KR101856465B1 - The environmental-friendly Windows Profile compositions with enhanced heat resistance and color - Google Patents
The environmental-friendly Windows Profile compositions with enhanced heat resistance and color Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
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- 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
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- C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
- E06B3/04—Wing frames not characterised by the manner of movement
- E06B3/06—Single frames
- E06B3/08—Constructions depending on the use of specified materials
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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
- C08F220/38—Esters containing sulfur
- C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
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Abstract
본 발명은 건축물의 창호와 문틀에 건축 자재로 사용되는 합성 수지 및 이를 이용한 제품에 관한 것으로, 보다 상세하게는 아크릴고무-스티렌계 단량체-부타디엔고무-비닐시안계 단량체 사원 공중합체수지와 분산도가 큰 스티렌계-비닐시안계 공중합체와 N-치환말레이미드단량체-α 알킬 스티렌 계-불포화니트릴 단량체로 이루어진 4원 괴상공중합체를 포함하는 합성수 지 조성물에 관한 것이다. 본 발명에 따른 합성수지 조성물을 이용하여 압출 제조된 창호나 문틀과 같은 건축 자재로는 기존의 폴리염화비닐(PVC )합성 수지이나, 기존ABS계 창호용 합성수지에 비교하여 우수한 내열 성능을 확 보로 인하여 대기 온도의 상승과 다양한 색상의 발현 시 창호와 문틀 등의 건축 자재로 제작 시에도 형상의 뒤틀림, 변형 등이 없으며, 또한 우수한 내 열성을 확보하면서, 창호나 문틀이 요구하는 건축자재의 기계적 물성 확보와 창호 형재 제작이 가능하다. 또한, 기존 염화비닐(PVC)합성 수지의 열안정 제로 사용되는 환경오염 물질인 카드뮴 스테아레이트, 납 스테아레이트 등을 사용하지 않으면서도 착색생과 내후성이 우수한 친환경 건축 자재인 창호와 문틀을 제조 할 수 있는 효과가 있다.More particularly, the present invention relates to an acrylic rubber-styrene-based monomer-butadiene rubber-vinylcyano-based monomer copolymer resin and a dispersion thereof, which are used as building materials in window and door frames of buildings, And a quaternary block copolymer consisting of a large styrene-based vinylene copolymer and an N-substituted maleimide monomer-alpha alkylstyrene-unsaturated nitrile monomer. As the building material such as window or door frame manufactured by extrusion using the synthetic resin composition according to the present invention, the excellent heat resistance performance compared with the conventional synthetic resin of polyvinyl chloride (PVC) When rising temperature and manifesting various colors, there is no distortion or distortion of shape even when it is made with building material such as window and door frame. In addition, while ensuring excellent heat resistance, it is necessary to secure the mechanical properties of building materials required by window and door frame It is possible to produce window frames. In addition, it is possible to manufacture window and door frames which are environmentally friendly building materials excellent in coloring and weatherability without using cadmium stearate, lead stearate, etc., which are environmental pollutants used as heat stabilizers for existing PVC (polyvinyl chloride) It is effective.
Description
본 발명은 친환경 창호재 조성물 및 이를 이용한 창호재에 관한 것으로서, 보다 상세하게는 내열성과 착색성이 우수한 친환경 창호재 조성물 및 이를 이용한 창호재에 관한 것이다. More particularly, the present invention relates to an environmentally friendly window-forming composition having excellent heat resistance and coloring property, and a window-supporting material using the composition.
종래 창호와 문틀의 건축용 자재 등으로 폭 넓게 사용되어온 폴리염화비닐(PVC)수지는 연소시 또는 압출 가공시에 환경유해물질, 예를 들어 다이옥신이 다량 발생된다는 문제가 있어왔다. 또한 열안정제로 사용중인 카드뮴스테아레이트(Cd-st)이나 납스테아레이트(Pb-st) 등의 중금속 이온은 또한 인체호르몬 교란물질로 작용하여 규제되고 있으며, 새집 증후군 등의 문제를 일으키는 주요 원인이 되고 있다. 또한 폴리염화비닐수지는 열안정성 낮아, 창호로 압출되는 과정에서 제조시 변색이 일어나 리사이클링이 어려운 문제가 있다. BACKGROUND ART Conventionally, polyvinyl chloride (PVC) resins widely used as building materials for window frames and door frames have been problematic in that a large amount of environmentally harmful substances such as dioxins are generated during combustion or extrusion processing. Heavy metal ions such as cadmium stearate (Cd-st) and lead stearate (Pb-st), which are used as heat stabilizers, are also regulated by acting as human hormone disturbances and are the main causes of problems such as sick house syndrome . In addition, the polyvinyl chloride resin has a low thermal stability and has a problem in that it is difficult to recycle due to discoloration during production in the process of being extruded into a window.
이러한 폴리염화비닐(PVC)수지를 ABS계 수지로 대체하고자 하는 연구가 이루어져 왔다. 출원인은 대한민국 특허공개 10-2007-0095142와 등록특허 10-0590821에서 아크릴고무-스티렌계단량체-부타디엔고무-비닐시안계 단량체로 이루어진 사원 공중합체수지와 분자량과 분산도가 큰 스틸렌계-비닐시안계 공중합체를 사용하는 수지 조성물을 공개하고 하고 있다.Studies have been made to replace such polyvinyl chloride (PVC) resins with ABS resins. The applicants have disclosed in Korean Patent Publication Nos. 10-2007-0095142 and 10-0590821 that an acrylic resin-styrene-based monomer-butadiene rubber-vinylcyanide monomer and a styrene-vinylidene chloride copolymer A resin composition using a copolymer is disclosed.
