KR20040044678A - Nontoxic and Odorless Polyvinyl Chloride Resin Composition - Google Patents

Nontoxic and Odorless Polyvinyl Chloride Resin Composition Download PDF

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KR20040044678A
KR20040044678A KR1020020072801A KR20020072801A KR20040044678A KR 20040044678 A KR20040044678 A KR 20040044678A KR 1020020072801 A KR1020020072801 A KR 1020020072801A KR 20020072801 A KR20020072801 A KR 20020072801A KR 20040044678 A KR20040044678 A KR 20040044678A
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polyvinyl chloride
chloride resin
weight
resin composition
stabilizer
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KR100508146B1 (en
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공동화
홍칠의
김현주
이계석
이규일
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주식회사 엘지화학
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L27/04—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 containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE: A non-toxic polyvinyl chloride resin composition with reduced odor is provided, which does not discharge environmental hormones and heavy metals while maintaining excellent properties including hardness, tensile strength, elongation, thermal reduction and odor. CONSTITUTION: The polyvinyl chloride resin composition comprises, based on the 100 pts.wt of polyvinyl chloride resin, 5-150 pts.wt. of a biphthalate plasticizer, 0.1-7 pts.wt of a Ca-Zn based stabilizer, and 0.1-4 pts.wt of an epoxy stabilizer, wherein the biphthalate plasticizer is a mixture containing trimethylol propane ester, specifically a mixture of trimethylol propane-tri-(2-ethyl hexanoate), benzoic acid 2,2-bis-(2-ethyl-hexanoyloxymethyl)-butyl ester, 2-ethylhexanoic acid 2,2-bis-(benzoyloxymethyl)-butyl ester and trimethylol propane-tri-benzoate. In the formula 1, each R1, R2 and R3 is a phenyl group, or an alkyl group having C3-C10.

Description

무독 및 저취의 폴리염화비닐 수지 조성물{Nontoxic and Odorless Polyvinyl Chloride Resin Composition}Non-toxic and Odorless Polyvinyl Chloride Resin Composition

본 발명은 무독 및 저취 폴리염화비닐 수지 조성물에 관한 것으로, 더욱 상세하게는 환경호르몬 및 중금속을 방출하지 않으면서도 경도, 인장강도, 신율, 가열감량, 냄새 등의 물성이 우수한 무독 및 저취 폴리염화비닐 수지 조성물에 관한 것이다.The present invention relates to a non-toxic and low-odor polyvinyl chloride resin composition, and more particularly, non-toxic and low-odor polyvinyl chloride having excellent physical properties such as hardness, tensile strength, elongation, heating loss, and odor without releasing environmental hormones and heavy metals. It relates to a resin composition.

폴리염화비닐 수지는 염화비닐의 단독 중합체 및 염화비닐을 50% 이상 함유한 혼성중합체로서 가소제(Plasticizer), 안정제(Stabilizer), 충전제(Filler), 안료(Pigment) 등 여러 가지 첨가제를 적절하게 혼합하여 다양한 가공 물성을 부여할 수 있는 범용 수지이다. 이러한 폴리염화비닐 수지는 압출성형, 사출성형, 캘린더링 등의 가공법에 의하여 파이프, 전선, 전기기계제품, 장난감, 필름, 시트, 인조가죽, 타포린, 테이프, 식품 포장지, 의료용품에 이르기까지 다양한 제품들의 소재로 광범위하게 사용된다.Polyvinyl chloride resin is a homopolymer of vinyl chloride and a copolymer containing 50% or more of vinyl chloride, and is appropriately mixed with various additives such as plasticizer, stabilizer, filler, pigment, and the like. It is a general purpose resin that can impart various processing properties. These polyvinyl chloride resins can be used for various products ranging from pipes, wires, electric machines, toys, films, sheets, artificial leather, tarpaulins, tapes, food packaging, and medical supplies by processing methods such as extrusion molding, injection molding, and calendering. It is widely used as a material for them.

폴리염화비닐 수지에 첨가되어 가공성, 유연성, 전기 절연성 등 여러 가지 물성 및 기능을 부여하는 필수 첨가제인 가소제의 대표적인 종류로는프탈레이트계(Phthalates), 아디페이트계(Adipates), 트리멜리테이트계 (Trimellitates) 등을 들 수 있으며, 이 중에서 프탈레이트계 가소제인 DEHP(di-ethyhexyl phthalate), DBP(di -butyl phthalate), DIDP(di-isodecyl phthalate), BBP(Butyl Benzyl phthalate), DINP(di-isononyl phthalate), DNOP(di-n-octyl phthalate) 등이 가장 널리 사용된다.Representative types of plasticizers, which are essential additives added to polyvinyl chloride resins to provide various properties and functions such as processability, flexibility, and electrical insulation, are phthalates, adipates, and trimellitates. Among these, phthalate-based plasticizers such as DE-HP (di-ethyhexyl phthalate), DBP (di-butyl phthalate), DIDP (di-isodecyl phthalate), BBP (Butyl Benzyl phthalate), DINP (di-isononyl phthalate) And di-n-octyl phthalate (DNOP) are the most widely used.

폴리염화비닐 수지의 또 다른 첨가제인 안정제로는 Ba-Zn계를 주로 사용하여 왔다.Ba-Zn type has been mainly used as a stabilizer which is another additive of polyvinyl chloride resin.

그러나, 프탈레이트계 가소제 및 Ba-Zn계 안정제는 인체에 유해한 환경호르몬 및 카드뮴, 납, 크롬, 안티몬, 비소, 수은, 바륨, 셀레늄과 같은 중금속을 방출하는 것으로 추정되고 있다.However, phthalate-based plasticizers and Ba-Zn-based stabilizers are believed to release environmental hormones and heavy metals such as cadmium, lead, chromium, antimony, arsenic, mercury, barium and selenium, which are harmful to humans.

또한, 폴리염화비닐 수지 조성물을 사용한 폴리염화비닐 시트(PVC Sheet)의 경우 환경호르몬 및 유해중금속 문제이외에도 가소제, 안정제 기타 첨가제에 의해 발생되는 냄새 문제로 그 적용에 있어서 제한되며, 소비자들의 불만이 증가하고 있는 실정이다.In addition, the polyvinyl chloride sheet (PVC Sheet) using the polyvinyl chloride resin composition is limited in its application to the odor problems caused by plasticizers, stabilizers and other additives, in addition to environmental hormones and harmful heavy metals problems, increasing consumer complaints I'm doing it.

더군다나, 최근 들어 중금속, 환경호르몬 및 냄새에 대한 규제가 강화되면서 기존의 폴리염화비닐 수지 제품들이 갖는 환경적인 문제점을 탈피한 열 가소성 플라스틱(Themo Plastic Elastomer, TPE)이나 폴리에틸렌(Polyethylene, PE) 수지 소재로의 대체가 빠르게 추진되고 있어 PVC사업이 위기에 당면해 있으며 PVC제품의 환경 및 냄새문제 해결에 대한 방안이 절실히 요구되고 있다.In addition, the recent tightening of regulations on heavy metals, environmental hormones and odors has prevented the environmental problems of conventional polyvinyl chloride resin products, such as Thermo Plastic Elastomer (TPE) or polyethylene (PE) resin materials. As the replacement of furnaces is being promoted rapidly, the PVC business is facing a crisis and there is an urgent need for measures to solve the environmental and odor problems of PVC products.

