KR20230091758A - Method for producing a PVC resin composition using 1-2 cyclohexane dicarboxylic acid diisononyl ester as a plasticizer - Google Patents
Method for producing a PVC resin composition using 1-2 cyclohexane dicarboxylic acid diisononyl ester as a plasticizer Download PDFInfo
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 52
- 239000011342 resin composition Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- TUOSWEIWIXJUAU-UHFFFAOYSA-N bis(7-methyloctyl) cyclohexane-1,1-dicarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1(C(=O)OCCCCCCC(C)C)CCCCC1 TUOSWEIWIXJUAU-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 25
- 239000003223 protective agent Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 13
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 8
- 229910001463 metal phosphate Inorganic materials 0.000 claims description 8
- 229920005596 polymer binder Polymers 0.000 claims description 8
- 239000002491 polymer binding agent Substances 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 229920000180 alkyd Polymers 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 235000021317 phosphate Nutrition 0.000 claims description 7
- -1 phosphate compound Chemical class 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 29
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 28
- 239000002952 polymeric resin Substances 0.000 abstract description 14
- 229920003002 synthetic resin Polymers 0.000 abstract description 14
- 230000000704 physical effect Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 229920001944 Plastisol Polymers 0.000 abstract 1
- 239000004999 plastisol Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- IRIAEXORFWYRCZ-UHFFFAOYSA-N n-butyl benzyl phthalate Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 3
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 2
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 239000004806 diisononylester Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- 230000003863 physical function Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
Classifications
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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
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- 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
- C08L29/00—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
본 발명은 가소제를 함유한 폴리염화비닐계 고분자 수지 조성물 및 그의 제조방법에 관한 것으로서, 더욱 상세하게는 식품용기 및 완구 등의 고분자 수지 물품 제조시 PVC계 고분자 수지 플라스티졸의 중요 물성인 고온 점도, 점도 안정성이 개선되고 PVC계 고분자 수지 물품의 인장 강도, 신율 및 가열 감량 등이 우수하여 고분자 수지 물품의 제조 공정의 효율성 및 물성을 향상시키고, 내이행성 측면에서도 우수하여 환경 문제를 효과적으로 방지할 수 있는, 1-2 사이클로헥산 디카르복실산 다이아이소노닐 에스테르를 가소제로 이용한 PVC 수지 조성물 및 그의 제조방법을 개시한다.The present invention relates to a polyvinyl chloride-based polymeric resin composition containing a plasticizer and a method for preparing the same, and more particularly, to high-temperature viscosity, which is an important physical property of PVC-based polymeric resin plastisol in manufacturing polymeric resin products such as food containers and toys , Viscosity stability is improved and the tensile strength, elongation and heating loss of PVC-based polymer resin articles are excellent, so that the efficiency and physical properties of the manufacturing process of polymer resin articles are improved, and environmental problems are effectively prevented by being excellent in migration resistance. Disclosed is a PVC resin composition using 1-2 cyclohexane dicarboxylic acid diisononyl ester as a plasticizer and a method for preparing the same.
Description
본 발명은 가소제를 함유한 폴리염화비닐계(Polyvinyl chlorides, 이하 "PVC계"라 칭함) 고분자 수지 조성물 및 그의 제조방법에 관한 것으로서, 더욱 상세하게는 식품용기 및 완구 등의 고분자 수지 물품 제조시 PVC계 고분자 수지 플라스티졸(plastisol)의 중요 물성인 고온 점도, 점도 안정성이 개선되고 PVC계 고분자 수지 물품의 인장 강도, 신율 및 가열 감량 등이 우수하여 고분자 수지 물품의 제조 공정의 효율성 및 물성을 향상시키고, 내이행성 측면에서도 우수하여 환경 문제를 효과적으로 방지할 수 있는 가소제를 포함한 PVC 수지 조성물 및 그의 제조방법에 관한 것이다.The present invention relates to a polyvinyl chloride-based ( Polyvinyl chlorides , hereinafter referred to as "PVC-based") polymer resin composition containing a plasticizer and a method for manufacturing the same, and more particularly, to PVC when manufacturing polymer resin articles such as food containers and toys. High-temperature viscosity and viscosity stability, which are important physical properties of plastisol- based polymeric resins, are improved, and the tensile strength, elongation, and heating loss of PVC-based polymeric resin products are excellent, improving the efficiency and physical properties of the manufacturing process of polymeric resin products It relates to a PVC resin composition including a plasticizer capable of effectively preventing environmental problems by being excellent in migration resistance and a method for producing the same.