그러나, 이러한 수지들은 기존 폴리염화비닐(PVC) 수지에서 발생되는 오염물질을 사용하지 않아 환경적인 문제를 해결할 수 있으며, 흰색으로만 이루어지는 PVC와 달리 다양한 칼라와 무늬를 구현할 수 있었으나, 건축용 외장재로 사용 시에는 광 흡수성이 좋은 칼라들을 사용할 경우, 대기 온도 상승과 결합하여 건축 외장재의 표면과 내부 온도가 상승되면서, 건축 자재의 뒤틀림, 변형, 색상 변색 등의 문제가 발생하는 문제가 있었다. 또한 다양한 칼라를 구현하기 위해서 사용되는 안료의 내후성이 저하되어 외부 기후에 노출시 변색되는 문제가 있어왔다. However, these resins can solve environmental problems because they do not use contaminants generated from conventional polyvinyl chloride (PVC) resin. Unlike PVC which is made of white, various colors and patterns can be realized, but they are used as building exterior materials There is a problem in that warpage, deformation, color discoloration and the like of the building material occur due to the increase in the surface temperature and the internal temperature of the building exterior material in combination with the increase in the atmospheric temperature. In addition, there has been a problem in that the weather resistance of the pigment used to realize various colors is lowered and discolored when exposed to the external climate.
이에 따라, 외부 대기온도의 상승과 다양한 색상에 의한 건축 자재의 표면 온도 상승으로 인하여 건축 소재로서의 물성과 내열성과 내후성을 동시에 확보할 수 있는 새로운 방법에 대한 요구가 계속되고 있다. Accordingly, there is a continuing need for a new method for securing the physical properties, heat resistance, and weatherability as building materials due to the increase of the outside air temperature and the increase of the surface temperature of the building materials by various colors.
본 발명에서 해결하고자 하는 과제는 창호와 문틀 등의 건축자재 적용되는 내열성과 내후성이 동시에 개선된 새로운 열가소성 수지 조성물을 제공하는 것이다.A problem to be solved by the present invention is to provide a novel thermoplastic resin composition in which heat resistance and weather resistance applied to building materials such as window frames and door frames are improved at the same time.
본 발명에서 해결하고자 하는 다른 과제는 내열성과 내후성이 동시에 개선된 새로운 열가소성 수지 조성물로 이루어진 창호와 문틀 등의 건축자재를 제공하는 것이다. Another object of the present invention is to provide a building material such as a window and a door frame made of a novel thermoplastic resin composition having improved heat resistance and weather resistance at the same time.
본 발명에서 해결하고자 하는 또 다른 과제는 PVC 생산설비에서 생산이 가능하고 내열성과 내후성이 동시에 개선된 새로운 창호 또는 문틀용 스티렌계 열가소성 수지 조성물을 제공하는 것이다.Another object of the present invention is to provide a styrene-based thermoplastic resin composition for a window or a door, which is capable of being produced in a PVC production facility and improved both in heat resistance and weather resistance.
본 발명에서 해결하고자 하는 또 다른 과제는 스티렌계 열가소성 수지 조성물을 재사용하여 창호 또는 문틀용 스티렌계 열가소성 수지 조성물을 제공하는 것이다.Another object of the present invention is to provide a styrenic thermoplastic resin composition for window or door frame by reusing a styrenic thermoplastic resin composition.
상기와 같은 문제를 해결하기 위해서, 본 발명의 열가소성 수지 조성물은 아크릴계 고무 수지 30~60중량%, 중량 평균 분자량이 150,000~400,000인 스티렌계-비닐시안계 공중합체 20~70중량%, N-치환 말레이미계 단량체, α-알킬스티렌계 단량체, 비닐 시안계 단량체 및 방향족 비닐 단량체로 이루어진 공중합체 3~20중량%으로 이루어지는 창호용 열가소성 합성수지 조성물을 제공한다.In order to solve the above problems, the thermoplastic resin composition of the present invention comprises 30 to 60% by weight of an acrylic rubber resin, 20 to 70% by weight of a styrene-vinylene-based copolymer having a weight average molecular weight of 150,000 to 400,000, And 3 to 20% by weight of a copolymer comprising a maleimide monomer, an? -Alkylstyrene monomer, a vinylcyanide monomer and an aromatic vinyl monomer.
본 발명에 있어서, 상기 아크릴계 고무 수지는 아크릴 고무 또는 아크릴 고무를 주성분으로 하는 고무를 방향족 비닐 화합물 단량체 및 비닐시안계 화합물 단량체를 주성분으로 하는 단량체와 공중합, 바람직하게는 그라프트 공중합한 수지를 의미한다. In the present invention, the acrylic rubber resin means a resin obtained by copolymerization, preferably graft copolymerization, of an acrylic rubber or an acrylic rubber as a main component with a monomer mainly composed of an aromatic vinyl compound monomer and a vinyl cyan compound monomer .
본 발명에 있어서, 아크릴 고무를 주성분으로 하는 고무는 아크릴 고무의 함량이 85 중량%이상인 것을 의미한다. 상기 아크릴 고무를 주성분으로 하는 고무는 다른 종류의 고무, 예를 들어 디엔계 고무, 일예로 부타디엔 고무를 15 중량%이하로 포함하는 고무이다. In the present invention, the rubber containing acrylic rubber as a main component means that the content of acrylic rubber is 85% by weight or more. The rubber containing the acrylic rubber as a main component is a rubber containing 15% by weight or less of another kind of rubber, for example, a diene rubber, for example, a butadiene rubber.
