KR101030513B1 - Methacrylate Copolymer for Processing Aids of Vinylchloride Resin and Method for Production Thereof - Google Patents
Methacrylate Copolymer for Processing Aids of Vinylchloride Resin and Method for Production Thereof Download PDFInfo
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F2/22—Emulsion polymerisation
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
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- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
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- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L27/06—Homopolymers or copolymers of vinyl chloride
Abstract
본 발명은 염화비닐 수지의 가공 조제용 메타크릴레이트 공중합체 및 그 제조방법에 관한 것으로서 (A) 메틸메타크릴레이트 60 내지 85 중량%, (B) 알킬아크릴레이트계 화합물 15 내지 30 중량% 및 (C) 에폭사이드계 화합물 1 내지 10 중량%를 중합하여 이루어지는 것을 특징으로 한다.The present invention relates to a methacrylate copolymer for processing aid of vinyl chloride resin and a method for preparing the same, (A) 60 to 85% by weight of methyl methacrylate, (B) 15 to 30% by weight of an alkyl acrylate compound, and ( C) It is characterized by polymerizing 1-10 weight% of epoxide type compounds.
염화비닐 수지, 가공 조제, 메타크릴레이트, 공중합체 Vinyl chloride resin, processing aid, methacrylate, copolymer
Description
발명의 분야Field of invention
본 발명은 염화비닐 수지의 가공 조제용 메타크릴레이트 공중합체 및 그 제조방법에 관한 것이다. 보다 구체적으로 본 발명은 염화비닐 수지의 고유 물성에 영향을 주지 않으면서 수지 가공에 있어서 용융시간을 단축할 수 있으며, 압출가공, 칼렌더링 가공에서 미겔화물(fish-eye)과 흐름자국 발생을 감소시킬 수 있는 염화비닐 수지의 가공 조제용 메타크릴레이트 공중합체 및 그 제조 방법에 관한 것이다.The present invention relates to a methacrylate copolymer for processing aid of vinyl chloride resin and a method for producing the same. More specifically, the present invention can shorten the melting time in the resin processing without affecting the intrinsic physical properties of the vinyl chloride resin, and reduce the occurrence of fish-eye and flow marks in the extrusion process and the calendering process. The methacrylate copolymer for processing aid of vinyl chloride resin which can be made, and its manufacturing method are related.
발명의 배경Background of the Invention
가정용품, 산업용품 등에 광범위하게 사용되는 염화비닐 수지는 물리적, 화 학적 성질이 우수하다. 그러나, 염화비닐 수지는 가공온도가 수지의 열분해 온도에 가까워 가공온도의 온도 영역이 좁고, 열분해를 막기 위해 낮은 온도에서 가공하기 때문에 용융상태로 되는 시간이 길다는 등의 여러 가지 가공상의 문제가 있다. Vinyl chloride resins, which are widely used in household goods and industrial goods, have excellent physical and chemical properties. However, vinyl chloride resins have various processing problems, such as the processing temperature is close to the thermal decomposition temperature of the resin, so that the temperature range of the processing temperature is narrow, and the processing time is low because the processing is performed at low temperature to prevent thermal decomposition. .
용융 시간을 단축하기 위해 염화비닐 수지에 가소제를 첨가하는 방법, 염화비닐에 초산비닐 등의 다른 단량체를 공중합시킨 염화비닐계 수지를 사용하는 방법, 염화비닐 수지에 다른 수지 성분을 혼합하는 방법이 알려져 있다. 그러나, 가공시 혼련에너지가 유동에 의하여 소비되므로 염화비닐 수지의 겔화가 불충분하게 되어 물리적 성질이 저하되며 미겔화물과 흐름자국 등이 발생하는 문제가 있다.In order to shorten melting time, a method of adding a plasticizer to vinyl chloride resin, a method of using vinyl chloride resin copolymerized with other monomers such as vinyl acetate and vinyl chloride, and a method of mixing other resin components with vinyl chloride resin are known. have. However, since the kneading energy is consumed by the flow during processing, the gelation of the vinyl chloride resin is insufficient, so that the physical properties are deteriorated, and there is a problem in that the gelate and flow traces occur.
미국특허 제6,730,741은 메틸메타크릴레이트와 알킬아크릴레이트를 공중합하여 미겔화물(Fish-eye)을 방지하고, 용융시간을 단축하고자 하였으나 과량의 알킬아크릴레이트를 사용함으로 인하여 전체적인 용융점도가 저하되어 가공이 잘 이루어지지 않았으며 기포발생 등의 문제점이 있었다.U.S. Pat.No. 6,730,741 attempts to prevent fish-eye and shorten the melting time by copolymerizing methyl methacrylate and alkyl acrylate, but the overall melt viscosity is reduced due to the use of excess alkyl acrylate. It was not well done and there were problems such as bubble generation.
또한, 미국특허 제4,268,636에서는 메틸메타크릴레이트를 주성분으로 하는 고분자와 메틸메타크릴레이트에 디올레핀이나 이타콘산등을 중합시킨 고분자를 혼합하여 제조한 가공조제로 염화비닐수지의 미겔화물과 흐름자국 발생을 저하시키는 방법을 제시하고 있다. 그러나, 이 방법은 상기 고분자들의 혼합 불균일성에 의해 가공된 염화비닐 수지의 미겔화물과 흐름자국의 발생이 증가할 수 있다.In addition, U.S. Patent No. 4,268,636 is a processing aid prepared by mixing a polymer containing methyl methacrylate as a main component and a polymer obtained by polymerizing diolefin or itaconic acid with a methyl methacrylate, and thus generating a gelate and a flow trace of vinyl chloride resin. It suggests a way to reduce this. However, this method can increase the generation of microglides and flow marks of the processed vinyl chloride resin due to the mixing heterogeneity of the polymers.
