KR20020063986A - Resin composition for tube or pipe in electronic and industrial field - Google Patents
Resin composition for tube or pipe in electronic and industrial field Download PDFInfo
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- KR20020063986A KR20020063986A KR1020010004546A KR20010004546A KR20020063986A KR 20020063986 A KR20020063986 A KR 20020063986A KR 1020010004546 A KR1020010004546 A KR 1020010004546A KR 20010004546 A KR20010004546 A KR 20010004546A KR 20020063986 A KR20020063986 A KR 20020063986A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/105—Esters; Ether-esters of monocarboxylic acids with phenols
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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Abstract
Description
본 발명은 전자소재 및 공업용 튜브, 파이프용 수지 조성물에 관한 것으로, 보다 상세하게는 에틸렌비닐아세테이트 수지, 수지 보강제, 내화학제, 산화방지제 및 자외선 안정제를 포함하는 내피로성 및 내화학성이 우수한 전자소재 및 공업용 튜브, 파이프용 수지 조성물에 관한 것이다.The present invention relates to an electronic material and a resin composition for industrial tubes and pipes, and more particularly, to an electronic material having excellent fatigue resistance and chemical resistance, including ethylene vinyl acetate resin, a resin reinforcing agent, a chemical agent, an antioxidant, and an ultraviolet stabilizer. The resin composition for industrial tubes and pipes.
지금까지의 전자소재 및 공업용 튜브, 파이프용 수지 조성물은 단순히 기본수지인 PVC 수지와 산화방지제로 이루어졌으나, 이러한 수지 조성물로 제조된 최종 제품은 반복피로에 의한 열화, 및 화학 약품에 의한 산화 및 분해로 인하여 제품의 사용수명이 단축되는 문제점이 있었다.Until now, resin compositions for electronic materials, industrial tubes, and pipes simply consisted of basic resins, PVC resins and antioxidants. However, the final products made of such resin compositions are subject to degradation due to repeated fatigue and oxidation and decomposition by chemicals. Due to the problem of shortening the service life of the product.
한편, 일반적으로 상이한 물성을 지닌 두 가지의 수지를 단순 혼합하는 경우 고유의 기계적 물성이나 가공성 등이 저하되게 된다. 이러한 물성 저하를 극복하기 위해서 제안된 것이 블렌딩 기술이다.On the other hand, in general, in the case of simply mixing two kinds of resins having different physical properties, the inherent mechanical properties, processability and the like is lowered. Blending techniques have been proposed to overcome these degradations.
고분자 블렌드는 두 가지 이상의 고분자들이 서로 균일하게 혼합되어 공유결합에 의해 연결되어 있지 않으면서도 분자 단위로 서로 섞여 있거나 또는 계면에서의 접착력을 가지고 분산되어 있는 혼합물이다.A polymer blend is a mixture in which two or more polymers are uniformly mixed with each other and mixed with each other in a molecular unit without being covalently linked or dispersed with adhesive force at an interface.
고분자는 수많은 저분자량의 단량체들이 연결되어 긴 사슬모양의 구조를 갖는 높은 분자량의 물질이므로, 이들을 블렌딩하는데는 저분자량의 물질을 혼합하는 경우와 달리 각 성분간의 상용성(compatibility)이 큰 문제가 된다. 여기에서 상용성이란 각각의 성분들이 분자 수준에서 서로 균일하게 혼합되어 열역학적 평형상태를 유지하는 것을 의미한다. 상용성의 차이는 혼합된 고분자간의 상분리 또는 불연속상을 형성하며, 열전도도, 열팽창율의 차이에 의해 상호 계면에서의 열응력을 야기시켜 연속상을 이루는 혼합체에 비해 유연성, 내충격성 등의 기계적 물성이 저하되는 문제를 야기시킨다.Since polymer is a high molecular weight substance having a long chain structure by connecting a number of low molecular weight monomers, the compatibility between components is a big problem unlike blending low molecular weight substances. . Compatibility here means that the individual components are uniformly mixed with each other at the molecular level to maintain thermodynamic equilibrium. The difference in compatibility forms a phase separation or discontinuous phase between the mixed polymers, and the mechanical properties such as flexibility and impact resistance are higher than those of the continuous phase mixture by causing thermal stress at the interface due to the difference in thermal conductivity and thermal expansion coefficient. It causes the problem of deterioration.
