confirmed that the impact is improved due to the high rubber properties of the core, but the physical properties of hardness and strength are reduced. In addition, Comparative Example 9, which does not include a (meth) acrylic acid derivative or maleic anhydride during shell polymerization, may have a weak weather resistance.
이상에서 본 발명의 기재된 구체예를 중심으로 상세히 설명하였지만, 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Although described in detail above with reference to the specific embodiments of the present invention, it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention, and such modifications and modifications belong to the appended claims. It is also natural.
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| WO2015016677A1 (en) * | 2013-08-02 | 2015-02-05 | 주식회사 엘지화학 | Resin |
| CN105593253A (en) * | 2013-08-02 | 2016-05-18 | Lg化学株式会社 | Resin |
| KR20180033653A (en) * | 2016-09-26 | 2018-04-04 | 주식회사 엘지화학 | MBS impact modifier, polyvinyl chloride resin composition comprising the same |
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| WO2015016677A1 (en) * | 2013-08-02 | 2015-02-05 | 주식회사 엘지화학 | Resin |
| CN105593253A (en) * | 2013-08-02 | 2016-05-18 | Lg化学株式会社 | Resin |
| KR20180033653A (en) * | 2016-09-26 | 2018-04-04 | 주식회사 엘지화학 | MBS impact modifier, polyvinyl chloride resin composition comprising the same |
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