또한, 한국특허공개 2004-0043951에 의하면 분자량 1,000,000의 메틸메타크릴레이트 수지와 분자량 4,500,000의 메틸메타크릴레이트 수지를 블렌딩하여 염화비닐수지의 미겔화물과 흐름자국 발생을 저하시키는 방법을 제시하고 있다. 그러 나, 이 방법은 두 가지 고분자를 제조한 후 혼합해야 하는 문제가 있으며, 다량의 저분자량 메틸메타크릴레이트 수지에 의한 기포 발생 등의 문제점이 발생하게 된다.In addition, according to Korean Patent Publication No. 2004-0043951, a method of blending a methylmethacrylate resin having a molecular weight of 1,000,000 and a methylmethacrylate resin having a molecular weight of 4,500,000 to reduce the generation of microchloride and flow traces of a vinyl chloride resin is disclosed. However, this method has a problem that the two polymers must be prepared and then mixed, and problems such as bubbles are generated due to a large amount of low molecular weight methyl methacrylate resin.
이에 본 발명자들은 상기 문제점을 해결하기 위하여, 에폭사이드 화합물을 도입함으로서, 염화비닐수지의 가공에서 용융시간을 단축할 수 있으며, 압출가공, 칼렌더링 가공에서 미겔화물(fish-eye)과 흐름자국 발생을 획기적으로 감소시킬 수 있는 메틸메타크릴레이트 삼원공중합체를 개발하기에 이른 것이다.In order to solve the above problems, the present inventors can shorten the melting time in the processing of vinyl chloride resin by introducing an epoxide compound, and generate a gel-eye and a flow trace in extrusion processing and calendering processing. It is to develop a methyl methacrylate terpolymer that can significantly reduce the amount of.
본 발명의 목적은 염화비닐 수지의 고유 물성에 영향을 주지 않는 가공 조제용 메타크릴레이트 공중합체 및 그 제조방법을 제공하기 위한 것이다.An object of the present invention is to provide a methacrylate copolymer for processing aid that does not affect the intrinsic physical properties of vinyl chloride resins and a method for producing the same.
본 발명의 다른 목적은 염화비닐 수지 가공의 용융시간을 단축시킬 수 있는 가공 조제용 메타크릴레이트 공중합체 및 그 제조방법을 제공하기 위한 것이다.Another object of the present invention is to provide a methacrylate copolymer for processing aid that can shorten the melting time of vinyl chloride resin processing and a method for producing the same.
본 발명의 또 다른 목적은 미겔화물 및 흐름자국 발생을 감소시킬 수 있는 가공 조제용 메타크릴레이트 공중합체 및 그 제조방법을 제공하기 위한 것이다.It is still another object of the present invention to provide a methacrylate copolymer for processing aid and a method for producing the same that can reduce the occurrence of microglides and flow marks.
본 발명의 또 다른 목적은 상기 메타크릴레이트 공중합체를 적용하여 칼렌더형 성형, 압출 성형에 적합한 염화비닐계 수지 조성물을 제공하기 위한 것이다.Still another object of the present invention is to provide a vinyl chloride-based resin composition suitable for calender type molding and extrusion molding by applying the methacrylate copolymer.
본 발명의 상기 및 기타 목적들은 하기 설명되는 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.
발명의 요약Summary of the Invention
본 발명은 염화비닐 수지의 가공 조제용 메타크릴레이트 공중합체를 제공한다. 상기 메타크릴레이트 공중합체는 (A) 메틸메타크릴레이트 60 내지 85 중량%; (B) 알킬아크릴레이트계 화합물 14 내지 30 중량%; 및 (C) 에폭사이드계 화합물 1 내지 10 중량%를 중합하여 이루어진다. The present invention provides a methacrylate copolymer for processing aid of vinyl chloride resin. The methacrylate copolymer (A) 60 to 85% by weight methyl methacrylate; (B) 14 to 30% by weight of an alkyl acrylate compound; And (C) polymerizing 1 to 10% by weight of an epoxide compound.
한 구체예에서는 상기 메타크릴레이트 공중합체는 중량평균분자량이 2,000,000 내지 5,000,000의 범위를 갖는다. In one embodiment, the methacrylate copolymer has a weight average molecular weight in the range of 2,000,000 to 5,000,000.
본 발명은 상기 메타크릴레이트 공중합체의 새로운 제조방법을 제공한다. 상기 방법은 메틸메타크릴레이트 60 내지 85 중량%, 알킬아크릴레이트계 화합물 14 내지 30 중량% 및 에폭사이드계 화합물 1 내지 10 중량%을 포함하는 단량체 혼합물을 수용성 개시제와 유화제 존재 하에서 중합하여 중합체 라텍스를 제조하고; 그리고 상기 중합체 라텍스를 응고하는 단계로 이루어진다.The present invention provides a new method for preparing the methacrylate copolymer. The method comprises polymerizing a polymer latex by polymerizing a monomer mixture comprising 60 to 85% by weight of methyl methacrylate, 14 to 30% by weight of an alkyl acrylate compound and 1 to 10% by weight of an epoxide compound in the presence of a water-soluble initiator and an emulsifier. To manufacture; And solidifying the polymer latex.
한 구체예에서 상기 중합은 40∼80℃에서 2∼12시간 동안 중합할 수 있다. In one embodiment, the polymerization may be polymerized at 40 to 80 ° C. for 2 to 12 hours.