PVC 고분자 수지는 염화비닐 단량체(vinyl chloride monomer)의 단독 중합체 또는 50% 이상의 염화비닐을 포함하는 혼성 중합체로서, 가소제(plasticizer), 안정제(stabilizer), 충진제(filler), 안료(pigment) 등 여러 가지 첨가제를 적절하게 첨가하여 다양한 가공 물성을 부여할 수 있다. 이러한 PVC 고분자 수지는 압출성형, 사출성형, 캘린더링 등의 일반적인 가공법에 의해 사용될 수 있는 범용 수지이며, 이같은 가공을 통하여 파이프, 전선, 전기 기계 제품, 장난감, 필름, 시트, 인조가죽, 타포린, 테이프, 식품 포장재 및 의료용품 등에 이르기까지 다양한 제품들의 소재로 광범위하게 사용된다.PVC polymer resin is a homopolymer of vinyl chloride monomer or a copolymer containing 50% or more of vinyl chloride, and is a plasticizer , stabilizer , filler , pigment , etc. Additives can be appropriately added to impart various processing properties. This PVC polymer resin is a general-purpose resin that can be used by general processing methods such as extrusion molding, injection molding, and calendering, and through such processing, pipes, wires, electric machine products, toys, films, sheets, artificial leather, tarpaulins, and tapes It is widely used as a material for various products ranging from food packaging materials and medical supplies.
상기 첨가제 중 가소제는 PVC계 고분자 수지에 첨가되어 가공성, 유연성, 전기 절연성 등의 여러 가지 물성 및 기능을 부여하는 필수 첨가제이다. 이러한 가소제의 대표적인 종류로는 프탈레이트계(phthalates), 아디페이트계(adipates) 등을 들 수 있다. 이 중에서 프탈레이트계 가소제인 디-2-에틸헥실프탈레이트(Di-2-ethylhexylphthalate, DEHP), 디-부틸 프탈레이트(Di-butyl phthalate, DBP), 디-이소데실 프탈레이트(Di-isodecylphthalate, DIDP), 부틸 벤질 프탈레이트(Butyl benzyl phthalate, BBP), 디-이소노닐 프탈레이트(Di-isononylphthalate, DINP), 디-n-옥틸 프탈레이트(di-n-octyl phthalate, DNOP) 등이 널리 사용된다.Among the additives, a plasticizer is an essential additive that is added to a PVC-based polymer resin to impart various physical properties and functions such as processability, flexibility, and electrical insulation. Representative types of such plasticizers include phthalates, adipates, and the like. Among them, phthalate-based plasticizers such as Di-2-ethylhexylphthalate (DEHP), di-butyl phthalate (DBP), di-isodecylphthalate (DIDP), butyl Butyl benzyl phthalate (BBP), di-isononylphthalate (DINP), and di-n-octyl phthalate (DNOP) are widely used.
그러나, 상기 프탈레이트계 가소제는 환경 호르몬의 발생으로 인해 인체에 유해하기 때문에 이에 대한 대체물질이 필요하다. However, since the phthalate-based plasticizer is harmful to the human body due to the generation of endocrine disruptors, alternative materials are needed.
참고로, 사이클로헥산-1,2-디에스터계 물질 및 다이소노닐 테레프탈레이트를 포함하는 가소제 조성물에 관한 기술이 대한민국 공개특허공보 공개번호 10-2020-0074020호(공개일자 2020년 06월 24일)의 "가소제 조성물 및 이를 포함하는 수지 조성물"에서 개시된 바 있다.For reference, a description of a plasticizer composition containing a cyclohexane-1,2-diester material and disononyl terephthalate is disclosed in Korean Patent Publication No. 10-2020-0074020 (published on June 24, 2020). ) of "Plasticizer composition and resin composition containing the same".