발명의 일 실시에 있어서, 상기 아크릴계 고무 수지는 예를 들어 부틸아크릴레이트나 에틸헥실아크릴레이트를 가교 중합한 아크릴 고무를 방향족 비닐화합물 및 비닐시안계 화합물과 그라프트 공중합한 3원 공중합체이다. 다른 실시에 있어서, 상기 아크릴계 고무 수지는 소량의 부타디엔 고무와 아크릴 고무를 혼합하여 방향족 비닐화합물 및 비닐시안계 단량체와 공중합한 4원 공중합체일 수 있으며, 또 다른 실시에 있어서 아크릴 고무와 비닐시안계 단량체 및 방향족 비닐화합물 단량체가 공중합된 수지와 부타디엔 고무와 비닐시안계 단량체 및 방향족 비닐화합물 단량체가 공중합된 수지의 혼합물일 수 있으며, 혼합은 라텍스 또는 파우더 상태의 혼합이 가능하다. 본 발명의 바람직한 실시에 있어서, 상기 아크릴계 고무 수지는 아크릴 고무와 부타디엔 고무의 함량이 85:15~99:1의 중량비, 보다 바람직하게는 90:10~97:3 중량비로 혼합된 고무가 방향족 비닐화합물 및 비닐시안계 화합물과 그라프트 공중합된 공중합체 수지이다. In one embodiment of the invention, the acrylic rubber resin is a ternary copolymer obtained by, for example, graft copolymerizing an acrylic rubber obtained by cross-linking butyl acrylate or ethylhexyl acrylate with an aromatic vinyl compound and a vinyl cyanide compound. In another embodiment, the acrylic rubber resin may be a quaternary copolymer obtained by copolymerizing a small amount of butadiene rubber with acrylic rubber and copolymerizing with an aromatic vinyl compound and a vinylcyanide monomer. In another embodiment, the acrylic rubber and the vinyl cyanoacrylate The monomer and the aromatic vinyl compound monomer may be a copolymer of the resin, the butadiene rubber, the vinyl cyanide monomer and the resin copolymerized with the aromatic vinyl compound monomer, and the mixing may be performed in the latex or powder state. In a preferred embodiment of the present invention, the acrylic rubber resin is a mixture of an acrylic rubber and a butadiene rubber in a weight ratio of 85:15 to 99: 1, more preferably 90:10 to 97: 3, And a graft copolymerized resin with a vinyl cyano compound.
발명의 바람직한 일 실시예에 있어서, 아크릴계 고무 수지는 상기 아크릴고무-아크릴로니트릴-부타디엔고무-스티렌(AABS) 공중합체이며, 상기 아크릴고무-부타디엔고무/아크릴로니트릴/스티렌의 조성이 40~70중량부/5~20중량부/25~40 중량부이다. In one preferred embodiment of the present invention, the acrylic rubber resin is the acrylic rubber-acrylonitrile-butadiene rubber-styrene (AABS) copolymer, and the composition of the acrylic rubber-butadiene rubber / acrylonitrile / styrene is 40 to 70 5 to 20 parts by weight / 25 to 40 parts by weight.
본 발명에 있어서, 상기 스틸렌계 단량체는 방향족 비닐단량체로서 스티렌, 알파-메틸스티렌, p-메틸스티렌, 비닐톨루렌 또는 이들의 2이상의 혼합물을 사용할 수 있으며, 이들과 공중합 가능한 단량체, 예를 들어 아크릴레이트계 단량체를 포함할 수 있다. 바람직한 실시예에서 상기 스티렌계 단량체는 스티렌이다. In the present invention, the styrene-based monomer may be an aromatic vinyl monomer such as styrene, alpha-methylstyrene, p-methylstyrene, vinyltoluene or a mixture of two or more thereof. Monomers copolymerizable therewith, Rate-based monomers. In a preferred embodiment the styrenic monomer is styrene.
본 발명에 있어서, 상기 비닐시안계 단량체는 아크릴로니트릴, 메타크릴로니틀리 , 또는 이들과 공중합 가능한 단량체, 예를 들어 메틸메타아크릴레이트, 아크릴레이트 등을 포함하는 단량체이며, 바람직하게는 아크릴로니트릴이다. In the present invention, the vinyl cyanide monomer is a monomer including acrylonitrile, methacrylonitrile, or a copolymerizable monomer such as methyl methacrylate and acrylate, and preferably acrylonitrile to be.
본 발명에 있어서, 상기 아크릴계 고무 수지는 창호용 열가소성 합성 수지에 요구되는 강도와 내충격성과 같은 내구성을 충족시킬 수 있도록 아크릴계 고무의 함량이 30-60 중량%, 보다 바람직하게는 35-55 중량부를 사용하는 것이 좋다. In the present invention, the content of the acrylic rubber is preferably 30 to 60% by weight, more preferably 35 to 55 parts by weight, in order to satisfy durability such as strength and impact resistance required for a thermoplastic synthetic resin for a window It is good to do.
본 발명에 있어서, 상기 스티렌계-비닐시안계 공중합체는 스티렌계 단량체와 비닐시안계 단량체의 공중합이다. In the present invention, the styrene-based vinylene copolymer is a copolymer of a styrene-based monomer and a vinylcyanide-based monomer.
본 발명에 있어서, 상기 스티렌-비닐시안계 공중합체는 최종 제품이 물리적 특성, 특히 강성을 유지할 수 있도록 중량평균 분자량이 150,000 이상인 것이 바람직하며, 보다 바람직하게는 중량평균분자량이 30만에서 50만인 것이 더욱 바람직하다. In the present invention, the styrene-vinyl cyanide copolymer preferably has a weight average molecular weight of 150,000 or more, more preferably a weight average molecular weight of 300,000 to 500,000 in order to maintain physical properties, particularly rigidity, More preferable.