본 발명의 다른 구체예에서는 상기 중합은 메틸메타크릴레이트, 알킬아크릴레이트계 화합물 및 에폭사이드계 화합물을 포함하는 단량체 혼합물중 60∼90 중량%을 수용성 개시제와 유화제 존재 하에서 1차 중합하고; 그리고 잔량의 단량체 혼합물 10∼40 중량%를 수용성 개시제와 유화제 존재 하에서 2차 중합하는 단계로 이루어진다. In another embodiment of the present invention, the polymerization is carried out by first polymerizing 60 to 90% by weight of a monomer mixture comprising methyl methacrylate, an alkyl acrylate compound and an epoxide compound in the presence of a water-soluble initiator and an emulsifier; And 10 to 40% by weight of the residual monomer mixture in the second polymerization in the presence of a water-soluble initiator and an emulsifier.
또한 상기 응고 단계에서 상기 중합체 라텍스에 산화방지제를 부가한 후 응 고할 수 있다. In the coagulation step, an antioxidant may be added to the polymer latex to coagulate.
본 발명은 상기 메타크릴레이트 공중합체를 가공 조제로 적용한 염화비닐계 수지 조성물을 제공한다. 상기 염화비닐계 수지 조성물은 본 발명의 염화비닐수지 100중량부에 대하여 메타크릴레이트 공중합체 0.1 내지 40 중량부를 포함하여 이루어진다. The present invention provides a vinyl chloride resin composition to which the methacrylate copolymer is applied as a processing aid. The vinyl chloride-based resin composition comprises 0.1 to 40 parts by weight of the methacrylate copolymer based on 100 parts by weight of the vinyl chloride resin of the present invention.
발명의 구체예에 대한 상세한 설명Detailed Description of the Invention
본 발명은 염화비닐 수지의 가공 조제용 메타크릴레이트 공중합체에 관한 것이다. The present invention relates to a methacrylate copolymer for processing aid of vinyl chloride resin.
상기 메타크릴레이트 공중합체는 (A) 메틸메타크릴레이트 60 내지 85 중량%, (B) 알킬아크릴레이트계 화합물 14 내지 30 중량% 및 (C) 에폭사이드계 화합물 1 내지 10 중량%의 공중합체이다. The methacrylate copolymer is a copolymer of (A) 60 to 85% by weight of methyl methacrylate, (B) 14 to 30% by weight of an alkyl acrylate compound and (C) 1 to 10% by weight of an epoxide compound. .
본 발명의 메타크릴레이트 공중합체는 메틸메타크릴레이트 성분이 60 내지 85 중량%이며, 바람직하게는 65 내지 82 중량%, 더 바람직하게는 70 내지 80 중량%이다. 메틸메타크릴레이트의 함량이 60 중량% 미만일 경우 용융시간의 단축효과가 미미하고, 85 중량%를 초과하는 경우 전체적인 물성밸런스가 저하될 수 있으며, 중합이 원활하게 이루어지지 않을 수 있기 때문이다.The methacrylate copolymer of the present invention has a methyl methacrylate component of 60 to 85% by weight, preferably 65 to 82% by weight, more preferably 70 to 80% by weight. When the content of methyl methacrylate is less than 60% by weight, the shortening effect of the melting time is insignificant, and when it exceeds 85% by weight, the overall physical balance may be lowered and polymerization may not be performed smoothly.
상기 메틸메타크릴레이트에 공중합되는 단량체로는 알킬아크릴레이트계 화합물 및 에폭사이드계 화합물이 사용된다. As the monomer copolymerized with the methyl methacrylate, an alkyl acrylate compound and an epoxide compound are used.
상기 알킬아크릴레이트로는 탄소수 1∼18의 선형 또는 가지형 알킬기를 갖는 아크릴레이트가 사용될 수 있다. 예컨대, 메틸아크릴레이트, 에틸아크릴레이트, 프로필아크릴레이트, 부틸아크릴레이트, 2-에틸헥실아크릴레이트 및 스테아릴아크릴레이트 등이 사용될 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용될 수 있다. As the alkyl acrylate, an acrylate having a linear or branched alkyl group having 1 to 18 carbon atoms may be used. For example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate and the like can be used. These can be used individually or in mixture of 2 or more types.
본 발명의 메타크릴레이트 공중합체에서 상기 알킬아크릴레이트계 화합물은 14내지 30 중량%, 바람직하게는 17 내지 28 중량%, 더 바람직하게는 18 내지 25 중량%를 사용한다. 상기 알킬아크릴레이트계 화합물의 함량이 14 중량% 미만일 경우 용융시간 단축 및 미겔화물의 발생량이 감소하는 효과를 기대하기 어렵고, 30 중량%를 초과하는 경우 물성밸런스가 저하되어 상용성에 문제가 발생할 수 있다.In the methacrylate copolymer of the present invention, the alkyl acrylate-based compound uses 14 to 30% by weight, preferably 17 to 28% by weight, more preferably 18 to 25% by weight. When the content of the alkyl acrylate compound is less than 14% by weight, it is difficult to expect the effect of shortening the melting time and reducing the generation amount of the gelling agent, and when the content of the alkyl acrylate compound exceeds 30% by weight, physical properties may be lowered, thereby causing compatibility problems. .
상기 에폭사이드계 화합물은 글리시딜메타크릴레이트, 트리글리시딜아이소시아누레이트, 비스(4-에폭시사이클로헥실메틸)아디페이트 및 사이클로옥타디엔디에폭사이드 등이 있으며, 반드시 이에 제한되는 것은 아니다. 이들은 2종 이상 혼합하여 사용될 수 있다. The epoxide-based compound includes glycidyl methacrylate, triglycidyl isocyanurate, bis (4-epoxycyclohexylmethyl) adipate, and cyclooctadiene diepoxide, but is not necessarily limited thereto. These can be used in mixture of 2 or more types.