비상용성인 두 수지가 용이하게 혼합되기 위해서는 이들의 분자운동을 방해하는 배열상의 제한요소(conformational resistance)를 극소화해야 한다. 이러한 측면에서 비교적 유사한 수지끼리 혼합하면 두 상간의 계면에너지 감소, 혼련시 분산상의 보다 균일한 분산, 거시적 상분리 현상 억제 및 계면 접착력 향상 등의 효과를 얻을 수 있으므로 물성의 향상을 가져 오게된다.In order for two incompatible resins to be easily mixed, the configurational resistance that interferes with their molecular motion must be minimized. Relatively similar resins can be mixed in this respect, resulting in improved physical properties, because of the reduction of interfacial energy between two phases, more uniform dispersion of dispersed phases during kneading, inhibition of macroscopic phase separation, and improved interfacial adhesion.
본 발명은 상기와 같은 종래기술의 문제점을 해결하기 위한 것으로, 에틸렌비닐아세테이트 수지를 기본수지로 사용하고 여기에 상기 에틸렌비닐아세테이트 수지와의 혼련성이 우수한 수지 보강제 및 내화학제를 첨가하여 다른 기계적 물성의저하없이 내피로성과 내화학성을 증가시킨 전자소재 및 공업용 튜브, 파이프용 수지 조성물을 제공함을 목적으로 한다.The present invention is to solve the problems of the prior art as described above, by using an ethylene vinyl acetate resin as a base resin and adding a resin reinforcing agent and a chemical resistant agent excellent in kneading with the ethylene vinyl acetate resin to other mechanical properties An object of the present invention is to provide a resin composition for electronic materials, industrial tubes and pipes, which has increased fatigue resistance and chemical resistance without deterioration.
즉, 본 발명은 (1) 에틸렌비닐아세테이트 수지, 및 (2) 저밀도 폴리에틸렌 수지, 선형저밀도 폴리에틸렌 수지, 에틸렌-프로필렌-디엔 고무(EPDM), 또는 그들의 혼합물인 수지 보강제를 95:5~20:80의 중량비로 혼합하고, 상기 에틸렌비닐아세테이트 수지 및 수지 보강제의 혼합물 100 중량부에 대하여 (3) 내화학제 0.01~3 중량부, (4) 산화방지제 0.1~0.2 중량부, 및 (5) 자외선 안정제 0.1~0.2 중량부를 첨가한 후 용융혼합하여 제조된, 전자소재 및 공업용 튜브, 파이프용 수지 조성물을 제공한다.Namely, the present invention provides a resin reinforcing agent which is (1) ethylene vinyl acetate resin, and (2) low density polyethylene resin, linear low density polyethylene resin, ethylene-propylene-diene rubber (EPDM), or a mixture thereof. (3) 0.01 to 3 parts by weight of chemical resistant agent, (4) 0.1 to 0.2 part by weight of antioxidant, and (5) UV stabilizer based on 100 parts by weight of the mixture of the ethylene vinyl acetate resin and the resin reinforcing agent. To provide a resin composition for electronic materials and industrial tubes, pipes produced by adding ~ 0.2 parts by weight to melt mixing.
이하, 본 발명을 보다 상세히 설명하고자 한다.Hereinafter, the present invention will be described in more detail.