본 발명에 있어서, 상기 스틸렌계-비닐시안계 공중합체는 스티렌계와 비닐시안계의 조성비율은 각각 60~80중량% 및 20~40%인 것이 더욱 바람직하다. 비닐시안계의 함량이 높아질 경우 중합체의 열안정성이 낮아지게 되며, 스티렌계의 함량이 높아질 경우에는 제품의 중합체의 강성이 약해질 수 있게 된다. 본 발명에 있어서, 상기 스티렌계-비닐시안계 공중합체는 분자량 분포가 넓어 소량의 저분자량체와 분자량 100만 이상의 고분자량체가 혼합되는 것이 보다 바람직하다. In the styrene-based vinyl chloride copolymer of the present invention, it is more preferable that the composition ratios of the styrene-based and vinylcyanide are 60 to 80% by weight and 20 to 40%, respectively. When the content of the vinyl cyano group is increased, the thermal stability of the polymer is lowered. When the content of the styrene series is increased, the rigidity of the polymer of the product can be weakened. In the present invention, it is more preferable that the styrene-based vinyl cyanide copolymer has a broad molecular weight distribution so that a small amount of a low molecular weight monomer and a high molecular weight monomer having a molecular weight of 1,000,000 or more are mixed.
본 발명에 있어서, 공중합체의 제조방법은 상기의 분자량을 범위를 충족할 수 있는 한 특별한 제한은 없으며, 통상의 유화 중합, 괴상 중합 또는 현탁 중합을 이용하여 제조할 수 있다. 발명의 일 실시에 있어서, 스티렌-아크릴로니트릴 공중합체는 유화중합 또는 현탁중합을 사용하는 것이 바람직하다.In the present invention, the production method of the copolymer is not particularly limited as long as the above-mentioned molecular weight can be met, and can be produced by using ordinary emulsion polymerization, bulk polymerization or suspension polymerization. In one embodiment of the invention, the styrene-acrylonitrile copolymer is preferably subjected to emulsion polymerization or suspension polymerization.
본 발명에 있어서, 상기 스티렌계-비닐시안계 공중합체는 창호용 열가소성 합성 수지에 요구되는 인장 강도나 굴곡 강도 및 탄성율과 같은 강성을 충족시킬 수 있도록 20~70 중량%, 보다 바람직하게는 25~55중량%를 사용하는 것이 좋다. 구체적으로 스티렌계-비닐시안계 공중합체의 양이 상기 범위보다 많으면 충격 강도가 낮아지게 되고, 너무 적으면 가공성이 낮아지게 되는 문제가 있게 된다.In the present invention, the styrenic-vinyl cyanide copolymer is used in an amount of 20 to 70% by weight, more preferably 25 to 70% by weight, in order to satisfy rigidity such as tensile strength, flexural strength and elastic modulus required for a thermoplastic synthetic resin for a window, 55% by weight is preferably used. Specifically, when the amount of the styrene-based vinyl cyanide copolymer is more than the above range, the impact strength is lowered, and when it is too small, the workability is lowered.
본 발명에 있어서, N-치환 말레이미계 단량체, α-알킬스티렌계 단량체, 비닐 시안계 단량체 및 방향족 비닐 단량체로 이루어진 공중합체는 변색 안정성, 강도를 위해 사원 괴상 공중합체로 이루어지는 것이 바람직하다. 특히, 본 발명에 따른 사원 괴상 공중합체는 아크릴 고무 및 스티렌계-비닐시안계 공중합체와 상용성이 좋고 용융점도가 낮아 종래의 PVC 압출기와 같은 낮은 온도에서 창호의 압출 및 성형이 용이하다. In the present invention, a copolymer composed of an N-substituted maleimide monomer, an? -Alkylstyrene monomer, a vinyl cyan monomer and an aromatic vinyl monomer is preferably composed of a massive block copolymer for color stability and strength. In particular, the massive block copolymer of the present invention has good compatibility with acrylic rubber and styrene-based vinyl cyanide copolymer and has a low melt viscosity, so that it is easy to extrude and form a window at a low temperature such as a conventional PVC extruder.
본 발명에 있어서, 상기 N-치환 말레이미드 단량체는 N-페닐 말레이미드, 말레이미드. N-메틸 말레이미드, N-에틸 말레이미드, N-프로필 말레이미드, N-이소프로필 말레이미드, N-부틸 말레이미드, N-이소부틸 말레이미드, N-t-부틸 말레이미드, N-시클로헥실 말레이미드, N-클로로페닐 말레이미드, N-메틸페닐 말레이미드, N-브로모페닐 말레이미드, N-나프틸 말레이미드, N-라이릴 말레이미드, N-히드록시페닐 말레이미드, N-메톡시 페닐말레이미드, N-라우틸 말레이미드, N-히드록시페닐 말레이미드, N-메톡시페닐말레이미드, N-카르복시 페닐말레이미드, N-니트로페닐 말레이미드,N-벤질 말레이미드 및 이들과 공중합 가능한 소량의 단량체를 포함하는 단량체이다.In the present invention, the N-substituted maleimide monomer is N-phenylmaleimide, maleimide. N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, Nt-butylmaleimide, N-cyclohexylmaleimide , N-chlorophenylmaleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, N-naphthylmaleimide, N-lylylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide Hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenylmaleimide, N-nitrophenylmaleimide, N-benzylmaleimide and a small amount copolymerizable therewith Of monomers.
본 발명에 있어서, 상기 N-치환 말레이미드 단량체는 사원 괴상중합체에서 내열 특성의 발현과 열안정성의 감소를 방지하고 용융점도 및 취성의 상승을 억제하여 혼합 수지와의 배합 시 가공성과 혼련성을 유지하고 또한 발열제어가 용이하도록 사원 괴상 공중합체에서 5~60중량%범위로 사용한다.In the present invention, the N-substituted maleimide monomer prevents the decrease of the thermal stability and the manifestation of the heat resistance characteristic in the massive block copolymer and suppresses the increase of the melt viscosity and the brittleness so as to maintain the processability and the kneading property And is used in the range of 5 to 60% by weight in the massive block copolymer for easy control of heat generation.