본 발명이 해결하고자 하는 과제는, 가소제를 고분자 수지에 첨가 하였을때, 가소제 본연의 성능인 유연성이 우수하면서, 내이행성이 우수하여 가소제의 용출을 현저하게 억제하는 비프탈레이트계 가소제를 함유한 PVC 수지 조성물 및 그의 제조방법을 제공하는 것이다.The problem to be solved by the present invention is, when a plasticizer is added to a polymer resin, a PVC resin containing a non-phthalate plasticizer that remarkably suppresses the elution of the plasticizer due to its excellent flexibility and excellent migration resistance, which is the inherent performance of the plasticizer It is to provide a composition and a method for producing the same.
상기 목적을 달성하기 위한 수단으로서 본 발명의 구성은, 다이아이소노닐 프탈산(Diisononyl phthalate)을 수소반응(hydrogenation)시킴으로서 얻은 1-2 사이클로헥산 디카르복실산 다이아이소노닐 에스테르를 포함하는 가소제; 및 인산염 화합물을 포함하는 보호제;를 포함하고, 상기 가소제는 밀도 0.944 ~ 0.954 g/cm3, 점도 44 ~ 60 mPa*s인 것을 사용한다.As a means for achieving the above object, the configuration of the present invention is a plasticizer comprising 1-2 cyclohexane dicarboxylic acid diisononyl ester obtained by hydrogenation of diisononyl phthalate ; and a protective agent containing a phosphate compound, wherein the plasticizer has a density of 0.944 to 0.954 g/cm3 and a viscosity of 44 to 60 mPa*s.
본 발명의 상기 보호제는, 하나 이상의 금속 인산염(metal phosphates)을 포함하고, 입자 형태로 평균 크기는 0.5 내지 10μm인 것을 사용한다.The protective agent of the present invention includes one or more metal phosphates, and is used in the form of particles having an average size of 0.5 to 10 μm.
본 발명의 상기 조성물은, 가소제와 보호제를 각각 2:15 내지 15:2, 및 바람직하게는 각각 1:5 내지 5:1, 및 바람직하게는 각각 1:4 내지 4:1, 및 바람직하게는 각각 1:3 내지 3:1의 사용 가능한 중량비 범위로 포함한다.The composition of the present invention contains a plasticizer and a protectant in an amount of 2:15 to 15:2, respectively, and preferably 1:5 to 5:1, and preferably 1:4 to 4:1, respectively, and preferably Each is included in a usable weight ratio range of 1:3 to 3:1.
본 발명의 상기 조성물은, 알키드 폴리우레탄(alkyd polyurethane), 또는 폴리비닐 부티랄(polyvinyl butyral) 중 선택되는 하나 이상의 고분자 결합제를 포함한다.The composition of the present invention includes at least one polymer binder selected from alkyd polyurethane and polyvinyl butyral.
상기 목적을 달성하기 위한 수단으로서 본 발명의 제조방법의 구성은, 다이아이소노닐 프탈산(Diisononyl phthalate)을 수소반응(hydrogenation)시킴으로서 가소제를 제조하는 단계; 전체 PVC 수지 조성물 기준으로, 상기 가소제 1 내지 70 중량부, 인산염 화합물을 포함하는 보호제 1 내지 7 중량부, 고분자 결합제 0.5 내지 3 중량부를 혼합하는 단계; 및 상기 혼합하는 단계에서의 혼합물을 용융하는 단계;를 포함하고, 상기 가소제를 얻는 단계에서 가소제는 밀도 0.944 ~ 0.954 g/cm3, 점도 44 ~ 60 mPa*s인 1-2 사이클로헥산 디카르복실산 다이아이소노닐 에스테르이다.As a means for achieving the above object, the composition of the manufacturing method of the present invention includes preparing a plasticizer by hydrogenation of diisononyl phthalate ( Diisononyl phthalate ); Mixing 1 to 70 parts by weight of the plasticizer, 1 to 7 parts by weight of a protective agent containing a phosphate compound, and 0.5 to 3 parts by weight of a polymer binder based on the total PVC resin composition; and melting the mixture in the mixing step; wherein, in the obtaining plasticizer, the plasticizer is 1-2 cyclohexane dicarboxylic acid having a density of 0.944 to 0.954 g/cm3 and a viscosity of 44 to 60 mPa*s. It is a diisononyl ester.
본 발명의 상기 혼합하는 단계에서 보호제는, 하나 이상의 금속 인산염(metal phosphates)을 포함하고, 입자 형태로 평균 크기는 0.5 내지 10 μm인 것을 사용한다.The protective agent in the mixing step of the present invention includes one or more metal phosphates, and is used in the form of particles having an average size of 0.5 to 10 μm.