본 발명에서는 전자소재 및 공업용 튜브, 파이프의 중요 물성인 내피로성과 내화학성을 향상시키기 위하여, 기본수지인 에틸렌비닐아세테이트 수지에 용융혼합시 동일 도메인을 형성할 수 있는 수지 보강제와 내화학제 등을 용융혼합하였다. 본 발명의 수지 조성물의 각 구성성분을 더욱 상세히 설명하면 다음과 같다.In the present invention, in order to improve fatigue resistance and chemical resistance, which are important properties of electronic materials, industrial tubes, and pipes, a resin reinforcing agent and a chemical agent that can form the same domain when melt-mixing with ethylene vinyl acetate resin, which is a basic resin, are melted. Mixed. Each component of the resin composition of the present invention will be described in more detail as follows.
본 발명에서 기본수지로는 용융지수(ASTM D1238, 230℃, 2.16kg) 0.1~10.0g/10분, 비닐아세테이트 함량 1~50 중량%의 에틸렌 비닐아세테이트(이하, EVA라 함) 수지를 사용한다.In the present invention, the basic resin is an ethylene vinyl acetate (hereinafter referred to as EVA) resin having a melt index (ASTM D1238, 230 ° C., 2.16 kg) of 0.1 to 10.0 g / 10 minutes and a vinyl acetate content of 1 to 50 wt%. .
본 발명에서 수지 보강제로는 (a)용융지수(ASTM D1238, 230℃, 2.16kg)0.1~20.0g/10분, 밀도 0.88~0.935g/㎤의 저밀도 폴리에틸렌(이하, LDPE라 함) 수지, (b)용융지수(ASTM D1238, 230℃, 2.16kg) 0.1~20.0g/10분, 밀도 0.900~0.945g/㎤의 선형저밀도 폴리에틸렌(이하, LLDPE라 함) 수지, 및/또는 (c)무니점도 10~100, 에틸렌 함량 10~90 중량%의 에틸렌-프로필렌-디엔 고무(EPDM)를 사용한다.In the present invention, the resin reinforcing agent is (a) a melt index (ASTM D1238, 230 ° C., 2.16 kg) of 0.1-20.0 g / 10 minutes, a low density polyethylene (hereinafter referred to as LDPE) resin having a density of 0.88 to 0.935 g / cm 3, ( b) melt index (ASTM D1238, 230 ° C., 2.16 kg) 0.1-20.0 g / 10 min, linear low density polyethylene (hereinafter referred to as LLDPE) resin with a density of 0.900 to 0.945 g / cm 3, and / or (c) a Mooney viscosity Ethylene-propylene-diene rubber (EPDM) with 10-100, ethylene content 10-90% by weight is used.
상기 기본수지와 수지 보강제의 혼합비율은 중량비로 95:5 ~ 20:80인 것이 바람직하다.The mixing ratio of the base resin and the resin reinforcing agent is preferably 95: 5 to 20:80 by weight.
본 발명에서 내화학제로는 하기 화학식 1의 N-O-R(Nitrogen-Oxygen-Alkyl) 할스(HALS: Hindered Amine Light Stablizer)계 화합물을 사용하였다.In the present invention, as the chemical agent, an N-O-R (Nitrogen-Oxygen-Alkyl) Hals (HALS) compound of Formula 1 was used.
(상기 식에서, R은 C1∼C20의 알킬기, 수산화기에 의해 치환된 C1∼C20의 알킬기, C5∼C12의 시클로알킬기, C1∼C4의 알킬기에 의해 치환된 C5∼C12의 시클로알킬기, 또는 사슬 중간에 O 원자 또는 S 원자를 포함하는 C2∼C20의 알킬기임)(Wherein, R is C 1 ~C 20 alkyl group, an alkyl group of C 1 ~C 20 is substituted by a hydroxyl group, a C 5 ~C 12 cycloalkyl group, optionally substituted by an alkyl group of C 1 ~C 4 C 5 ~ of A cycloalkyl group of C 12 or a C 2 -C 20 alkyl group containing an O atom or an S atom in the middle of a chain)
상기 내화학제의 함량은 기본수지 및 수지 보강제 100 중량부에 대하여 0.01~3 중량부인 것이 바람직하다.The content of the chemical resistant agent is preferably 0.01 to 3 parts by weight based on 100 parts by weight of the base resin and the resin reinforcing agent.