이에 본 발명자는 종래의 폴리염화비닐 수지의 문제점을 해결하기 위하여 첫째로 기존의 폴리염화비닐 수지가 갖는 신율, 인장강도, 가열감량, 냄새 등의 물성을 유지하면서도 환경호르몬을 방출하지 않는 가소제를 선택 하였고, 둘째로 유해 중금속 물질인 카드뮴, 납, 크롬, 안티몬, 비소, 수은, 바륨, 셀레늄 등이 검출되지 않는 무독 안정제를 선택하였으며, 셋째로 무독안정제 사용시 발생할 수 있는 내열성 등의 물성 약화를 방지하고, 넷째로 첨가제 등에 의하여 발생하는 냄새 문제를 개선하여 무독 및 저취 폴리염화비닐 수지 조성물을 발명하기에 이르렀다.In order to solve the problems of the conventional polyvinyl chloride resin, the present inventors first select a plasticizer that does not release environmental hormones while maintaining physical properties such as elongation, tensile strength, heating loss, and smell of the existing polyvinyl chloride resin. Second, we selected non-toxic stabilizers that do not detect harmful heavy metals such as cadmium, lead, chromium, antimony, arsenic, mercury, barium and selenium. Third, we prevent the weakening of physical properties such as heat resistance that can occur when non-toxic stabilizers are used. Fourthly, odor problems caused by additives and the like have been improved to invent non-toxic and low-odor polyvinyl chloride resin compositions.

본 발명의 목적은 신율, 인장강도, 가열감량, 냄새 등의 물성이 우수하면서도 중금속 및 환경호르몬이 발생하지 않는 무독 및 저취 폴리염화비닐 수지 조성물을 제공하기 위한 것이다.An object of the present invention is to provide a non-toxic and low-odor polyvinyl chloride resin composition excellent in physical properties such as elongation, tensile strength, heating loss, odor, etc., and does not generate heavy metals and environmental hormones.

본 발명의 상기 목적 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.

본 발명에 따른 무독 및 저취 폴리염화비닐 수지 조성물은 폴리염화비닐 수지100중량부에 대하여 비프탈레이트 가소제 5 내지 150중량부, Ca-Zn계 안정제 0.1 내지 7중량부, 에폭시계 안정제 0.1내지 4중량부를 포함하여 이루어진다.Non-toxic and low-odor polyvinyl chloride resin composition according to the present invention is 5 to 150 parts by weight of non-phthalate plasticizer, 0.1 to 7 parts by weight of Ca-Zn-based stabilizer, 0.1 to 4 parts by weight of epoxy stabilizer based on 100 parts by weight of polyvinyl chloride resin It is made to include.

상기 비프탈레이트 가소제는 하기 화학식 1로 표시되는 트리메틸올프로판(Trimethylolpropane, TMP) 에스테르를 포함하는 혼합물로서 a) 트리메틸올프로판-트리-(2-에틸헥사노에이트)(trimethylolpropane-tri-(2-ethyl hexanoate)), b) 벤조산 2,2- 비스-(2-에틸-헥사노일옥시메틸)-부틸에스테르(benzoic acid 2,2-bis-(2-ethyl-hexanoyloxymethyl)-butyl ester), c) 2-에틸헥산산 2,2- 비스-(벤조일옥시메틸)-부틸 에스테르(2-ethylhexanoic acid 2,2-bis-(benzoyloxymethyl)-butyl ester) 및 d) 트리메틸올프로판-트리- 벤조에이트(trimethylol propane-tri-benzoate) 4종의 에스테르 화합물의 혼합물이다.The non-phthalate plasticizer is a mixture containing a trimethylolpropane (TMP) ester represented by the following Formula 1 a) trimethylolpropane-tri- (2-ethylhexanoate) (trimethylolpropane-tri- (2-ethyl hexanoate)), b) benzoic acid 2,2-bis- (2-ethyl-hexanoyloxymethyl) -butyl ester, c) 2 2-ethylhexanoic acid 2,2-bis- (benzoyloxymethyl) -butyl ester and d) trimethylolpropane-tri-benzoate (trimethylol propane) -tri-benzoate) A mixture of four ester compounds.

[화학식 1][Formula 1]

상기식에서, R1, R2및 R3는 각각 페닐기(Phenyl group) 또는 탄소수가 3 내지 10, 바람직하게는 4 내지 8인 알킬 그룹(Alkyl group)이다.Wherein R 1 , R 2 and R 3 are each a phenyl group or an alkyl group having 3 to 10, preferably 4 to 8 carbon atoms.

상기 Ca-Zn계 안정제는 Ca-Zn 유기복합 안정제이다. 상기 에폭시계 안정제는 에폭시화된 소이빈 오일(Epoxidized soybean oil)이다.The Ca-Zn-based stabilizer is a Ca-Zn organic composite stabilizer. The epoxy stabilizer is an epoxidized soybean oil.

또한 본 발명은 상기 무독 및 저취 폴리염화비닐 수지 조성물로 제조된 폴리염화비닐 시트 및 폴리염화비닐 컴파운드를 제공한다.The present invention also provides a polyvinyl chloride sheet and a polyvinyl chloride compound prepared from the non-toxic and low-odor polyvinyl chloride resin composition.

이하, 본 발명을 하기에 보다 상세하게 설명하고자 한다.Hereinafter, the present invention will be described in more detail.

본 발명의 무독 및 저취 폴리염화비닐 수지 조성물은 폴리염화비닐 수지, 트리메틸올프로판(Trimethylolpropane, TMP) 에스테르를 포함하는 혼합물 가소제, Ca-Zn계 안정제, 에폭시계 안정제를 포함하여 이루어진다.The non-toxic and low-odor polyvinyl chloride resin composition of the present invention comprises a polyvinyl chloride resin, a mixture plasticizer containing trimethylolpropane (TMP) ester, a Ca-Zn-based stabilizer and an epoxy stabilizer.

종래의 폴리염화비닐 수지의 가소제로 널리 사용되는 프탈레이트 가소제가환경호르몬을 방출하는 주요성분인 것으로 추정되고 있는 바, 이를 대체하기 위하여 본 발명은 비프탈레이트 가소제로서 상기 트리메틸올프로판(Trimethylolpropane, TMP) 에스테르를 포함하는 혼합물 가소제를 선택하였다. 상기 가소제는 대한민국 특허출원 제2001-0000655호에 게재된 것으로 하기 화학식 1로 표시되는 트리메틸올프로판 에스테르를 포함한다. 즉, a) 트리메틸올프로판-트리-(2-에틸헥사노에이트)(trimethylolpropane-tri-(2-ethyl hexanoate)), b) 벤조산 2,2- 비스-(2-에틸-헥사노일옥시메틸)-부틸 에스테르(benzoic acid 2,2-bis-(2-ethyl-hexanoyloxymethyl)-butyl ester), c) 2-에틸헥산산 2,2- 비스-(벤조일옥시메틸)-부틸 에스테르(2-ethylhexanoic acid 2,2-bis-(benzoyloxymethyl)-butyl ester) 및 d) 트리메틸올프로판-트리- 벤조에이트(trimethylol propane-tri-benzoate)를 포함하는 것으로, 상기 서로 다른 4종의 에스테르 화합물의 혼합물이다.Phthalate plasticizer widely used as a plasticizer of the conventional polyvinyl chloride resin is estimated to be the main component to release the environmental hormone, in order to replace the present invention is a non-phthalate plasticizer, the trimethylolpropane (TMP) ester A mixture plasticizer containing was selected. The plasticizer is disclosed in Korean Patent Application No. 2001-0000655 and includes a trimethylolpropane ester represented by the following Chemical Formula 1. That is, a) trimethylolpropane-tri- (2-ethyl hexanoate), b) benzoic acid 2,2-bis- (2-ethyl-hexanoyloxymethyl) Butyl ester (benzoic acid 2,2-bis- (2-ethyl-hexanoyloxymethyl) -butyl ester), c) 2-ethylhexanoic acid 2,2-bis- (benzoyloxymethyl) -butyl ester (2-ethylhexanoic acid 2,2-bis- (benzoyloxymethyl) -butyl ester) and d) trimethylolpropane-tri-benzoate, which is a mixture of the four different ester compounds.