본 발명의 바람직한 실시에 있어서, α-알킬스티렌계 단량체, 비닐시안계 단량체 및 방향족 비닐 단량체는 40-95 중량% 사용되며, 4원 공중합체의 유동성과 강성을 고려하여 상대적인 함량을 조절할 수 있다. 바람직하게는 상기 사원 괴상 공중합체의 분자량은 7~15만 미만이고, N-치환말레이미드 5~60중량%, α-알킬스티렌계 단량체 10~70중량%, 비닐시안계 단량체 5~50중량%, 방향족 비닐단량체 3~50중량%로 이루어진 것을 좋다. In a preferred embodiment of the present invention, 40-95% by weight of the? -Alkylstyrene monomer, the vinylcyanide monomer and the aromatic vinyl monomer are used, and the relative content can be controlled in consideration of the flowability and rigidity of the quaternary copolymer. Preferably, the molecular weight of the mass of the block copolymer is less than 7 to 150,000, and 5 to 60% by weight of the N-substituted maleimide, 10 to 70% by weight of the? -Alkylstyrene monomer, 5 to 50% And 3 to 50% by weight of an aromatic vinyl monomer.
본 발명에 있어서, N-치환 말레이미계 단량체, α-알킬스티렌계 단량체, 비닐 시안계 단량체 및 방향족 비닐 단량체로 이루어진 공중합체는 창호용 열가소성 합성 수지에 요구되는 내열성과 내구성 및 변색성이 조화될 수 있도록 3~20 중량%, 바람직하게는 5-15 중량%를 사용하는 것이 바람직하다. In the present invention, a copolymer composed of an N-substituted maleimide monomer, an? -Alkylstyrene monomer, a vinyl cyan monomer and an aromatic vinyl monomer can be combined with heat resistance, durability and discoloration required for a thermoplastic synthetic resin for window It is preferable to use 3 to 20% by weight, preferably 5 to 15% by weight.
본 발명은 다른 일 측면에 있어서, 아크릴계 고무 수지 30~60중량%, 중량 평균 분자량이 150,000~400,000인 스티렌계-비닐시안계 공중합체 20~70중량%, N-치환 말레이미계 단량체, α-알킬스티렌계 단량체, 비닐 시안계 단량체 및 방향족 비닐 단량체로 이루어진 공중합체 3~20중량%으로 이루어진 열가소성 수지 조성물에 산화방지제, 자외선흡수제, 활제를 포함하는 창호용 열가소성 조성물을 제공한다.According to another aspect of the present invention, there is provided a rubber composition comprising 30 to 60% by weight of an acrylic rubber resin, 20 to 70% by weight of a styrene-based vinylene copolymer having a weight average molecular weight of 150,000 to 400,000, And 3 to 20% by weight of a copolymer composed of a styrenic monomer, a vinyl cyan monomer and an aromatic vinyl monomer is provided in a thermoplastic composition for a window comprising an antioxidant, an ultraviolet absorber and a lubricant.
본 발명의 실시에 있어서, 상기 산화방지제, 자외선흡수제, 활제는 열가소성 수지 조성물 100 중량부에 산화방지제 0.01~1.0중량부, 자외선흡수제 0.01~~1.0중량부, 활제 0.3~5.0중량부로 포함되는 것이 바람직하다.In the practice of the present invention, it is preferable that the antioxidant, the ultraviolet absorber and the lubricant are contained in an amount of 0.01 to 1.0 part by weight, 0.01 to 1.0 part by weight of an ultraviolet absorbent, and 0.3 to 5.0 parts by weight of an antioxidant in 100 parts by weight of the thermoplastic resin composition Do.
본 발명에 따른 창호용 스티렌계 열가소성 수지 조성물에 있어서, 상기 산화방지제, 자외선흡수제 및 활제는 제품의 열안정성과 자외선 안정성 및 가공성의 향상을 위하여 첨가되는 것이다. 상기 산화방지제는 페놀계, 인계 또는 황에스테르계를 각각 혹은 혼합 사용 가능하며, 첨가량은 0.01~1.0중량부이다. 또한 본 발명에 있어서, 첨가제로 사용되는 자외선 흡수제는 벤조트리아졸 혹은 HALS계를 각각 혹은 혼합하여 사용하며, 첨가량은 0.01~1.0중량부이다. 활제는 에틸렌비스스테아르아미드, 폴리에틸렌왁스 혹은 스테아린산 등이 사용되며 0.3~5.0중량부를 첨가한다.In the styrene-based thermoplastic resin composition for a window according to the present invention, the antioxidant, the ultraviolet absorber and the lubricant are added for the purpose of improving the thermal stability of the product, ultraviolet stability and processability. The antioxidant may be a phenol-based, phosphorus-based or sulfur-ester-based antioxidant. The amount of the antioxidant added is 0.01 to 1.0 part by weight. In the present invention, the ultraviolet absorber to be used as an additive is benzotriazole or HALS, and the amount thereof is 0.01 to 1.0 part by weight. As the lubricant, ethylene bisstearamide, polyethylene wax or stearic acid is used, and 0.3 to 5.0 parts by weight of the lubricant is added.
본 발명은 또 다른 일 측면에 있어서, 아크릴계 고무 수지 30~60중량%, 중량 평균 분자량이 150,000~400,000인 스티렌계-비닐시안계 공중합체 20~70중량%, N-치환 말레이미계 단량체, α-알킬스티렌계 단량체, 비닐 시안계 단량체 및 방향족 비닐 단량체로 이루어진 공중합체 3~20중량%으로 이루어진 열가소성 수지 조성물에 산화방지제, 자외선흡수제, 활제, 및 안료를 압출하여 제조되는 착색 창호를 제공한다. In another aspect of the present invention, there is provided a rubber composition comprising 30 to 60% by weight of an acrylic rubber resin, 20 to 70% by weight of a styrene-based vinylene copolymer having a weight average molecular weight of 150,000 to 400,000, An antioxidant, an ultraviolet absorber, a lubricant, and a pigment to a thermoplastic resin composition comprising 3 to 20% by weight of a copolymer comprising an alkyl styrene monomer, a vinyl cyan monomer and an aromatic vinyl monomer.