본 발명의 상기 혼합하는 단계는, 가소제와 보호제를 각각 10:1 내지 1:7, 및 바람직하게는 각각 1:5 내지 5:1, 및 바람직하게는 각각 1:4 내지 4:1, 및 바람직하게는 각각 1:3 내지 3:1의 사용 가능한 중량비 범위로 혼합하는 단계를 포함한다.In the mixing step of the present invention, the plasticizer and the protective agent are respectively 10:1 to 1:7, and preferably each 1:5 to 5:1, and preferably each 1:4 to 4:1, and preferably each Preferably, it includes the step of mixing each in a usable weight ratio range of 1:3 to 3:1.
본 발명의 상기 혼합하는 단계는, 알키드 폴리우레탄(alkyd polyurethane), 또는 폴리비닐 부티랄(polyvinyl butyral) 중 선택되는 하나 이상의 고분자 결합제를 혼합하는 단계를 포함한다.The mixing step of the present invention includes mixing one or more polymeric binders selected from alkyd polyurethane and polyvinyl butyral.
본 발명에 따른 가소제는 물리적 그리고 열적 특성이 완전히 다른 분자체로서 PVC 수지 조성물에 혼합함으로써, 가공성이 용이하게 하고, PVC의 유연성을 증가시킬 수 있는 효과가 있다. The plasticizer according to the present invention is a molecular sieve having completely different physical and thermal properties, and by mixing with the PVC resin composition, it has an effect of facilitating processability and increasing the flexibility of PVC.
그리고 석유자원에서 합성되는 기존의 환경호르몬 유발물질을 발생시키지 않는 효과를 갖는다.In addition, it has an effect of not generating existing environmental hormone-inducing substances synthesized from petroleum resources.
이하, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 본 발명을 용이하게 실시할 수 있을 정도로 상세히 설명하기 위하여 본 발명의 바람직한 실시예와 첨부된 도면을 참조하기로 한다. 본 발명의 목적, 작용, 효과를 포함하여 다른 목적들, 특징점들, 그리고 동작상의 이점들이 바람직한 실시예의 설명에 의하여 더욱 명확해질 것이다.Hereinafter, reference will be made to the preferred embodiments of the present invention and the accompanying drawings in order to explain in detail enough to allow those skilled in the art to easily practice the present invention. Other objects, features, and operational advantages, including the object, action, and effect of the present invention, will become clearer from the description of the preferred embodiment.
참고로, 여기에서 개시되는 실시예는 여러 가지 실시 가능한 예 중에서 당업자의 이해를 돕기 위하여 가장 바람직한 실시예를 선정하여 제시한 것일 뿐, 본 발명의 기술적 사상이 반드시 제시된 사상을 벗어나지 않는 범위 내에서 다양한 변화와 부가가 가능함은 물론, 균등한 타의 실시예가 가능함을 밝혀 둔다.For reference, the embodiments disclosed herein are only presented by selecting the most preferred embodiments to help those skilled in the art to understand among various possible examples, and the technical spirit of the present invention can be varied within a range that does not necessarily deviate from the presented spirit. It should be noted that not only changes and additions are possible, but also other equivalent embodiments are possible.
또한, 명세서 및 청구범위에 사용된 용어나 단어의 표현은, 발명자가 그 자신의 발명을 가지고 최선의 방법으로 설명하기 위하여 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각한 것으로써, 통상적이거나 사전적인 의미로만 한정하여서 해석되어서는 아니되며, 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다. 일례로서, 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한 복수의 표현을 포함한다.In addition, the expression of terms or words used in the specification and claims is based on the principle that the inventor can appropriately define the concept of the term in order to explain in the best way with his or her invention, It should not be construed as being limited only to a dictionary meaning, and should be interpreted as a meaning and concept consistent with the technical spirit of the present invention. As an example, singular expressions include plural expressions unless the context clearly dictates otherwise.
본 발명은 우수한 가공성 및 물성을 갖는 PVC 수지 조성물을 제공한다. The present invention provides a PVC resin composition having excellent processability and physical properties.