[화학식 1][Formula 1]

상기식에서, R1, R2및 R3는 각각 페닐기(Phenyl group) 또는 탄소수가 3 내지 10, 바람직하게는 4 내지 8인 알킬 그룹(Alkyl group)이다.Wherein R 1 , R 2 and R 3 are each a phenyl group or an alkyl group having 3 to 10, preferably 4 to 8 carbon atoms.

상기 가소제의 제조방법, 작용, 효능 및 기타 사항에 대해서는 대한민국 특허출원 제2001-0000655호에 게재된 바와 같으며, 엘지화학에서 엘지프렉스비이티(LGflex BET) 이란 상품명으로 이미 시판되고 있다. 본 발명에 첨가되는 비프탈레이트 가소제로서는 상기 이외에도 아세틸 트리 부틸 사이트레이트(Acetyl tributyl citrate, ATBC, 미국 Morflex사) 및 페놀과 크레설의 알킬 설폰산(Alkyl sulfonic acid of phenol and cresol, 메사몰, 독일 Buyer사), 디이소노닐 아디페이트(Diisononyl adipate, DINA, LG화학)를 사용할 수도 있으나, 엘지프렉스 비이티(LGflex BET)를 제외한 상기 가소제는 환경호르몬이 발생하지는 않으나, 기타 다른 물성을 저하시키는 단점이 있다.The method, action, efficacy and other matters of the plasticizer are as described in Korean Patent Application No. 2001-0000655, which is already marketed under the trade name LGflex BET by LG Chem. Non-phthalate plasticizers added to the present invention include acetyl tributyl citrate (ATBC, Morflex, USA) and alkyl sulfonic acid of phenol and cresol (mesamol, Germany Buyer). 4), Diisononyl adipate (DINA, LG Chemical) may be used, but the plasticizer except LGflex BET does not generate environmental hormones, but has other disadvantages of degrading other physical properties. have.

본 발명에서는 트리메틸올프로판(Trimethylolpropane, TMP) 에스테르를 포함하는 혼합물 가소제를 폴리염화비닐 수지 100중량부에 대하여 5 내지 150중량부인 것이 바람직한데, 5중량부 미만에서는 가소제의 효과를 발휘하지 못하며, 150중량부를 초과하는 경우에는 가소제가 수지로 완전히 흡수되지 못하며, 경도가 너무 낮아 가공시 어려움이 있으며, 설령 가공이 되었다 하더라도 가소제가 밖으로 이행되어 제품으로의 적용이 어렵다. 더욱 바람직하게는 폴리염화비닐 수지 100중량부에 대하여 30 내지 80중량부이다.In the present invention, it is preferable that the mixture plasticizer containing trimethylolpropane (TMP) ester is 5 to 150 parts by weight based on 100 parts by weight of polyvinyl chloride resin, but less than 5 parts by weight does not exhibit the effect of the plasticizer. If it exceeds the weight part, the plasticizer is not completely absorbed by the resin, the hardness is too low, there is difficulty in processing, even if processed, the plasticizer is transferred to the outside is difficult to apply to the product. More preferably, it is 30-80 weight part with respect to 100 weight part of polyvinyl chloride resins.

또한, 본 발명은 유해 중금속을 방출하지 않는 폴리염화비닐 수지를 제공하기 위하여 안정제로서 Ca-Zn 유기복합안정제를 선택하는데, 상기 Ca-Zn 유기복합안정제로는 KCZ-08(코오롱사), CZ-11(독일 Witco사), LTX-15(한국대협사) 및 CZ-2000(독일 Henkel사)를 들 수 있다.In addition, the present invention selects a Ca-Zn organic composite stabilizer as a stabilizer to provide a polyvinyl chloride resin that does not emit harmful heavy metals, KCZ-08 (Kolon Corporation), CZ- 11 (Witco, Germany), LTX-15 (Korea Consortium) and CZ-2000 (Henkel, Germany).

상기 안정제는 폴리염화비닐 수지 100중량부에 대하여 0.1 내지 7중량부인 것이 바람직한데 0.1중량부 이하에서는 내열성 효과가 거의 없으며, 7중량부 이상에서는 냄새가 심하게 발생되어 무취 제품에는 적용이 곤란하다. 더욱 바람직하게는 폴리염화비닐 수지 100중량부에 대하여 2 내지 3중량부이다.The stabilizer is preferably 0.1 to 7 parts by weight with respect to 100 parts by weight of polyvinyl chloride resin, but less than 0.1 parts by weight has almost no heat resistance effect, the odor is badly generated at 7 parts by weight or more difficult to apply to odorless products. More preferably, it is 2-3 weight part with respect to 100 weight part of polyvinyl chloride resins.

또한, 본 발명은 가소제와 Ca-Zn계 안정제의 첨가로 인하여 폴리염화비닐 수지의 내열성이 약화된 점을 보완하기 위하여 에폭시계 안정제를 채택하는데, 상기 에폭시계 안정제로는 에폭시화된 소이빈 오일 (epoxidized soybean oil, REOPLAST 39, 독일 Witco사)을 들 수 있다. 에폭시계 안정제는 구조적으로 옥시란(oxirane, -C-O-C-)기를 가지고 있어 폴리염화비닐 수지의 열화시에 폴리염화비닐 수지내 체인(Chain)의 열화(Zipper현상)를 방지해준다. 또한 옥시란(Oxirane)기의 함량 및 순도가 수지의 내열성 및 냄새에 영향을 많이 미치는데, 에폭시화된 소이빈 오일(Epoxidized soybean oil, REOPLAST 39, 독일 Witco사)은 옥시란(Oxirane)기의 함량이4.5% 이상이고 순도가99.5% 이상으로 본 발명에 적합하다.In addition, the present invention adopts an epoxy stabilizer to compensate for the weakening of the heat resistance of the polyvinyl chloride resin due to the addition of a plasticizer and a Ca-Zn-based stabilizer, the epoxy stabilizer (epoxidized soybean oil ( epoxidized soybean oil, REOPLAST 39, Germany, Witco). Epoxy stabilizers structurally have oxirane (-C-O-C-) groups to prevent deterioration of the chain in the polyvinyl chloride resin during the deterioration of the polyvinyl chloride resin. In addition, the content and purity of the oxirane group affects the heat resistance and the smell of the resin.Epoxidized soybean oil (REOPLAST 39, Witco, Germany) is used for the oxirane group. The content is at least 4.5% and the purity is at least 99.5%, which is suitable for the present invention.