상기 성분들 이외에도, 본 발명의 수지 조성물에는 메틸렌(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트 및 디-t-부틸-히드록시톨루엔 등의 산화 방지제와, 비스(2,2',6,6'-테트라메틸-4-피페리딘)세바케이트 및 그외의 2,2',6,6'-테트라알킬피페리딘 유도체와 같은 HALS(Hindered Amine Light Stabilizer)계 화합물 등의 자외선 안정제가 첨가될 수 있다. 상기 산화 방지제와 자외선 안정제의 함량은 기본수지 및 수지 보강제의 혼합물 100 중량부에 대하여 각각 0.1∼0.2중량부인 것이 바람직하다.In addition to the above components, the resin composition of the present invention includes an antioxidant such as methylene (3,5-di-t-butyl-4-hydroxyphenyl) propionate and di-t-butyl-hydroxytoluene, and bis ( HLS (Hindered Amine Light Stabilizer) system, such as 2,2 ', 6,6'-tetramethyl-4-piperidine) sebacate and other 2,2', 6,6'-tetraalkylpiperidine derivatives Ultraviolet stabilizers, such as a compound, can be added. The content of the antioxidant and ultraviolet stabilizer is preferably 0.1 to 0.2 parts by weight based on 100 parts by weight of the mixture of the base resin and the resin reinforcing agent.
이하, 실시예를 통하여 본 발명을 보다 구체적으로 설명하고자 하나, 이러한 실시예들은 단지 설명의 목적을 위한 것으로 본 발명을 제한하는 것으로 해석되어서는 안된다.Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
실시예 1∼10 및 비교예 1~2Examples 1-10 and Comparative Examples 1-2
하기 표 1에 나타낸 바와 같이 각 성분들을 평량한 후, 이들을 건식혼합기에 넣고 30분간 혼합한 다음, 다시 압출혼합기에 넣고 용융혼합시켰다. 이로부터 수득한 용융혼합체를 펠렛 형태로 만든 후, 파이프 성형기로 파이프를 성형하고, 물성을 평가하였다.As shown in Table 1, after weighing each component, they were put in a dry mixer and mixed for 30 minutes, and then again put in an extrusion mixer and melt mixed. After the molten mixture obtained in the form of pellets, the pipe was molded by a pipe molding machine, and the physical properties were evaluated.
[비고][Remarks]
(1) 산화방지제 1: 메틸렌(3,5-디-t-부틸-4-히드록시페닐)프로피오네이트(1) Antioxidant 1: Methylene (3,5-di-t-butyl-4-hydroxyphenyl) propionate
(2) 산화방지제 2: 디-t-부틸히드록시톨루엔(2) Antioxidant 2: Di-t-butylhydroxytoluene
(3) 자외선 안정제: 비스(2,2',6,6'-테트라메틸-4-피페리딘)세바케이트(3) Ultraviolet stabilizer: Bis (2,2 ', 6,6'-tetramethyl-4-piperidine) sebacate
(4) 내화학제: N-O-R(Nitrogen-Oxygen-Alkyl) 할스(HALS: Hindered Amine Light Stablizer)계 화합물(4) Chemical Resistant: N-O-R (Nitrogen-Oxygen-Alkyl) Hals (HALS: Hindered Amine Light Stablizer) Compound
[물성 평가 방법][Property evaluation method]
(1)내피로성: 밴딩시 균열이 일어나기 까지의 밴딩횟수로 나타내었다.(1) Fatigue resistance: It is expressed as the number of bandings until cracking occurs during bending.