본 발명의 구성은, 다이아이소노닐 프탈산(Diisononyl phthalate)을 수소반응(hydrogenation)시킴으로서 얻은 1-2 사이클로헥산 디카르복실산 다이아이소노닐 에스테르를 포함하는 가소제; 및 인산염 화합물을 포함하는 보호제;를 포함한다.The composition of the present invention is a plasticizer containing 1-2 cyclohexane dicarboxylic acid diisononyl ester obtained by hydrogenation of diisononyl phthalate ; and a protective agent including a phosphate compound.
본 발명의 상기 가소제는 다이아이소노닐 프탈산의 수소반응으로 얻은 밀도 0.944 ~ 0.954 g/cm3, 점도 44 ~ 60 mPa*s인 것을 사용한다. The plasticizer of the present invention is used having a density of 0.944 to 0.954 g/cm3 and a viscosity of 44 to 60 mPa*s obtained by hydrogenation of diisononyl phthalic acid.
본 발명은 하기 반응식 1을 통해 얻을 수 있는 가소제를 폴리염화비닐 수지에 첨가하여 수지 조성물을 제조할 수 있다. 이때, 수지에 투입되는 가소제의 투입량은 PVC 수지 30 내지 99 중량% 및 가소제 1 내지 70 중량% 포함하는 것이 바람직하다. In the present invention, a resin composition may be prepared by adding a plasticizer obtained through Reaction Scheme 1 to a polyvinyl chloride resin. At this time, the amount of the plasticizer added to the resin preferably includes 30 to 99% by weight of the PVC resin and 1 to 70% by weight of the plasticizer.
본 발명에 따른 가소제를 포함하는 조성물은 수지 조성물의 용도에 따라 가소제를 적절히 증감할 수 있으나, 상기한 1 중량부 미만으로 첨가되는 경우에는 가소제에 의하여 발현될 수 있는 유연성이나 가공성을 달성할 수 없으며, 70 중량부를 초과하여 첨가되는 경우에는 적정 기계적 물성의 확보가 어렵고, 지나치게 점성이 높아지며 블리딩 현상이 발생할 수도 있어 바람직하지 않다.The composition containing the plasticizer according to the present invention can appropriately increase or decrease the plasticizer depending on the use of the resin composition, but when added in less than 1 part by weight, flexibility or processability that can be expressed by the plasticizer cannot be achieved, , When added in excess of 70 parts by weight, it is difficult to secure appropriate mechanical properties, excessively high viscosity, and bleeding may occur, which is not preferable.
[반응식 1][Scheme 1]
상기 보호제는, 하나 이상의 금속 인산염(metal phosphates)을 포함하고, 입자 형태로 평균 크기는 0.5 내지 10μm인 것을 사용한다.The protective agent includes one or more metal phosphates, and is used in the form of particles having an average size of 0.5 to 10 μm.
상기 금속 인산염은 인산아연(zinc phosphate)을 사용하고, 0.001 내지 0.01 중량%로 함유한다.The metal phosphate uses zinc phosphate and contains 0.001 to 0.01% by weight.
상기 보호제는 PVC 조성물에 보호층을 제공하여 부식을 방지하여 장기 보관 안정성을 향상시킨다. 특히, 금속 인산염을 사용했을때 가소제와의 혼합시 더욱 단단한 응집 혼합물을 형성하여 PVC 조성물의 내구성을 향상시키는데 유리할 수 있다.The protective agent provides a protective layer to the PVC composition to prevent corrosion and improve long-term storage stability. In particular, when a metal phosphate is used, it may be advantageous to improve durability of the PVC composition by forming a more hard cohesive mixture when mixed with a plasticizer.
상기 조성물은, 가소제와 보호제를 각각 2:15 내지 15:2, 및 바람직하게는 각각 1:5 내지 5:1, 및 바람직하게는 각각 1:4 내지 4:1, 및 바람직하게는 각각 1:3 내지 3:1의 사용 가능한 중량비 범위로 포함한다. 가소제와 보호제의 중량비가 상기 정의된 범위 내에 있는 경우, 본 발명에 따른 PVC 조성물은 가소제, 보호제, 및 고분자 결합제를 응집 혼합물 형태로 포함하여 특히 가공성이 우수하다.The composition comprises a plasticizer and a protectant in an amount of 2:15 to 15:2, respectively, and preferably 1:5 to 5:1, respectively, and preferably 1:4 to 4:1, and preferably 1: It is included in the usable weight ratio range of 3 to 3:1. When the weight ratio of the plasticizer and the protective agent is within the range defined above, the PVC composition according to the present invention includes the plasticizer, the protective agent, and the polymeric binder in the form of an aggregated mixture, and thus has excellent processability.