상기 에폭시계 안정제는 폴리염화비닐 수지 100중량부에 대하여 0.1내지 4중량부 첨가하는 것이 바람직한데, 0.1중량부 미만에서는 내열성 상승효과가 나타나지 않으며, 4중량부를 초과하는 경우에는 내열성은 개선되지만 냄새가 심하여 무취 제품에의 적용이 곤란하다. 더욱 바람직하게는 폴리염화비닐 수지 100중량부에 대하여 2 내지 3중량부이다.The epoxy stabilizer is preferably added in an amount of 0.1 to 4 parts by weight based on 100 parts by weight of the polyvinyl chloride resin, but less than 0.1 part by weight does not exhibit a synergistic effect on heat resistance. It is very difficult to apply to odorless products. More preferably, it is 2-3 weight part with respect to 100 weight part of polyvinyl chloride resins.

또한, 본 발명은 상기 폴리염화비닐 수지 조성물로 제조된 시트 및 컴파운드를 제공할 수 있다.In addition, the present invention can provide a sheet and a compound made of the polyvinyl chloride resin composition.

이하, 본 발명을 실시예 및 비교예를 통하여 더욱 상세하게 설명하겠는바, 본 발명이 하기 실시예에 의해 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited by the following Examples.

실시예 및 비교예를 통하여 제조된 폴리염화비닐 수지 조성물에 대한 물성평가는 하기와 같은 방법들에 의하여 시행되었다.Evaluation of physical properties of the polyvinyl chloride resin composition prepared through the Examples and Comparative Examples was carried out by the following methods.

◎ 인장강도 및 신율: 시편을 ASTM D412방법인 U.T.M기기의 크로스헤드스피드(Cross Head Speed)를 500mm/min으로 당긴 후, 시편이 절단되는 지점의 신율과 인장강도를 측정하였다. 인장 강도(kgf/㎟) 계산은 로드(load)값 (kgf)/두께(㎜)×폭(㎜)로 계산하였고, 신율(%)은 익스텐션 (extension)/초기길이×100으로 계산하였다.◎ Tensile strength and elongation: After pulling the cross head speed (500mm / min) of the U.T.M apparatus of ASTM D412 method, the elongation and tensile strength of the specimen was measured. Tensile strength (kgf / mm 2) was calculated by load value (kgf) / thickness (mm) × width (mm), and elongation (%) was calculated as extension / initial length × 100.

◎ 경도: ASTM D2240방법인 경도시험기(A Type)의 침을 시편의 한 곳에 완전히 내려 10초 후의 경도 값을 읽었는데, 각각의 시편에 대해 5곳을 시험한 후 그 평균값을 계산하였다.◎ Hardness: The hardness tester (A Type) of ASTM D2240 method was completely lowered to one place of the specimen, and the hardness value was read after 10 seconds, and the average value was calculated after testing five places for each specimen.

◎ 가열감량: MS200-38방법 즉, 각각의 시편에 대해 소수점 4 자리까지 초기 무게(Wi)를 측정하고 130 ℃의 오븐에 크램프를 이용하여 시편을 고정시키고, 3 시간 후 시편을 꺼내어 항온조에서 4 시간 이상 보관 후, 시편 무게(Wo)를 측정한 후 수학식 1에 의하여 계산하였다.◎ Loss of heating: MS200-38 method, that is, measure the initial weight (Wi) to 4 decimal places for each specimen, fix the specimen by using a clamp in the oven at 130 ℃, and take out the specimen after 3 hours. After storage for more than one hour, the specimen weight (Wo) was measured and then calculated by Equation 1.

[수학식 1][Equation 1]

가열감량 = {(Wi-Wo) / Wi} x 100Heat loss = {(Wi-Wo) / Wi} x 100

◎ 중금속 검출 여부: EN-71-3 시험방법에 의하여 유해 중금속인 카드뮴(Cd), 납(Pb), 크롬(Cr), 안티몬(Sb), 비소(As), 수은(Hg), 바륨(Ba) 및 셀레늄(Se)에 대한 검출여부를 한국 생활용품시험연구원에 의뢰하여 확인하였다.◎ Detecting heavy metals: Cadmium (Cd), lead (Pb), chromium (Cr), antimony (Sb), arsenic (As), mercury (Hg), barium (Ba) ) And selenium (Se) was confirmed by the Korea Household Products Testing Institute.

◎ 환경호르몬의 검출 여부: 한국 생활용품시험연구원으로부터 ASTM D3421-75 시험 방법에 의하여 확인하였다.◎ Detection of environmental hormone: It was confirmed by ASTM D3421-75 test method from Korea Household Products Testing Institute.

◎ 냄새측정 : 각 샘플을 밀폐용기에 넣고 80±2℃의 온도로 4시간 동안 가열(Heating)한 후 샘플을 꺼내어 관능검사에 의해 냄새를 느끼지 않는 경우를 5등급, 보통의 사람으로는 냄새를 느끼지 못하는 경우를 4등급, 냄새는 느껴지나 크게 괴로움은 없는 경우를 3등급, 취기를 충분히 느끼고 괴로움이 생기는 경우를 2등급, 취기가 불쾌감을 느끼게 하는 경우를 1등급으로 하여 5사람이 측정한 값을 평균하였다.◎ Odor measurement: Each sample is placed in an airtight container, heated to a temperature of 80 ± 2 ℃ for 4 hours, and then taken out of the sample. The value measured by five people, with 4 grades for not being able to feel, 3 grades for smelling, but no great pain, 2 grades for feeling enough odor and suffering, and 1 grade for odor feeling unpleasant Was averaged.

실시예 1 및 비교예 1∼4Example 1 and Comparative Examples 1-4

[실시예 1]Example 1

중합도가 1000인 폴리염화비닐 수지LS100(엘지화학) 100kg, 엘지프렉스 비이티(LGflex BET, 엘지화학) 가소제 70kg, Ca-Zn계 안정제 KCZ-08(코오롱사) 3kg, 에폭시계 안정제로REOPLAST 39(독일 Witco사) 1kg을 배합기에 투여한 후 120℃까지 승온하면서 15분간 교반하여 배합한 후 가소제가 폴리염화비닐 수지내에 완전히 흡수되게 하였다. 교반이 완료된 후 배합물을 이미 165℃의 온도로 유지된 캘린더에 투입하여 일정 두께의 시트(Sheet)를 제조하였다.100 kg of polyvinyl chloride resin LS100 (LG Chem) with polymerization degree 1000, LGflex BET (LG Chem) plasticizer 70 kg, Ca-Zn stabilizer KCZ-08 (Kolon) 3 kg, epoxy stabilizer REOPLAST 39 1 kg of German Witco) was administered to the blender, and the mixture was stirred for 15 minutes while raising the temperature to 120 ° C., so that the plasticizer was completely absorbed into the polyvinyl chloride resin. After the stirring was completed, the compound was put into a calender already maintained at a temperature of 165 ° C. to prepare a sheet having a predetermined thickness.