본 발명에 따른 착색 창호는 창호 자체의 열안정성과 내열성이 우수하여 시장에서 요구하는 다양한 칼라의 조색이 가능하다.The colored window according to the present invention is excellent in heat stability and heat resistance of a window itself, and it is possible to color various colors required in the market.
본 발명에 따른 창틀용 스티렌계 열가소성 수지 조성물은 제품의 재활용과 원가 절감 및 폐수지 발생으로 인한 환경오염의 예방을 위하여, 제조공정 중 칼라의 색상차이나 또는 표면 불량과 같은 문제로 발생하는 규격외 제품을 함께 사용할 수 있다. 통상적으로 규격외 제품들은 파쇄 후 원재료와 함께 혼합하여 사용할 수 있으며, 바람직하게는 70중량%이내로 혼합하여 재사용 하는 것이 바람직하다.The styrene-based thermoplastic resin composition for a window frame according to the present invention may be used in a non-standard product which is caused by problems such as color difference in color or surface defects during the manufacturing process in order to recycle the product, reduce the cost and prevent environmental pollution due to the generation of waste water Can be used together. Normally, non-standard products may be mixed together with the raw materials after crushing, preferably mixed by less than 70 wt%, and reused.
본 발명에 따른 창호용 스티렌계 열가소성 수지 조성물은 창틀용 PVC 압출장비를 이용하여 창틀용 PVC 합성수지 압출 조건을 이용하여 제조할 수 있다. 본 발명의 실시에 있어서, 상기 창틀용 스티렌계 열가소성 수지는 통상적으로 창틀용 PVC의 압출 조건인 150~250℃의 압출기 온도범위에서 압출 가능하며, 원료 중 70중량% 이하의 스크랩을 혼합한 제품을 사용하여 제조할 수 있다.The styrene thermoplastic resin composition for window according to the present invention can be manufactured by using PVC extrusion conditions for window frames using PVC extrusion equipment for window frames. In the practice of the present invention, the styrenic thermoplastic resin for a window frame can be extruded at an extruder temperature range of 150 to 250 ° C, which is an extrusion condition of PVC for window frames, and a product obtained by mixing 70 wt% or less of scrap in the raw material . ≪ / RTI >
본 발명은 또 다른 일 측면에서, 본 발명의 창호는 아크릴계 고무가 PMI를 포함하는 SAN 수지에 분산되어 있으며, 상기 창호에서 PMI의 함량이 0.15~9.0 중량%인 것을 특징으로 한다. In another aspect of the present invention, the window of the present invention is characterized in that the acrylic rubber is dispersed in a SAN resin containing PMI, and the content of PMI is 0.15 to 9.0% by weight in the window.
이하 실시예 및 비교예를 통해 본 발명을 보다 구체적으로 설명하지만 하기 예에 본 발명의 범주가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to the following examples.
<압출조건><Extrusion conditions>
아래에 제조되는 열가소성 수지들은 창호의 제조는 압출 기계를 통하여 창틀로 제조되었다. 창틀 제조 기계로 PVC 압출기인 트윈 스크루 95mm (제작회사 삼부기계공업)를 이용하였으며 하기의 압출조건에 따라 제조되었다. 제조된 모델은 P샤시 BF-115이다.The thermoplastics produced below are manufactured from window frames through extrusion machines. A twin screw 95 mm (manufactured by Sambu Machinery Co., Ltd.), which is a PVC extruder, was used as a window frame manufacturing machine and was manufactured in accordance with the following extrusion conditions. The manufactured model is P chassis BF-115.
압출기 조건Extruder conditions
[표1][Table 1]
(1) 유동성(1) Fluidity
ASTM D 1238법에 준하여 하중 10kg 하중에 의해 측정하였으며, 창호재 압출에 적합한 유동성 범위는 5~8g/10min 이어야 창호 형재화가 가능한 범위이다.It was measured by a load of 10 kg according to ASTM D 1238, and the range of flowability suitable for extrusion of the window was 5 ~ 8g /
(2) 충격강도(2) Impact strength
샤르피 충격강도 시험으로 KS M3056법에 준하여 5호 시험편(A형 노치)으로 온도 23℃ ± 2에서 표준시험실시하였고 -10℃ ± 2에서 저온시험을 실시하였다. KS F5602 규격에 의하면 12.7 kJ/M2 (표준)이상이고 4.9 kJ/M2 (저온)이상이어야 창호 형재로서 사용 가능한 기준이다.Charpy impact strength test was carried out in accordance with KS M3056 method using a No. 5 test piece (type A notch) at a temperature of 23 ° C ± 2 and a low temperature test at -10 ° C ± 2. According to KS F5602 standard, it should be more than 12.7 kJ / M 2 (standard) and 4.9 kJ / M 2 (low temperature).
(2) 인장강도 (2) Tensile strength
인장강도 및 신장률 시험은 KS M3006법에 준하여 온도 23℃ ± 2에서 시험을 실시하였다. KS F5602 규격에 의하면 인장강도는 36.8 MN/m2 이상이어야 창호 형재로서 사용 가능한 기준이다.Tensile strength and elongation were tested in accordance with KS M3006 at a temperature of 23 ° C ± 2. According to the KS F5602 standard, the tensile strength must be 36.8 MN / m 2 or more, which is a standard that can be used as a window frame.
(4) 내후성시험 (4) Weathering test
장기내후성을 평가하기 위하여 촉진시험기 Q-UV(제조사 ; 미국 Q-PANEL)를 이용하여 200시간(1사이클 시험조건 8시간 동안 60℃ UV(A 타입 310nm) 0.74W/m2(광량세기) 조사 + 3분간 수분분무 + 3시간 57분 동안 45 ℃ 응축) 동안 시험 후 색차 변화를 측정하였다.In order to evaluate the long-term weatherability, irradiation of 0.74 W / m 2 (intensity of light intensity) at 60 ° C UV (A type 310 nm) for 200 hours (one cycle test condition for 8 hours) was performed using an accelerated tester Q- ≪ / RTI > + 3 minutes water spray + 3 hours 57 minutes 45 < 0 > C condensation).