본 발명의 메타크릴레이트 공중합체에서 상기 에폭사이드계 화합물은 1 내지 10 중량%를 사용하며, 바람직하게는 2 내지 9 중량%, 더 바람직하게는 3 내지 7 중량%를 사용한다. 상기 에폭사이드계 화합물의 함량이 1 중량% 미만일 경우에서는 에폭사이드 화합물에 의한 겔화시간의 단축효과가 없어질 수 있으며, 10 중량%를 초과하는 경우 에폭사이드 화합물의 자체 가교화에 의해 가공조제와 염화비닐수지와의 상용성이 저하되고 가교화에 의한 분자량 증가로 가공성이 저하되는 문제가 나타날 수 있다.In the methacrylate copolymer of the present invention, the epoxide compound is used in an amount of 1 to 10% by weight, preferably 2 to 9% by weight, more preferably 3 to 7% by weight. When the content of the epoxide-based compound is less than 1% by weight, the gelation time by the epoxide compound may be shortened. When the content of the epoxide-based compound exceeds 10% by weight, the processing aid and chloride may be reduced by self-crosslinking of the epoxide compound. The compatibility with the vinyl resin is lowered and there is a problem that the workability is lowered due to the increase in molecular weight by crosslinking.
상기 메타크릴레이트 공중합체는 중량평균분자량이 2,000,000 내지 5,000,000의 범위를 가지며, 바람직하게는 2,300,000 내지 4,000,000, 더 바람직하게는 2,500,000 내지 3,500,000이다. The methacrylate copolymer has a weight average molecular weight in the range of 2,000,000 to 5,000,000, preferably 2,300,000 to 4,000,000, more preferably 2,500,000 to 3,500,000.
상기 메타크릴레이트 공중합체는 유화중합, 괴상중합, 현탁중합, 용액중합 등 다양한 방법을 적용하여 중합될 수 있으며, 가공조제용 고분자를 제조하기 위해서는 유화중합 방식으로 하는 것이 가장 바람직하다.The methacrylate copolymer may be polymerized by applying a variety of methods such as emulsion polymerization, block polymerization, suspension polymerization, solution polymerization, it is most preferred to use the emulsion polymerization method to prepare a polymer for processing aids.
본 발명은 상기 메타크릴레이트 공중합체를 유화중합방식을 적용하여 제조하는 방법을 제공한다. 상기 방법은 메틸메타크릴레이트, 알킬아크릴레이트계 화합물 및 에폭사이드계 화합물로 이루어지는 군으로부터 1종 이상 선택되는 단량체를 수용성 개시제와 유화제 존재하에서 중합하여 중합체 라텍스를 제조하고, 그리고 상기 중합체 라텍스를 응고하는 단계로 이루어진다. The present invention provides a method for preparing the methacrylate copolymer by applying an emulsion polymerization method. The method comprises polymerizing at least one monomer selected from the group consisting of methyl methacrylate, alkyl acrylate compound, and epoxide compound in the presence of a water-soluble initiator and an emulsifier to produce a polymer latex, and solidifying the polymer latex. Consists of steps.
하나의 구체예에서는 메틸메타크릴레이트 60 내지 85 중량%, 알킬아크릴레이트계 화합물 14 내지 30 중량% 및 에폭사이드계 화합물 1 내지 10 중량%을 포함하는 단량체 혼합물을 수용성 개시제와 유화제 존재 하에서 중합하여 중합체 라텍스를 제조하고, 그리고 상기 중합체 라텍스를 응고하는 단계로 이루어진다.In one embodiment, a monomer mixture comprising 60 to 85% by weight of methyl methacrylate, 14 to 30% by weight of an alkyl acrylate compound and 1 to 10% by weight of an epoxide compound is polymerized in the presence of a water-soluble initiator and an emulsifier to polymerize the polymer. Preparing a latex and solidifying the polymer latex.
상기 수용성 개시제로는 과산화수소 등의 과산화물, 포타슘 퍼설페이트, 소디움 퍼설페이트, 암모늄 퍼설페이트 등의 설페이트류 등이 있으며, 총 단량체 100 중량부에 대하여 0.03∼0.2 중량부로 사용된다. Examples of the water-soluble initiator include peroxides such as hydrogen peroxide, sulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, and are used in an amount of 0.03 to 0.2 parts by weight based on 100 parts by weight of the total monomers.
상기 유화제로는 스테아릴산염, 로진산염, 올레인산염, 지방산염, 고분자량 알킬설페이트-, 알칼리설페이트- 및 설포네이트 알칼리금속염 등을 사용할 수 있 고, 바람직하게는 스테아릴산칼륨, 올레인산칼륨, 로진산 나트륨 또는 지방산 칼륨 등이다. 상기 유화제의 함량은 총 단량체 100 중량부에 대하여0.6∼2 중량부가 바람직하다. As the emulsifier, stearic acid salts, rosin salts, oleate salts, fatty acid salts, high molecular weight alkyl sulfates, alkali sulfate salts, and sulfonate alkali metal salts, and the like, and preferably, potassium stearate, potassium oleate, rosin Acid sodium or potassium potassium. The content of the emulsifier is preferably 0.6 to 2 parts by weight based on 100 parts by weight of the total monomers.