제조된 시트에 대한 물성을 측정하여 그 결과를 표 1에 나타내었다.The physical properties of the prepared sheet were measured, and the results are shown in Table 1.

[비교예 1]Comparative Example 1

가소제를 프탈산계 가소제인 디에틸헥실프탈레이트(DEHP, 엘지화학)를 사용하고 Ba-Zn 계 안정제로는 BZ-806F(송원산업사)을 사용한 것을 제외하고는 실시예 1과 동일하게 제조하여 그 결과를 표 1에 나타내었다.The plasticizer was prepared in the same manner as in Example 1 except that diethylhexylphthalate (DEHP, LG Chemical), a phthalic acid plasticizer, and BZ-806F (Songwon Industrial Co., Ltd.) were used as Ba-Zn stabilizers. Table 1 shows.

[비교예 2]Comparative Example 2

가소제를 비프탈산계 가소제인 에이티비이씨(ATBC, 미국, Morflex사)를 사용한 것을 제외하고는 실시예 1과 동일하게 제조하여 그 결과를 표 1에 나타내었다.A plasticizer was prepared in the same manner as in Example 1 except for using a nonphthalic acid-based plasticizer ABT (ATBC, Morflex Co., USA) and the results are shown in Table 1.

[비교예 3]Comparative Example 3

가소제를 비프탈산계 가소제인 메사몰(Mesamoll, 독일, Bayer)를 사용한 것을 제외하고는 실시예 1과 동일하게 제조하여 그 결과를 표 1에 나타내었다.A plasticizer was prepared in the same manner as in Example 1 except that Mesamol (Mesamoll, Germany, Bayer), a nonphthalic acid-based plasticizer, was used and the results are shown in Table 1.

[비교예 4][Comparative Example 4]

가소제를 비프탈산계 가소제인 엘지플렉스 디아이엔에이(LGflex DINA ㈜엘지화학)를 사용한 것을 제외하고는 실시예 1과 동일하게 제조하여 그 결과를 표 1에 나타내었다.A plasticizer was prepared in the same manner as in Example 1 except that LGflex DINA (LGflex DINA Co., Ltd.), which is a nonphthalic acid-based plasticizer, was shown in Table 1 below.

물성Properties 실시예 1Example 1 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비교예 3Comparative Example 3 비교예 4Comparative Example 4 인장강도(Kgf/cm2)Tensile Strength (Kgf / cm 2 ) 165165 150150 145145 160160 150150 신율 (Shore"A")Elongation (Shore "A") 411411 422422 420420 396396 442442 경도(%)Hardness(%) 8282 8181 8181 8282 7878 가열감량(%)Heating loss (%) 0.210.21 0.550.55 0.990.99 0.450.45 1.321.32 중금속 검출 여부Heavy metals detected 무radish 무radish 무radish 무radish 무radish 환경호르몬 검출 여부Environmental hormone detection 무radish 유U 무radish 무radish 무radish 냄새smell 3.53.5 2.02.0 2.02.0 2.02.0 2.52.5

표 1에 나타낸 바와 같이, 폴리염화비닐 수지 시트에 가장 널리 사용되던 프탈산계 가소제 디에틸헥실프탈레이트(DEHP)를 첨가한 비교예 1의 경우 환경호르몬이 검출됨을 알 수 있었다.As shown in Table 1, in the case of Comparative Example 1 to which the phthalic acid-based plasticizer diethylhexyl phthalate (DEHP), which was most widely used, was detected in the polyvinyl chloride resin sheet, environmental hormones were detected.

또한, 엘지프렉스 비이티(LGflex BET, 엘지화학)가소제 이외의 비프탈산계 가소제를 첨가한 비교예 2, 3 및 4의 경우 유해중금속 및 환경호르몬은 검출되지않았으나, 비교예 1의 경우보다도 가열감량이나 냄새 등의 물성이 다소 떨어짐을 보였다.In addition, in the case of Comparative Examples 2, 3, and 4 to which non-phthalic acid-based plasticizers other than LGflex BET (LG Chem) plasticizer were added, no harmful heavy metals and environmental hormones were detected. The physical properties such as or odors showed a slight drop.

이에 비하여 엘지프렉스 비이티(LGflex BET, 엘지화학) 가소제를 첨가한 실시예 1의 경우, 중금속 및 환경호르몬이 발생하지 않으면서도 기본 물성인 인장강도, 신율 및 경도가 프탈산계 가소제 DEHP를 첨가한 비교예 1의 경우와 비슷하였으며 특히, 잔량 알코올의 휘발로 인한 냄새 유발 물질이 적고, 가열감량이 매우 우수하여 폴리염화비닐 수지 조성물에 적용하기에 적당하였다. 또한, 실시예 1에 대한 유해중금속 검출 결과를 나타내는 한국생활용품시험연구원의 시험성적서(2002년 8월 2일자, 문서번호:T02-2539/1, 시료명:난연/무독 의료용 시트)에 의하면 하기 표 2와 같은 결과를 얻었다.Compared to Example 1 in which LGflex BET (LG Chem) plasticizer was added, the tensile strength, elongation, and hardness of phthalic acid-based plasticizer DEHP, which are basic physical properties, without generating heavy metals and environmental hormones, were compared. It was similar to the case of Example 1, in particular, less odor-causing substances due to the volatilization of the residual alcohol, and very good heating loss was suitable for application to the polyvinyl chloride resin composition. In addition, according to the test report (Date of August 2, 2002, document number: T02-2539 / 1, sample name: flame retardant / non-toxic medical sheet) of the Korea Household Appliance Testing Institute showing the detection result of harmful heavy metal for Example 1 2 result was obtained.

원소명Element Name 단위unit 시험결과Test result 기준치Reference value 납(Pb)Pb mg/kgmg / kg 10 미만Less than 10 90 미만Less than 90 카드뮴(Cd)Cadmium (Cd) 5 미만Less than 5 75 미만Less than 75 크롬(Cr)Chrome (Cr) 10 미만Less than 10 60 미만Less than 60 안티몬(Sb)Antimony (Sb) 10 미만Less than 10 60 미만Less than 60 비소(As)Arsenic (As) 5 미만Less than 5 25 미만Less than 25 수은(Hg)Mercury (Hg) 5 미만Less than 5 60 미만Less than 60 바륨(Ba)Barium (Ba) 10 미만Less than 10 1000 미만Less than 1000 셀레늄(Se)Selenium (Se) 25 미만Less than 25 500 미만Less than 500 시험방법Test Methods EN 71 Part 3 : 1994/A1:2000에 따라 전처리 후 원자분광광도계(AAS) 및 원자발광분광광도계(ICP)로 측정함.After pretreatment according to EN 71 Part 3: 1994 / A1: 2000, measured by AAS and Atomic Spectrophotometer (ICP).