상기 조성물은, 알키드 폴리우레탄(alkyd polyurethane), 또는 폴리비닐 부티랄(polyvinyl butyral) 중 선택되는 하나 이상의 고분자 결합제를 포함한다.The composition includes at least one polymer binder selected from alkyd polyurethane and polyvinyl butyral.
상기 고분자 결합제는 상기 가소제 및 보호제를 운반하여 결합시키는 역할을 하고, 실온 및 실압에서 액체인 것이 유리할 수 있다.The polymeric binder serves to transport and bind the plasticizer and the protective agent, and may advantageously be a liquid at room temperature and pressure.
상술한 바와 같이, 본 발명에 따르면, 고분자 결합제의 존재로 인하여, 혼합 과정에서 발생하는 전단력을 방지할 뿐만 아니라 보호제 내에 있는 인산염의 부하를 감소시켜 PVC 조성물의 가소제 및 보호제의 표면 특성이 크게 변하지 않고 우수한 기계적 물성을 유지할 수 있다.As described above, according to the present invention, due to the presence of the polymer binder, shear force generated in the mixing process is prevented and the load of phosphate in the protective agent is reduced, so that the surface properties of the plasticizer and the protective agent of the PVC composition do not change significantly. Excellent mechanical properties can be maintained.
본 발명은 또한 상기 우수한 가공성 및 물성을 갖는 수지 조성물의 제조방법을 제공한다.The present invention also provides a method for preparing a resin composition having the above excellent processability and physical properties.
본 발명의 제조방법은, 다이아이소노닐 프탈산(Diisononyl phthalate)을 수소반응(hydrogenation)시킴으로서 가소제를 제조하는 단계; 전체 PVC 수지 조성물 기준으로, 상기 가소제 1 내지 70 중량부, 인산염 화합물을 포함하는 보호제 1 내지 7 중량부, 고분자 결합제 0.5 내지 3 중량부를 혼합하는 단계; 및 상기 혼합하는 단계에서의 혼합물을 용융하는 단계;를 포함한다.The production method of the present invention comprises the steps of preparing a plasticizer by subjecting diisononyl phthalate to hydrogenation ; Mixing 1 to 70 parts by weight of the plasticizer, 1 to 7 parts by weight of a protective agent containing a phosphate compound, and 0.5 to 3 parts by weight of a polymer binder based on the total PVC resin composition; and melting the mixture in the mixing step.
상기 가소제를 얻는 단계에서 가소제는 밀도 0.944 ~ 0.954 g/cm3, 점도 44 ~ 60 mPa*s인 1-2 사이클로헥산 디카르복실산 다이아이소노닐 에스테르이다.In the step of obtaining the plasticizer, the plasticizer is 1-2 cyclohexane dicarboxylic acid diisononyl ester having a density of 0.944 to 0.954 g/cm3 and a viscosity of 44 to 60 mPa*s.
상기 혼합하는 단계에서 보호제는, 하나 이상의 금속 인산염(metal phosphates)을 포함하고, 입자 형태로 평균 크기는 0.5 내지 10 μm인 것을 사용한다.In the mixing step, the protective agent includes one or more metal phosphates, and is used in the form of particles having an average size of 0.5 to 10 μm.
상기 보호제 입자의 평균 입자 크기가 상기 정의된 범위 내에 있는 경우, 상기 혼합하는 단계에서 응집 혼합물을 얻을 수 있고, 여기서 보호제 입자는 충분히 자유 유동적이다. 여기서, 보호제 입자의 평균 입경은 통상적인 입도 측정기(Mastersizer 2000, Malvern Instruments)를 이용하여 레이저 회절법(정확도: ±1%)으로 측정하였다.When the average particle size of the protectant particles is within the range defined above, an aggregated mixture can be obtained in the mixing step, wherein the protectant particles are sufficiently free flowing. Here, the average particle diameter of the protective agent particles was measured by laser diffraction (accuracy: ±1%) using a conventional particle size meter (Mastersizer 2000, Malvern Instruments).