(2)내화학성: 성형된 파이프를 주 1회 0.1N H2SO3로 처리하면서 Atlas Weother-OMeter 내에서 1000시간 동안 방치한 후의 인장강도를 ASTM D638 방법에 의거하여 측정한 다음, 화학물질(즉, 0.1N H2SO3) 처리전의 파이프의 인장강도를기준으로 하였을 때의 인장강도 보지율(保持率)로 나타내었다.(2) Chemical resistance: Tensile strength after 1000 hours in the Atlas Weother-OMeter while the molded pipe was treated with 0.1 N H2SO3 once a week was measured according to ASTM D638 method, and then the chemical (ie 0.1 Tensile strength retention was shown based on the tensile strength of the pipe before N H2SO3) treatment.
이상에서 상세히 설명한 바와 같이, 본 발명의 수지 조성물은 지금까지 전자소재 및 공업용 튜브, 파이프용으로 사용되어온 기존 PVC 수지 조성물에 비하여 월등히 향상된 내피로성 및 내화학성을 가지므로, 농업용, 전자용,흡기 및 공급용, 냉난방용, 의료용, 가정용 및 환경보호용 튜브 및 파이프 제조에 매우 유용하다.As described in detail above, the resin composition of the present invention has significantly improved fatigue resistance and chemical resistance compared to the existing PVC resin composition which has been used for electronic materials, industrial tubes, and pipes until now, and thus for agricultural, electronic, intake and It is very useful for manufacturing tube and pipe for supply , air-conditioning, medical, household and environmental protection.
Claims (6)
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KR1020010004546A KR20020063986A (en) | 2001-01-31 | 2001-01-31 | Resin composition for tube or pipe in electronic and industrial field |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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KR100796121B1 (en) * | 2001-12-26 | 2008-01-21 | 삼성토탈 주식회사 | Resin composition for pipe with excellent resistance against chlorine chemicals |
KR101506326B1 (en) * | 2013-10-14 | 2015-03-26 | 넥쌍 | Polymer resin composition for preparing insulating material having reinforced thermal stability |
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KR960006148A (en) * | 1994-07-12 | 1996-02-23 | 길레 마르셀 | Electrical connection of the cable to the contact terminals and the terminals connected accordingly |
KR100239581B1 (en) * | 1996-12-30 | 2000-01-15 | 이정국 | Insulating material for electric wire |
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JP2000178386A (en) * | 1998-12-14 | 2000-06-27 | Fujikura Ltd | Nonhalogen flame-retarded resin composition |
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US5204473A (en) * | 1987-09-21 | 1993-04-20 | Ciba-Geigy Corporation | O-substituted N-hydroxy hindered amine stabilizers |
US5004770A (en) * | 1988-10-19 | 1991-04-02 | Ciba-Geigy Corporation | Polymeric substrates stabilized with N-substituted hindered amines |
US5096950A (en) * | 1988-10-19 | 1992-03-17 | Ciba-Geigy Corporation | Polyolefin compositions stabilized with NOR-substituted hindered amines |
KR960006148A (en) * | 1994-07-12 | 1996-02-23 | 길레 마르셀 | Electrical connection of the cable to the contact terminals and the terminals connected accordingly |
KR100239581B1 (en) * | 1996-12-30 | 2000-01-15 | 이정국 | Insulating material for electric wire |
KR20000009561A (en) * | 1998-07-20 | 2000-02-15 | 최영재 | Fabrication method for thermal shrinkage tube |
JP2000178386A (en) * | 1998-12-14 | 2000-06-27 | Fujikura Ltd | Nonhalogen flame-retarded resin composition |
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Publication number | Priority date | Publication date | Assignee | Title |
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KR100796121B1 (en) * | 2001-12-26 | 2008-01-21 | 삼성토탈 주식회사 | Resin composition for pipe with excellent resistance against chlorine chemicals |
KR101506326B1 (en) * | 2013-10-14 | 2015-03-26 | 넥쌍 | Polymer resin composition for preparing insulating material having reinforced thermal stability |
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