(5) 굴곡 탄성율(5) Flexural modulus
굴곡 탄성률 시험은 KS M 178 규격에 의해 시험된다. 시험편의 수는 5개로 실시한다. KS F5602 규격에 의하면 굴곡 탄성율은 1960 MN/m2 이상이어야 창호 형재로서 사용 가능한 기준이다.The flexural modulus test is tested by the KS M 178 standard. The number of specimens shall be five. According to the KS F5602 standard, the flexural modulus is 1960 MN / m 2 or more, which is a standard that can be used as a window frame.
(6) HDT(열변형 온도)(6) HDT (heat distortion temperature)
열변형 온도 시험은 KS M ISO75-2에 규정한 방법 B로 하되 평평한 방향으로 시험편을 시험한다. 시험편의 수는 2개로 한다. The thermal deformation temperature test shall be carried out in the direction B as specified in KS M ISO 75-2, but in the direction of the test specimen. The number of specimens shall be two.
(7) 내열 변색(7) Heat discoloration
내열 변색 시험은 시험편의 치수는 길이 L : 100±2.0mm로 항온항습 장치내에 시험편을 25±2℃, 50RH% 조건에 24시간 동안 일정하게 유지 후 , 건조기 조건(온도 150℃, 3시간)에 일정시간 동안 유지한다. CR-300 색차계를 사용하여 ΔEab* 값을 측정한다. In the heat discoloration test, the specimens were maintained at 25 ± 2 ° C and 50RH% for 24 hours in a constant temperature and humidity apparatus with a length of L: 100 ± 2.0 mm, and then dried in a dryer condition (temperature: 150 ° C., 3 hours) It is maintained for a certain period of time. Measure the ΔEab * value using the CR-300 color difference meter.
(8) 내열 변형율(8) Heat Strain Rate
내열 변형율 시험은 시험편의 치수는 길이 L : 100±2.0mm로, 건조기 조건(온도 85℃, 3시간)에 일정시간 동안 유지한 후 시험편의 변화율을 측정한다.변형율이 0.5%이내이어야 건축용으로 사용가능하다.For the heat resistance strain test, the specimen dimensions shall be 100 ± 2.0mm in length and maintained at the dryer condition (temperature 85 ℃, 3 hours) for a certain period of time and then the change rate of test specimens shall be measured. It is possible.
종래의 사용되는 폴리염화비닐수지나 기존 ABS계 합성수지 창호 조성물 로 제조된 창호재는 대기 온도의 상승과 다양한 색상 보유로 인하여 창호 표면 온도 상승으로 인하여 창호의 변형, 뒤틀림 등의 문제가 있으나, 본 발명에 따른 창호는 높은 열변형 온도로 인하여 다양한 색상발현과 기계적 물성이 높으며, 창호 형재로서의의 압출 작업성이 우수하며 기존 친환경 ABS계 창호용 합성수지에 비해 우수한 물성을 제공하는 효과가 있다.The conventional window material made of polyvinyl chloride resin or existing ABS resin synthetic resin composition has problems such as deformation and warping of window due to rise of surface temperature of window due to increase of atmospheric temperature and various color retention, Due to its high heat distortion temperature, exhibits various colors and mechanical properties, has excellent extrusion workability as a window shape material, and has an effect of providing excellent physical properties as compared with a synthetic resin for an environment friendly ABS resin window.
실시예 1-6Examples 1-6
고무질중합체인 아크릴레이트계 고무를 유화중합법을 사용하여 부틸아크릴레이트단량체와 가교제를 혼합한후 먼저 개시제, 유화제, 분산매인 순수를 중합조에 투입후 70℃까지 승온후 교반하면서 단량체와 가교제를 연속첨가하여 만들어진 일부가교된 고형분기준 아크릴계고무질라텍스 60중량부에 고형분기준 스티렌 30중량부, 아크릴로니트릴10중량부를 통상의 유화제, 개시제등과 연속첨가하여 아크릴계고무에 스티렌-아크릴로니트릴이 그라프트된 공중합체라텍스를 제조하였다. 또한 이와 별도로 또한 폴리부타디엔 라텍스 60중량부(고형분기준)를 우선 중합조에 투입하여 교반하면서 70℃까지 승온한다. 그리고 유화제, 개시제, 그리고 스티렌단량체 30중량부, 아크릴로니트릴 10중량부를 연속첨가하여 중합을 시키면 부타디엔계고무에 스티렌, 아크릴로니트릴이 그라프트된 공중합체(B)라텍스를 제조하였다. 황산마그네슘을 전해질로 사용하여 상기 고형분기준으로 공중합체(A)85중량부와 공중합체 (B)15중량부를 혼용하여 응집하여 4원공중합체(C)인 AABS수지를 만들었다 또한 SAN 공중합체 제조 방법은 After mixing the butyl acrylate monomer and the crosslinking agent using the emulsion polymerization method as the rubbery polymer, the pure water as the initiator, the emulsifier and the dispersion medium is added to the polymerization vessel, and the temperature is elevated to 70 ° C., and the monomer and the crosslinking agent are continuously added Acrylonitrile grafted onto an acrylic rubber by continuously adding 30 parts by weight of styrene based on solid basis and 10 parts by weight of acrylonitrile to 60 parts by weight of a partially crosslinked acrylic based rubbery latex based on a crosslinked solid, To prepare a coalesced latex. Separately, 60 parts by weight (based on solid content) of polybutadiene latex was first charged into the polymerization vessel and the temperature was raised to 70 캜 while stirring. Then, 30 parts by weight of an emulsifier, an initiator, and a styrene monomer and 10 parts by weight of acrylonitrile were continuously added to polymerize to prepare a copolymer (B) latex in which styrene and acrylonitrile were grafted to butadiene rubber. 85 parts by weight of the copolymer (A) and 15 parts by weight of the copolymer (B) were coagulated by using magnesium sulfate as an electrolyte to prepare an AABS resin as the quaternary copolymer (C) silver