한 구체예에서 상기 중합은 40∼80℃에서 2∼12시간 동안 중합할 수 있다. 다른 구체예에서는 상기 중합은 50∼80℃에서 3∼10시간 동안 반응시킬 수 있다. In one embodiment, the polymerization may be polymerized at 40 to 80 ° C. for 2 to 12 hours. In another embodiment, the polymerization may be reacted at 50 to 80 ° C. for 3 to 10 hours.
본 발명에서는 상기 단량체 혼합물을 한꺼번에 투입하여 중합하거나 단량체 혼합물을 나누어 투입하여 단계별로 중합할 수 있다. 단량체 혼합물을 나누어 단계별로 중합할 경우, 제1단계에서는 전체 단량체 혼합물중 60∼90 중량%, 제2단계에서는 10∼40 중량%로 투입한다. 한 구체예에서는 상기 중합은 메틸메타크릴레이트, 알킬아크릴레이트계 화합물 및 에폭사이드계 화합물을 포함하는 단량체 혼합물중 60∼90 중량%을 수용성 개시제와 유화제 존재 하에서 1차 중합하고; 그리고 잔량의 단량체 혼합물 10∼40 중량%를 수용성 개시제와 유화제 존재 하에서 2차 중합하는 단계로 이루어진다. 2단계로 중합하는 이유는 가공조제 특성, 표면 특성 등을 개선할 수 있고, 최상의 물성을 나타내기 때문이다. 또한 고분자의 용융이 원활하기 때문에 미용융 현상이 현저하게 줄어드는 효과가 있다.In the present invention, the monomer mixture may be added at one time to polymerize, or the monomer mixture may be divided and added to polymerize step by step. When the monomer mixture is divided and polymerized step by step, 60 to 90% by weight of the total monomer mixture in the first step, 10 to 40% by weight in the second step. In one embodiment, the polymerization comprises firstly polymerizing 60 to 90% by weight of a monomer mixture comprising methyl methacrylate, an alkyl acrylate compound and an epoxide compound in the presence of a water-soluble initiator and an emulsifier; And 10 to 40% by weight of the residual monomer mixture in the second polymerization in the presence of a water-soluble initiator and an emulsifier. The reason for the polymerization in two stages is that the processing aid properties, the surface properties, etc. can be improved, and the best physical properties are exhibited. In addition, since the melting of the polymer is smooth, there is an effect that the unmelting phenomenon is significantly reduced.
또한 상기 응고 단계에서는 응고하기 전 상기 중합체 라텍스에 산화방지제를 부가한 후 응고할 수 있다. 상기 중합체 라텍스를 응고하는 방법은 본 발명이 속하는 분야의 통상의 지식을 가진 자에 의해 잘 알려져 있다. 예컨대, 상기 제조된 메틸메타크릴레이트-알킬아크릴레이트-에폭사이드계 공중합체 수지는 염화칼슘으로 응집할 수 있다. 응고된 공중합체는 통상의 방법으로 탈수 및 건조시켜 분말상태의 가공조제를 수득할 수 있다.In the coagulation step, an antioxidant may be added to the polymer latex before coagulation and then coagulated. Methods of solidifying the polymer latex are well known by those of ordinary skill in the art. For example, the prepared methyl methacrylate-alkyl acrylate-epoxide copolymer resin may be aggregated with calcium chloride. The coagulated copolymer may be dehydrated and dried in a conventional manner to obtain a powder processing aid.
본 발명은 상기 메타크릴레이트 공중합체를 가공 조제로 적용한 염화비닐계 수지 조성물을 제공한다. 상기 염화비닐계 수지 조성물은 본 발명의 염화비닐 수지 100 중량부에 대하여 메타크릴레이트 공중합체 0.1 내지 40 중량부를 포함하여 이루어진다. 더 바람직하게는 염화비닐수지 100 중량부에 대하여 본 발명의 메타크릴레이트 공중합체 0.5 내지 20 중량부를 포함한다. The present invention provides a vinyl chloride resin composition to which the methacrylate copolymer is applied as a processing aid. The vinyl chloride-based resin composition comprises 0.1 to 40 parts by weight of methacrylate copolymer based on 100 parts by weight of vinyl chloride resin of the present invention. More preferably, 0.5 to 20 parts by weight of the methacrylate copolymer of the present invention is included based on 100 parts by weight of vinyl chloride resin.
또한 상기 염화비닐계 수지 조성물은 각각의 용도에 따라 난연제, 항균제, 이형제, 열안정제, 산화방지제, 광안정제, 상용화제, 염료, 무기물 첨가제, 계면활성제, 핵제, 커플링제, 충전제, 가소제, 충격보강제, 혼화제, 착색제, 안정제, 활제, 정전기방지제, 안료, 방염제 등의 통상의 첨가제가 부가될 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 적용될 수 있다. In addition, the vinyl chloride resin composition may be flame retardant, antibacterial agent, mold release agent, heat stabilizer, antioxidant, light stabilizer, compatibilizer, dye, inorganic additive, surfactant, nucleating agent, coupling agent, filler, plasticizer, and impact modifier according to each use. Ordinary additives such as admixtures, colorants, stabilizers, lubricants, antistatic agents, pigments, flame retardants and the like can be added, these can be applied alone or in combination of two or more.