또한, 실시예 1에 대한 환경호르몬(프탈산계 가소제) 검출 결과를 나타내는 한국생활용품시험연구원의 시험성적서(2002년 8월 2일자, 문서번호: T02-2539, 시료명:난연/무독 의료용 시트)에 의하면 프탈레이트계 가소제인 DEHP(di-ethyhexyl phthalate), DBP(di -butyl phthalate), DIDP(di-isodecyl phthalate), BBP(Butyl Benzyl phthalate), DINP(di-isononyl phthalate) 및 DNOP(di-n-octyl phthalate) 성분이 전혀 검출되지 않았다.In addition, the test report (Date of August 2, 2002, Document No .: T02-2539, Sample name: Flame-retardant / non-toxic medical sheet) of the Korea Household Appliance Testing Institute showing the results of detecting environmental hormone (phthalic acid-based plasticizer) for Example 1 Phthalate-based plasticizers such as di-ethyhexyl phthalate (DEHP), di -butyl phthalate (DBP), di-isodecyl phthalate (DIDP), butyl benzyl phthalate (BBP), di-isononyl phthalate (DINP) and di-n- No octyl phthalate component was detected.

실시예 2∼5 및 비교예 5Examples 2-5 and Comparative Example 5

[실시예 2]Example 2

엘지프렉스 비이티(LGflex BET, 엘지화학) 가소제의 양을 5kg으로 한 것을 제외하고는 실시예 1과 동일하게 제조하여 경도, 작업성 및 시트의 외관상태를 평가하였고, 그 결과를 하기 표 3에 나타내었다.LGflex BET (LGflex BET, LG Chem) was prepared in the same manner as in Example 1 except that the amount of the plasticizer was 5kg to evaluate the hardness, workability and the appearance of the sheet, the results are shown in Table 3 below. Indicated.

[실시예 3]Example 3

엘지프렉스 비이티(LGflex BET, 엘지화학) 가소제의 양을 100kg으로 한 것을 제외하고는 실시예 1과 동일하게 제조하여 그 결과를 하기 표 3에 나타내었다.LGflex BET (LGflex BET, LG Chem) except that the amount of the plasticizer to 100kg was prepared in the same manner as in Example 1 and the results are shown in Table 3 below.

[실시예 4]Example 4

엘지프렉스 비이티(LGflex BET, 엘지화학)가소제의 양을 120kg으로 한 것을 제외하고는 실시예 1과 동일하게 제조하여 그 결과를 하기 표 3에 나타내었다.LGflex BET (LGflex BET, LG Chemical) was prepared in the same manner as in Example 1 except that the amount of the plasticizer was 120kg and the results are shown in Table 3 below.

[실시예 5]Example 5

엘지프렉스 비이티(LGflex BET, 엘지화학)가소제의 양을 150kg으로 한 것을 제외하고는 실시예 1과 동일하게 제조하여 그 결과를 하기 표 3에 나타내었다.LGflex BET (LGflex BET, LG Chemical) was prepared in the same manner as in Example 1 except that the amount of the plasticizer was 150kg and the results are shown in Table 3 below.

[비교예 5][Comparative Example 5]

엘지프렉스 비이티(LGflex BET, 엘지화학)가소제의 양을 170kg으로 한 것을 제외하고는 실시예 1과 동일하게 하여 그 결과를 하기 표 3에 나타내었다.LGflex BET (LGflex BET, LG Chem) The same as in Example 1 except that the amount of the plasticizer was shown in Table 3 below.

물성Properties 실시예 2Example 2 실시예 3Example 3 실시예 4Example 4 실시예 5Example 5 비교예 5Comparative Example 5 경도 (Shore"A")Hardness (Shore "A") 9595 6060 5050 4040 3030 작업성Workability 가능possible 가능possible 가능possible 가능possible 곤란Difficulty 시트 외관 상태Sheet appearance status 양호Good 양호Good 양호Good 양호Good 불량Bad

엘지프렉스 비이티(LGflex BET, 엘지화학)가소제 함량에 따른 물성, 작업성(배합 포함) 및 시트 외관상태의 결과를 표 3에 나타낸 바와 같이, PVC 100중량부에 대하여 5 내지 150중량부의 가소제를 첨가한 경우에는 PVC 시트 작업시 문제점은 크게 없었으나, 5중량부인 경우에는 경도가 너무 높아 가소제 기능을 나타내기에는 문제가 있었으며, 170중량부인 경우에는 가소제가 수지로 완전히 흡수되지 못하였으며, 경도가 너무 낮아 가공시 어려움이 있으며, 설령 가공이 되었다 하더라도 가소제가 밖으로 이행되어 제품으로의 적용이 어려웠다.LGflex BET (LG Chem) According to the plasticizer content, physical properties, workability (including blending) and the results of the sheet appearance state, as shown in Table 3, 5 to 150 parts by weight of plasticizer based on 100 parts by weight of PVC When added, there was no problem when working with PVC sheet, but when 5 parts by weight, the hardness was too high to show the plasticizer function, and when it was 170 parts by weight, the plasticizer was not completely absorbed into the resin. It is too low and difficult to process. Even if it is processed, the plasticizer is transferred out, making it difficult to apply to the product.

실시예 6∼9 및 비교예 6Examples 6-9 and Comparative Example 6

[실시예 6]Example 6

안정제로서 Ca-Zn계 안정제인 KCZ-08(코오롱㈜사)를 사용한 것을 제외하고는 실시예 1과 동일하게 제조하여 냄새, 중금속 검출 여부 및 내열성을 평가하여 그 결과를 표 4에 나타내었다.Except for using the Ca-Zn-based stabilizer KCZ-08 (Kolon Co., Ltd.) was prepared in the same manner as in Example 1 to evaluate the smell, heavy metal detection and heat resistance and the results are shown in Table 4.

[실시예 7]Example 7

안정제로서 Ca-Zn계 안정제인 CZ11(독일, Witco사)를 사용한 것을 제외하고는 실시예 1과 동일하게 제조하여 냄새, 중금속 검출 여부 및 내열성을 평가하여 그 결과를 표 4에 나타내었다.Except for using the Ca-Zn-based stabilizer CZ11 (Germany, Witco Co.) was prepared in the same manner as in Example 1 to evaluate the smell, heavy metal detection and heat resistance and the results are shown in Table 4.

[실시예 8]Example 8

안정제로서 Ca-Zn계 안정제인 CZ-2000(독일, Henkel사)를 사용한 것을 제외하고는 실시예 1과 동일하게 제조하여 냄새, 중금속 검출 여부 및 내열성을 평가하여 그 결과를 표 4에 나타내었다.Except for using the Ca-Zn-based stabilizer CZ-2000 (Germany, Henkel Co.) was prepared in the same manner as in Example 1 to evaluate the smell, heavy metal detection and heat resistance and the results are shown in Table 4.

[실시예 9]Example 9

안정제로서 Ca-Zn계 안정제인 LTX-15(한국대협사)를 사용한 것을 제외하고는 실시예 1과 동일하게 제조하여 냄새, 중금속 검출 여부 및 내열성을 평가하여 표 4에 나타내었다.Except for using the Ca-Zn-based stabilizer LTX-15 (Korea Grand Co., Ltd.) was prepared in the same manner as in Example 1 to evaluate the odor, heavy metal detection and heat resistance are shown in Table 4.

[비교예 6]Comparative Example 6

안정제로서 기존 사용중인 안정제인BZ-806F(Ba-Zn 유기복합안정제, 송원산업사)를 사용한 것을 제외하고는 실시예 1과 동일하게 제조하여 냄새, 중금속 검출 여부 및 내열성을 평가하여 표 4에 나타내었다.Except for using the stabilizer BZ-806F (Ba-Zn organic complex stabilizer, Songwon Industrial Co., Ltd.) as a stabilizer was prepared in the same manner as in Example 1 to evaluate the odor, heavy metal detection and heat resistance are shown in Table 4 .