괴상중합의 반응조에 온도를 150 ℃가온시킨후 스티렌 66중량부 아크릴로니트릴44중량부, 톨루엔 10중량부 그리고 분자량조절제로 터셔리도데실메르캅탄 을 0.1중량부를 라인에서 먼저 혼용하면서 연속적으로 중합조에 첨가하여 중합을 시킨다. 전환율이 70%되는싯점에서 중합물을별도의 탱크로 이송시켜 220 ℃로 가온시킨후 그런다음 탈휘발장치로 이송하여 - 720mmHg로 진공상태로 하여 미반응단량체와 톨루엔을 제거한다 . 이렇게 하여 얻어진 제품은 중량평균분자량이 18만이며 조성이 스티렌과 아크릴로니트릴비율이 66/34인 SAN공중합체수지가 얻어진다 또한 PMI-SAN 공중합체 제조는 먼저 페닐말레이드20중량부와 아크릴로니트릴 20중량부를 혼용한후 알파메틸스티렌 50중량부와 스티렌10중량부를계량하여 혼용한후 중합온도 100℃에서 연속첨가하여 중합시킨다. After the temperature was raised to 150 ° C in a reaction tank for bulk polymerization, styrene 66 parts by weight, acrylonitrile 44 parts by weight, toluene 10 parts by weight, and molecular weight regulator 0.1 part by weight of tertiary dodecyl mercaptan were continuously mixed in the polymerization vessel And polymerization is carried out. At a point where the conversion rate is 70%, the polymerized material is transferred to a separate tank, which is then heated to 220 ° C., and then transferred to a devolatilizer to be vacuumed to -720 mmHg to remove unreacted monomers and toluene. The product thus obtained had a weight average molecular weight of 180,000 and a SAN copolymer resin having a styrene / acrylonitrile ratio of 66/34 was obtained. The preparation of the PMI-SAN copolymer was carried out by first mixing 20 parts by weight of phenyl maleate, And 20 parts by weight of nitrile are mixed together, 50 parts by weight of alpha methylstyrene and 10 parts by weight of styrene are weighed and mixed together, and the mixture is continuously added at a polymerization temperature of 100 占 폚.
전환율이 50%가 도달하는싯점에서 중합물을 240℃까지 승온시켜 탈휘발장치에서 진공으로 미반응 단량체를 제거하여 중량평균분자량이 10만이며 PMI/AMS/ST/AN의 비율이 20/50/10/20조성을 갖는 내열성이 우수한 PMI-SAN 공중합체를 얻어진다.The polymer was heated to 240 ° C at the point where the conversion rate reached 50%, and unreacted monomers were removed by vacuum in a devolatilizer to give a weight average molecular weight of 100,000 and a ratio of PMI / AMS / ST / AN of 20/50/10 / 20 composition having excellent heat resistance can be obtained.
하기 표와 같은 SAN공중합체수지와 PMI계 SAN수지와 AABS수지와 혼합비율을 조절하고 또한 산화방지제는 산화방지제(송원산업 6260) 0.3 중량부, 자외선흡수제(시바스페셜 주식회사 TINUVIN-P) 0.3 중량부, 이산화티탄 4중량부를 추가하여 균일한 배합 후 제조된 수지를 Pellet화 하였다. 그 Pellet화 된 합성수지 조성물을 사용하여 PVC 압출기를 이용하여 창호 프로파일을 제조하였다. The blending ratio of SAN copolymer resin, PMI SAN resin and AABS resin as shown in the following table was adjusted. In addition, 0.3 parts by weight of an antioxidant (Songwon Industry 6260) and 0.3 parts by weight of an ultraviolet absorber (TINUVIN-P, And 4 parts by weight of titanium dioxide were added, and the resin prepared after homogeneous blending was pelletized. A window profile was prepared using a PVC extruder using the pelletized synthetic resin composition.
비교예 1Comparative Example 1
하기 표와 같이 PMI SAN수지를 첨가하지 않고 창호 프로파일을 제조하였다.A window profile was prepared without adding PMI SAN resin as shown in the following table.
비교예 2Comparative Example 2
하기 표와 같이 PMI SAN수지를 20중량% 첨가하여 창호 프로파일을 제조하였다.A window profile was prepared by adding 20 wt% of PMI SAN resin as shown in the following table.
비교예 3Comparative Example 3
하기 표와 같이 PMI SAN수지를 25중량% 첨가하여 창호 프로파일을 제조하였다.A window profile was prepared by adding 25 wt% of PMI SAN resin as shown in the following table.
[표2][Table 2]
[표3][Table 3]
Claims (11)
중량평균 분자량이 150,000~400,000인 스티렌계-비닐시안계 공중합체 35~55 중량%와,
N-치환 말레이미드계 단량체, α-알킬스티렌계 단량체, 비닐시안계 단량체, 및 방향족 비닐 단량체로 이루어진 중량평균 분자량이 70,000~150,000미만의 4원 괴상 공중합체 3~15 중량%로 이루어진 창호용 열가소성 수지. 40 to 50% by weight of a quaternary copolymer rubber comprising an acrylic rubber-butadiene rubber-acrylonitrile monomer-styrene monomer,
35 to 55% by weight of a styrene-based vinylene copolymer having a weight average molecular weight of 150,000 to 400,000,
A thermoplastic resin for a window made of an N-substituted maleimide-based monomer, an? -Alkylstyrene-based monomer, a vinylcyanide-based monomer and an aromatic vinyl monomer and having a weight average molecular weight of 70,000 to less than 150,000 and 3 to 15% Suzy.
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