본 발명의 메타크릴레이트 공중합체를 가공 조제로 적용한 염화비닐계 수지 조성물은 염화비닐 수지의 고유 물성을 유지하면서 용융시간을 단축할 수 있고, 가공안정성이 매우 우수하다. 특히, 압출가공, 칼렌더링 가공에서 미겔화물(fish-eye)과 흐름자국 발생을 감소시킬 수 있으므로 가장 적합하며, 각종 용도의 성형품 제조에도 다양하게 적용될 수 있다. 본 발명의 가공조제를 적용한 성형품은 광택, 표면의 평활성 등의 외관과 2차 가공성이 우수한 장점이 있다.The vinyl chloride-based resin composition to which the methacrylate copolymer of the present invention is applied as a processing aid can shorten the melting time while maintaining the intrinsic physical properties of the vinyl chloride resin, and is excellent in processing stability. In particular, it is most suitable because it can reduce the occurrence of fish-eye and flow marks in extrusion processing and calendering processing, and can be variously applied to manufacturing molded articles of various uses. The molded article to which the processing aid of the present invention is applied has an advantage in appearance and secondary processability such as gloss and surface smoothness.
상기 염화비닐계 수지 조성물은 압출하여 펠렛으로 제조될 수도 있고, 상기 수지 조성물을 성형하여 전선피복, 합성피혁, 튜브, 식품포장제, 완구, 벽지, 장갑 등의 완제품으로 제조될 수도 있다.The vinyl chloride-based resin composition may be manufactured by pellets by extrusion, or may be manufactured into finished products such as wire coating, synthetic leather, tubes, food packaging agents, toys, wallpaper, gloves, etc. by molding the resin composition.
본 발명은 하기의 실시예에 의하여 보다 구체화될 것이며, 하기 실시예는 본 발명의 구체적인 예시에 불과하며 본 발명의 보호범위를 한정하거나 제한하고자 하는 것은 아니다.The present invention will be further illustrated by the following examples, which are merely illustrative of the present invention and are not intended to limit or limit the scope of the present invention.
실시예 Example
실시예 1Example 1
메틸메타크릴레이트 75 중량부, 부틸아크릴레이트 20 중량부, 글리시딜메타크릴레이트 5 중량부, 유화제 올레인산염 칼륨 1.0 중량부, 개시제 포타슘퍼설페이트 0.1 중량부, 개시 촉진제 황산 제1철 0.003 중량부 및 물 200 중량부를 함께 투입하여 45℃에서 10시간 동안 중합하여 중량평균분자량이 3,000,000인 메타크릴레이트 공중합체 라텍스를 제조하였다. 상기 기초수지 단량체 100 중량부에 대하여 산화방지제로 부틸화된 메틸페놀 0.2 중량부를 가하고, 염화칼슘으로 응고시킨 다음 세척하고 건조시켜 백색 분말을 수득하였다.75 parts by weight of methyl methacrylate, 20 parts by weight of butyl acrylate, 5 parts by weight of glycidyl methacrylate, 1.0 parts by weight of emulsifier potassium oleate, 0.1 parts by weight of initiator potassium persulfate, 0.003 parts by weight of initiator ferrous sulfate And 200 parts by weight of water were added together and polymerized at 45 ° C. for 10 hours to prepare a methacrylate copolymer latex having a weight average molecular weight of 3,000,000. To 100 parts by weight of the base resin monomer, 0.2 parts by weight of methylphenol butylated with antioxidant was added, coagulated with calcium chloride, washed and dried to obtain a white powder.
실시예 2Example 2
메틸메타크릴레이트 50 중량부, 부틸아크릴레이트 15 중량부, 글리시딜메타크릴레이트 2 중량부, 올레인산염 칼륨 1.0 중량부, 포타슘퍼설페이트 0.1 중량부, 황산 제1철 0.003 중량부 및 물 200 중량부를 함께 투입하여 45℃에서 7시간 동안 1차 중합하였다. 상기 1차 중합에서 제조된 1차 중합물 존재 하에 메틸메타크릴레 이트 20.5 중량부, 부틸아크릴레이트 10.5 중량부, 글리시딜메타크릴레이트 2 중량부, 올레인산 칼륨 0.2 중량부 및 포타슘퍼설페이트 0.02 중량부, 황산 제1철 0.0006 중량부를 투입한 후 45℃에서 4시간 동안 2차 중합하여 중량평균분자량이 2,700,000인 메타크릴레이트 공중합체 라텍스를 제조하였다. 상기 중합체 수지 100 중량부에 산화방지제로 부틸화된 메틸페놀 0.2 중량부를 가하고, 염화칼슘으로 응고시킨 다음 세척하고 건조시켜 백색 분말을 수득하였다. 50 parts by weight of methyl methacrylate, 15 parts by weight of butyl acrylate, 2 parts by weight of glycidyl methacrylate, 1.0 part by weight of potassium oleate, 0.1 part by weight of potassium persulfate, 0.003 part by weight of ferrous sulfate and 200 parts by weight of water. The parts were put together and firstly polymerized at 45 ° C. for 7 hours. 20.5 parts by weight of methyl methacrylate, 10.5 parts by weight of butyl acrylate, 2 parts by weight of glycidyl methacrylate, 0.2 parts by weight of potassium oleate and 0.02 parts by weight of potassium persulfate in the presence of the primary polymer prepared in the first polymerization. After the addition of 0.0006 parts by weight of ferrous sulfate, the second polymerization was carried out at 45 ° C. for 4 hours to prepare a methacrylate copolymer latex having a weight average molecular weight of 2,700,000. To 100 parts by weight of the polymer resin was added 0.2 parts by weight of methylphenol butylated with an antioxidant, solidified with calcium chloride, washed and dried to obtain a white powder.