물성Properties 실시예6Example 6 실시예7Example 7 실시예8Example 8 실시예9Example 9 비교예6Comparative Example 6 냄 새smell 3.53.5 4.04.0 3.53.5 3.53.5 3.03.0 중금속검출 유무Heavy metal detection 무radish 무radish 무radish 무radish 유U 내열성(비교예 1대비)Heat resistance (compared to Comparative Example 1) 90%90% 90%90% 90%90% 90%90% 100%100%

Ca-Zn계 안정제를 첨가한 실시예 들과 Ba-Zn계 안정제를 첨가한 비교예에 대한 냄새, 중금속 검출 유무 및 내열성의 결과를 상기 표 4에 나타낸 바와 같이,Ca-Zn계 안정제를 사용한 경우에는 중금속이 전혀 검출이 되지 않았으나, Ba-Zn계 안정제에 비하여 내열성에 있어서는 10%정도 저하됨을 보임에 따라 내열성 개선방안이 요구되었다.As shown in Table 4, the results of odor, heavy metal detection, and heat resistance of the examples in which the Ca-Zn-based stabilizer is added and the comparative examples in which the Ba-Zn-based stabilizer are added are shown. Although no heavy metals were detected, the heat resistance was reduced by about 10% compared to the Ba-Zn-based stabilizer.

냄새 측정결과에 있어서는 Ca-Zn계 안정제를 사용한 경우에 중금속 의 영향으로 인한 냄새만 발생하며, 유기복합체 성분 중 내열성 강화를 위해 주로 사용되어 냄새 발생의 원인이 되는 트리노닐페놀 포스페이트(TNPP) 및 트리노닐페놀(TNP)을 함유하고 있지 않으므로3.5등급 이상의 좋은 결과를 얻었다. 특히 CZ11(독일, Witco사)를 사용한 실시예 7의 경우 유기복합체 성분이 대부분 다분자 물질인14% 스테릭산(Stearic acid), 23% 올레익산(Oleic acid), 63% 리놀릭산(Linoleic acid) 등으로 이루어져 있어 4등급의 냄새평가 결과를 얻은 반면에 실시예 6, 8 및 9의 경우 상기의 다분자 물질(Oleic acid, Linoleic acid) 이외에도 점도를 낮추기 위한 단분자 물질인 옥틸산, 벤조익산 등을 40% 이상 함유하고 있어 가공시 및 기공 후에 제품으로부터의 많은 휘발감량으로 인하여 내열성 및 냄새 특성에 있어서 실시예 7의 CZ11보다도 다소 떨어진다.In the odor measurement results, only the odor caused by the influence of heavy metals when Ca-Zn-based stabilizer is used, and it is mainly used to enhance the heat resistance of the organic composite components, trinonylphenol phosphate (TNPP) and trino, which cause odors. Since it does not contain Nylphenol (TNP), a good result of grade 3.5 or higher was obtained. Especially in Example 7 using CZ11 (Germany, Witco), the organic compound component is mostly a multimolecular substance 14% steric acid, 23% oleic acid, 63% linoleic acid In the case of Examples 6, 8, and 9, in addition to the above-mentioned multi-molecular substances (Oleic acid, Linoleic acid), the monomolecular substance octylic acid, benzoic acid, etc. to lower the viscosity It contains more than 40%, slightly lower than the CZ11 of Example 7 in heat resistance and odor characteristics due to the large amount of volatilization from the product during processing and after pore.

실시예 10∼12 및 비교예 7Examples 10-12 and Comparative Example 7

[실시예 10]Example 10

내열성을 강화하기 위하여 REOPLAST 39(독일 Witco사) 1kg을 첨가한 것을 제외하고는 실시예 7과 동일하게 제조하여 냄새 및 내열성을 평가하여 그 결과를 표 5에 나타내었다.Except for the addition of 1kg REOPLAST 39 (Germany Witco) to enhance the heat resistance was prepared in the same manner as in Example 7 to evaluate the smell and heat resistance and the results are shown in Table 5.

[실시예 11]Example 11

내열성을 강화하기 위하여 REOPLAST 39 (독일 Witco사) 2kg을 첨가한 것을 제외하고는 실시예 7과 동일하게 제조하여 냄새 및 내열성을 평가하여 그 결과를 표 5에 나타내었다.Except for the addition of 2kg REOPLAST 39 (Germany Witco) to enhance the heat resistance was prepared in the same manner as in Example 7 to evaluate the smell and heat resistance and the results are shown in Table 5.

[실시예 12]Example 12

내열성을 강화하기 위하여 REOPLAST 39 (독일 Witco사)3kg을 첨가한 것을 제외하고는 실시예 7과 동일하게 하여 냄새 및 내열성을 평가하여 표 5에 나타내었다.Except for the addition of REOPLAST 39 (Germany Witco) 3kg to enhance the heat resistance was the same as in Example 7 to evaluate the odor and heat resistance are shown in Table 5.

[비교예 7]Comparative Example 7

내열성을 강화하기 위하여 REOPLAST 39 (Epoxidized soybean oil, 독일, Witco사) 5kg을 첨가한 것을 제외하고는 실시예 7과 동일하게 하여 냄새 및 내열성을 평가하여 표 5에 나타내었다.Except for the addition of REOPLAST 39 (Epoxidized soybean oil, Witco, Germany) 5kg to enhance the heat resistance was the same as in Example 7 to evaluate the odor and heat resistance are shown in Table 5.

물성Properties 실시예10Example 10 실시예11Example 11 실시예12Example 12 비교예7Comparative Example 7 냄 새smell 4.04.0 4.04.0 4.04.0 3.53.5 내열성(비교예 1대비)Heat resistance (compared to Comparative Example 1) 95%95% 100%100% 100%100% 100%100%

상기 표 5에서 보여주는 바와 같이, 내열성을 강화하기 위하여 REOPLAST 39 (Epoxidized soybean oil, 독일, Witco사)를 첨가한 경우 함량이 증가함에 따라 내열성은 개선이 되었으나, 비교예 7의 경우와 같이 사용량이 5kg이상인 경우 냄새가 심하여 무취 제품에의 적용이 곤란하였다.As shown in Table 5, when the addition of REOPLAST 39 (Epoxidized soybean oil, Germany, Witco) in order to enhance the heat resistance, the heat resistance was improved as the content is increased, but as used in the case of Comparative Example 7 5kg In the above case, the smell was severe and it was difficult to apply to odorless products.

상기 실시예의 결과에서 제시된 바와 같이, 본 발명에 따른 무독 및 저취 폴리염화비닐 수지 조성물은 기존의 폴리염화비닐 수지 조성물이 갖는 신율, 인장강도, 가열감량, 냄새 등의 물성을 유지하면서도 환경 친화적인 무독 및 저취 폴리염화비닐 수지 조성물을 소비자들에 제공하여 폴리염화비닐 수지 산업을 발전시키는 효과가 있다. 또한, 친환경적인 폴리염화비닐 제품을 생산하여 소비자들의 국민건강증진에도 효과가 크다.As shown in the results of the above examples, the non-toxic and low-odor polyvinyl chloride resin composition according to the present invention is environmentally friendly non-toxic while maintaining the properties such as elongation, tensile strength, heating loss, smell, etc. that the existing polyvinyl chloride resin composition has And providing a low odor polyvinyl chloride resin composition to consumers to develop the polyvinyl chloride resin industry. In addition, by producing eco-friendly polyvinyl chloride products, it is also effective in promoting the national health of consumers.