실시예 3Example 3
글리시딜메타크릴레이트 대신 비스(4-에폭시사이클로 헥실메틸)아디페이트 5 중량부를 사용한 것을 제외하고는 상기 실시예 1과 동일하게 수행하였다. 제조된 메타크릴레이트 공중합체 라텍스의 중량 평균 분자량은 2,950,000 이었다. The same procedure as in Example 1 was carried out except that 5 parts by weight of bis (4-epoxycyclohexylmethyl) adipate was used instead of glycidyl methacrylate. The weight average molecular weight of the prepared methacrylate copolymer latex was 2,950,000.
실시예 4Example 4
글리시딜메타크릴레이트 대신 비스(4-에폭시사이클로 헥실메틸)아디페이트 3 중량부를 사용하고, 메틸메타크릴레이트 71 중량부, 부틸아크릴레이트 26 중량부를 사용한 것을 제외하고는 상기 실시예 1과 동일하게 수행하였다. 제조된 메타크릴레이트 공중합체의 중량 평균 분자량은 2,800,000 이었다.In the same manner as in Example 1, except that 3 parts by weight of bis (4-epoxycyclohexylmethyl) adipate was used instead of glycidyl methacrylate, and 71 parts by weight of methyl methacrylate and 26 parts by weight of butyl acrylate were used. Was performed. The weight average molecular weight of the prepared methacrylate copolymer was 2,800,000.
실시예 5Example 5
글리시딜메타크릴레이트 대신 사이클로옥타디엔 디에폭사이드 5 중량부를 사 용한 것을 제외하고는 상기 실시예 1과 동일하게 수행하였다. 제조된 메타크릴레이트 공중합체의 중량 평균 분자량은 3,050,000 이었다. The same procedure as in Example 1 was carried out except that 5 parts by weight of cyclooctadiene diepoxide was used instead of glycidyl methacrylate. The weight average molecular weight of the prepared methacrylate copolymer was 3,050,000.
실시예 6Example 6
글리시딜메타크릴레이트 대신 비스(4-에폭시사이클로헥실메틸)아디페이트를 사용한 것을 제외하고는 실시예 2와 동일한 방법으로 중합하였다. 제조된 수지의 중량평균 분자량은 2,610,000이었다.Polymerization was carried out in the same manner as in Example 2, except that bis (4-epoxycyclohexylmethyl) adipate was used instead of glycidyl methacrylate. The weight average molecular weight of the produced resin was 2,610,000.
실시예 7Example 7
글리시딜메타크릴레이트 대신 사이클로옥타디엔 디에폭사이드를 사용한 것을 제외하고는 실시예 2와 동일한 방법으로 수행하였다. 제조된 수지의 중량평균 분자량은 2,800,000이었다.The same procedure as in Example 2 was carried out except that cyclooctadiene diepoxide was used instead of glycidyl methacrylate. The weight average molecular weight of the produced resin was 2,800,000.
비교실시예 1Comparative Example 1
글리시딜메타크릴레이트를 12 중량부, 메틸메타크릴레이트 66 중량부, 부틸아크릴레이트 20 중량부를 사용한 것을 제외하고는 상기 실시예 1과 동일하게 수행하였다. 제조된 메타크릴레이트 공중합체의 중량 평균 분자량은 2,900,000 이었다.Glycidyl methacrylate was carried out in the same manner as in Example 1 except that 12 parts by weight, methyl methacrylate 66 parts by weight, and 20 parts by weight of butyl acrylate were used. The weight average molecular weight of the prepared methacrylate copolymer was 2,900,000.
비교실시예 2Comparative Example 2
글리시딜메타크릴레이트를 사용하지 않고, 메틸메타크릴레이트 75 중량부, 부틸아크릴레이트 25 중량부를 사용한 것을 제외하고는 상기 실시예 1과 동일하게 수행하였다. 제조된 메타크릴레이트 공중합체의 중량 평균 분자량은 3,000,000 이었다.The same procedure as in Example 1 was carried out except that 75 parts by weight of methyl methacrylate and 25 parts by weight of butyl acrylate were used without glycidyl methacrylate. The weight average molecular weight of the prepared methacrylate copolymer was 3,000,000.
비교실시예 3Comparative Example 3
글리시딜메타크릴레이트를 사용하지 않고, 메틸메타크릴레이트 80 중량부, 부틸아크릴레이트 20 중량부를 사용한 것을 제외하고는 상기 실시예 2와 동일하게 수행하였다. 제조된 메타크릴레이트 공중합체의 중량 평균 분자량은 3,200,000이었다.The same procedure as in Example 2 was carried out except that 80 parts by weight of methyl methacrylate and 20 parts by weight of butyl acrylate were used without glycidyl methacrylate. The weight average molecular weight of the prepared methacrylate copolymer was 3,200,000.
상기 실시예 1∼7 및 비교실시예 1∼3에서 제조된 메타크릴레이트 공중합체에 대하여 하기의 방법으로 물성을 평가하고 그 결과를 표 1에 나타내었다. The physical properties of the methacrylate copolymers prepared in Examples 1 to 7 and Comparative Examples 1 to 3 were evaluated by the following method, and the results are shown in Table 1.
(1) 용융시간 (1) melting time
상기에서 제조된 메타크릴레이트 공중합체 5 중량부를 중합도 800의 폴리염화비닐 수지(중합도 800) 100 중량부와 각각 혼합하여 제조된 폴리염화비닐 조성물 60 g을 180 ℃, 30 rpm의 조건에서 브라벤더를 사용하여 최대 부하까지 걸리는 시간을 측정하였다.60 parts of the polyvinyl chloride composition prepared by mixing 5 parts by weight of the methacrylate copolymer prepared above with 100 parts by weight of a polyvinyl chloride resin (polymerization degree 800) having a polymerization degree of 800 ° C. was subjected to brabender at 180 ° C. and 30 rpm. Time to maximum load was measured.
(2) 분자량(2) molecular weight
GPC(Gel permeation chromatography)를 사용하여 측정하였다.It was measured using GPC (Gel permeation chromatography).
(3) 미겔화물(3) miguel
상기에서 제조된 메타크릴레이트 공중합체 5 중량부를 중합도 800의 폴리염화비닐 수지 100 중량부와 각각 혼합하여 제조된 폴리염화비닐 조성물을 T-die를 가지는 20mm 싱글 스핀들 압출기를 이용하여 0.1mm 두께의 필름을 실린더 온도 180℃와 40rpm의 스크류 속도로 압출하였다. 이때 필름 표면의 10cm X 10cm 영역 안에 있는 미겔화물의 개수를 측정하여 다음과 같이 평가하였다(미겔화물 개수 5 이하: Good, 미겔화물 개수 5 ∼ 15: Normal, 미겔화물 개수 15 이상: Poor).5 parts by weight of the methacrylate copolymer prepared above was mixed with 100 parts by weight of polyvinyl chloride resin having a polymerization degree of 800, respectively, and a film having a thickness of 0.1 mm using a 20 mm single spindle extruder having a T-die. Was extruded at a cylinder temperature of 180 ° C. and a screw speed of 40 rpm. At this time, by measuring the number of the gelate in the 10cm X 10cm area of the film surface was evaluated as follows (Miglide number 5 or less: Good, Miguelte number 5 to 15: Normal, Miguelte number 15 or more: Poor).
상기 표 2의 결과로부터, 실시예 1∼7은 비교실시예 1∼3과 비교할 때 용융시간이 짧고, 미겔화물이 거의 없는 결과를 나타냄을 확인할 수 있었고, 육안으로 관측하였을 시 흐름자국에 있어서 양호하였다. 따라서 본 발명에 따라 염화비닐수지용 가공제조 수지를 제조하면 용융시간과 미겔화물이 감소됨을 알 수 있다.From the results of Table 2, Examples 1 to 7 were found to have a shorter melting time and relatively little gelation when compared with Comparative Examples 1 to 3, and were good in flow marks when visually observed. It was. Therefore, it can be seen that the preparation of the resin for processing the vinyl chloride resin according to the present invention reduces the melting time and the gelation.
본 발명은 염화비닐 수지의 고유 물성에 영향을 주지 않으면서 수지 가공에 있어서 용융시간을 단축할 수 있으며, 압출가공, 칼렌더링 가공에서 미겔화물(fish-eye)과 흐름자국 발생을 감소시킬 수 있는 물성을 만족시킬 수 있는 염화비닐 수지의 가공 조제용 메타크릴레이트 공중합체 및 그의 제조 방법을 제공하는 발명의 효과를 갖는다.The present invention can shorten the melting time in the resin processing without affecting the inherent physical properties of the vinyl chloride resin, and can reduce the occurrence of fish-eye and flow marks in the extrusion processing and calendering processing It has the effect of the invention which provides the methacrylate copolymer for processing aids of vinyl chloride resin which can satisfy a physical property, and its manufacturing method.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020070126215A KR101030513B1 (en) | 2007-12-06 | 2007-12-06 | Methacrylate Copolymer for Processing Aids of Vinylchloride Resin and Method for Production Thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020070126215A KR101030513B1 (en) | 2007-12-06 | 2007-12-06 | Methacrylate Copolymer for Processing Aids of Vinylchloride Resin and Method for Production Thereof |
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| Publication Number | Publication Date |
|---|---|
| KR20090059385A KR20090059385A (en) | 2009-06-11 |
| KR101030513B1 true KR101030513B1 (en) | 2011-04-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020070126215A KR101030513B1 (en) | 2007-12-06 | 2007-12-06 | Methacrylate Copolymer for Processing Aids of Vinylchloride Resin and Method for Production Thereof |
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| Country | Link |
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| KR (1) | KR101030513B1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017165582A1 (en) | 2016-03-25 | 2017-09-28 | Arkema, Inc. | Functionalized acrylic process aids for gloss and surface finish modification |
| KR20230097905A (en) | 2021-12-24 | 2023-07-03 | 주식회사 케이씨씨 | Glycidyl Group-Containing Copolymer For Processing Aid Of Vinyl Chloride Resin And Vinyl Chloride-Based Resin Composition Comprising The Same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3038612B1 (en) * | 2015-07-09 | 2020-03-27 | Arkema France | POLYMER COMPOSITION, PROCESS FOR PREPARING THE SAME, AND USE THEREOF |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020002430A (en) * | 1999-04-23 | 2002-01-09 | 다케다 마사토시 | Processing aid for thermoplastic resin and thermoplastic resin composition containing the same |
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2007
- 2007-12-06 KR KR1020070126215A patent/KR101030513B1/en active IP Right Grant
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020002430A (en) * | 1999-04-23 | 2002-01-09 | 다케다 마사토시 | Processing aid for thermoplastic resin and thermoplastic resin composition containing the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017165582A1 (en) | 2016-03-25 | 2017-09-28 | Arkema, Inc. | Functionalized acrylic process aids for gloss and surface finish modification |
| US11220596B2 (en) | 2016-03-25 | 2022-01-11 | Arkema France | Functionalized acrylic process aids used for gloss and surface finish modification |
| KR20230097905A (en) | 2021-12-24 | 2023-07-03 | 주식회사 케이씨씨 | Glycidyl Group-Containing Copolymer For Processing Aid Of Vinyl Chloride Resin And Vinyl Chloride-Based Resin Composition Comprising The Same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20090059385A (en) | 2009-06-11 |
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