이상에서 본 발명은 기재된 구체예에 대해서만 상세히 설명되었지만 본 발명의 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속함은 당연한 것이다.Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications are within the scope of the appended claims.

Claims (7)

폴리염화비닐 수지 100중량부에 대하여 비프탈레이트 가소제 5 내지 150중량부, Ca-Zn계 안정제 0.1 내지 7중량부, 및 에폭시계 안정제 0.1내지 4중량부를 포함하여 이루어지는 것을 특징으로 하는 무독 및 저취 폴리염화비닐 수지 조성물.Non-toxic and odorless polychlorination comprising 5 to 150 parts by weight of a non-phthalate plasticizer, 0.1 to 7 parts by weight of a Ca-Zn-based stabilizer, and 0.1 to 4 parts by weight of an epoxy stabilizer, based on 100 parts by weight of the polyvinyl chloride resin. Vinyl resin composition. 제1항에 있어서,The method of claim 1, 상기 폴리염화비닐 수지 100중량부에 대하여 비프탈레이트 가소제 30-80중량부, Ca-Zn계 안정제 2 내지3중량부, 및 에폭시계 안정제 2 내지 3중량부를 포함하여 이루어지는 것을 특징으로 하는 무독 및 저취 폴리염화비닐 수지 조성물.Non-toxic and low odor poly, comprising 30 to 80 parts by weight of a non-phthalate plasticizer, 2 to 3 parts by weight of Ca-Zn-based stabilizer, and 2 to 3 parts by weight of epoxy-based stabilizer based on 100 parts by weight of the polyvinyl chloride resin. Vinyl chloride resin composition. 제1항 또는 제2항에 있어서,The method according to claim 1 or 2, 상기 비프탈레이트 가소제가 하기 화학식 1로 표시되는 트리메틸올프로판(Trimethylolpropane, TMP) 에스테르를 포함하는 혼합물로서 a) 트리메틸올프로판-트리-(2-에틸헥사노에이트)(trimethylolpropane-tri-(2-ethyl hexanoate)), b) 벤조산 2,2- 비스-(2-에틸-헥사노일옥시메틸)-부틸 에스테르(benzoic acid 2,2-bis-(2-ethyl-hexanoyloxymethyl)-butyl ester), c) 2-에틸헥산산 2,2- 비스-(벤조일옥시메틸)-부틸 에스테르(2-ethylhexanoic acid 2,2-bis-(benzoyloxymethyl)-butyl ester) 및 d) 트리메틸올프로판-트리- 벤조에이트(trimethylol propane-tri-benzoate) 4종의 에스테르 화합물의 혼합물임을 특징으로 하는 무독 및 저취 폴리염화비닐 수지 조성물.The non-phthalate plasticizer is a mixture containing a trimethylolpropane (TMP) ester represented by the following formula (a) trimethylolpropane-tri- (2-ethylhexanoate) (trimethylolpropane-tri- (2-ethyl hexanoate)), b) benzoic acid 2,2-bis- (2-ethyl-hexanoyloxymethyl) -butyl ester (benzoic acid 2,2-bis- (2-ethyl-hexanoyloxymethyl) -butyl ester), c) 2 2-ethylhexanoic acid 2,2-bis- (benzoyloxymethyl) -butyl ester and d) trimethylolpropane-tri-benzoate (trimethylol propane) -tri-benzoate) Non-toxic and low-odor polyvinyl chloride resin composition, characterized in that a mixture of four ester compounds. [화학식 1][Formula 1] 상기식에서, R1, R2및 R3는 각각 페닐기(Phenyl group) 또는 탄소수가 3 내지 10, 바람직하게는 4 내지 8인 알킬 그룹(Alkyl group)이다.Wherein R 1 , R 2 and R 3 are each a phenyl group or an alkyl group having 3 to 10, preferably 4 to 8 carbon atoms. 제1항 또는 제2항에 있어서,The method according to claim 1 or 2, 상기 Ca-Zn계 안정제가 Ca-Zn 유기복합안정제임을 특징으로 하는 무독 및 저취 폴리염화비닐 수지 조성물.Non-toxic and low-odor polyvinyl chloride resin composition characterized in that the Ca-Zn-based stabilizer is a Ca-Zn organic composite stabilizer. 제1항 또는 제2항에 있어서,The method according to claim 1 or 2, 상기 에폭시계 안정제가 에폭시화된 소이빈 오일(Epoxidized soybean oil) 임을 특징으로 하는 무독 및 저취 폴리염화비닐 수지 조성물.Non-toxic and low-odor polyvinyl chloride resin composition, characterized in that the epoxy stabilizer is epoxidized soybean oil (Epoxidized soybean oil). 제1항 또는 제2항의 조성물로 제조된 폴리염화비닐 시트.A polyvinyl chloride sheet prepared from the composition of claim 1. 제1항 또는 제2항의 조성물로 제조된 폴리염화비닐 컴파운드.A polyvinyl chloride compound prepared from the composition of claims 1 or 2.
KR10-2002-0072801A 2002-11-21 2002-11-21 Nontoxic and Odorless Polyvinyl Chloride Resin Composition KR100508146B1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100724553B1 (en) * 2005-01-31 2007-06-04 주식회사 엘지화학 Plasticizer composition and polyvinyl chloride resin composition containing the same
WO2016064125A1 (en) * 2014-10-22 2016-04-28 한화케미칼 주식회사 Plasticizer composition comprising di(2-ethylhexyl)cyclonucleic acid-1,4-dicarboxylate and citrate compound, and vinyl chloride resin composition comprising same

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JPH086002B2 (en) * 1991-12-06 1996-01-24 信越ポリマー株式会社 Polyvinyl chloride resin composition for food packaging
US5328330A (en) * 1993-08-02 1994-07-12 Hudson Products Corporation Extruded aluminum fan blade
JP3556022B2 (en) * 1995-10-20 2004-08-18 信越ポリマー株式会社 Composition and film for low-brominated vinyl chloride resin film
KR100426229B1 (en) * 2001-01-05 2004-04-08 주식회사 엘지화학 Trimethyl olpropane ester based plasticizer composition for polyvinyl chloride resin

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100724553B1 (en) * 2005-01-31 2007-06-04 주식회사 엘지화학 Plasticizer composition and polyvinyl chloride resin composition containing the same
WO2016064125A1 (en) * 2014-10-22 2016-04-28 한화케미칼 주식회사 Plasticizer composition comprising di(2-ethylhexyl)cyclonucleic acid-1,4-dicarboxylate and citrate compound, and vinyl chloride resin composition comprising same
CN107075218A (en) * 2014-10-22 2017-08-18 韩华化学株式会社 The plasticizer composition of compound comprising (2 ethylhexyl) ester of 1,4 dicarboxylic acids of hexamethylene two and based on citrate and the vinyl chloride resin composition for including the plasticizer composition

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