상기 혼합하는 단계는, 가소제와 보호제를 각각 10:1 내지 1:7, 및 바람직하게는 각각 1:5 내지 5:1, 및 바람직하게는 각각 1:4 내지 4:1, 및 바람직하게는 각각 1:3 내지 3:1의 사용 가능한 중량비 범위로 혼합하는 단계를 포함한다.In the mixing step, the plasticizer and the protective agent are each 10:1 to 1:7, and preferably each 1:5 to 5:1, and preferably each 1:4 to 4:1, and preferably each mixing in a usable weight ratio range of 1:3 to 3:1.
상기 혼합하는 단계는, 알키드 폴리우레탄(alkyd polyurethane), 또는 폴리비닐 부티랄(polyvinyl butyral) 중 선택되는 하나 이상의 고분자 결합제를 혼합하는 단계를 포함한다.The mixing step includes mixing one or more polymer binders selected from alkyd polyurethane and polyvinyl butyral.
(실시예) PVC 조성물 제조(Example) Preparation of PVC composition
하기 표 1의 조성(단위: 중량%)으로 각 성분을 혼합하고 150~220℃의 온도에서 용융하여 PVC 조성물을 제조하였다.A PVC composition was prepared by mixing each component with the composition (unit: weight%) of Table 1 below and melting at a temperature of 150 to 220 ° C.
상기와 표 1과 같이 실시예 1 내지 3을 제조하여 가공성 및 기계적 물성이 우수한 PVC 조성물을 제조하였다.As shown in Table 1 above, Examples 1 to 3 were prepared to prepare PVC compositions having excellent processability and mechanical properties.
Claims (8)
전체 PVC 수지 조성물 기준으로, 상기 가소제 1 내지 70 중량부, 인산염 화합물을 포함하는 보호제 1 내지 7 중량부, 고분자 결합제 0.5 내지 3 중량부를 혼합하는 단계; 및
상기 혼합하는 단계에서의 혼합물을 용융하는 단계;를 포함하고,
상기 가소제를 얻는 단계에서 가소제는 밀도 0.944 ~ 0.954 g/cm3, 점도 44 ~ 60 mPa*s인 1-2 사이클로헥산 디카르복실산 다이아이소노닐 에스테르인, PVC 수지 조성물의 제조방법.Preparing a plasticizer by subjecting diisononyl phthalate to hydrogenation ;
Mixing 1 to 70 parts by weight of the plasticizer, 1 to 7 parts by weight of a protective agent containing a phosphate compound, and 0.5 to 3 parts by weight of a polymer binder based on the total PVC resin composition; and
Including; melting the mixture in the mixing step;
In the step of obtaining the plasticizer, the plasticizer is 1-2 cyclohexane dicarboxylic acid diisononyl ester having a density of 0.944 to 0.954 g/cm3 and a viscosity of 44 to 60 mPa*s.
상기 혼합하는 단계에서 보호제는, 하나 이상의 금속 인산염(metal phosphates)을 포함하고, 입자 형태로 평균 크기는 0.5 내지 10 μm인 것을 사용하는, PVC 수지 조성물의 제조방법.According to claim 1,
In the mixing step, the protective agent includes one or more metal phosphates, and the average size in the form of particles is 0.5 to 10 μm, using a method for producing a PVC resin composition.
상기 혼합하는 단계는, 가소제와 보호제를 각각 10:1 내지 1:7, 및 바람직하게는 각각 1:5 내지 5:1, 및 바람직하게는 각각 1:4 내지 4:1, 및 바람직하게는 각각 1:3 내지 3:1의 사용 가능한 중량비 범위로 혼합하는 단계;를 포함하는 PVC 수지 조성물의 제조방법.According to claim 1,
In the mixing step, the plasticizer and the protective agent are each 10:1 to 1:7, and preferably each 1:5 to 5:1, and preferably each 1:4 to 4:1, and preferably each 1: 3 to 3: mixing in a usable weight ratio range of 1; method for producing a PVC resin composition comprising a.
상기 혼합하는 단계는, 알키드 폴리우레탄(alkyd polyurethane), 또는 폴리비닐 부티랄(polyvinyl butyral) 중 선택되는 하나 이상의 고분자 결합제를 혼합하는 단계를 포함하는, PVC 수지 조성물의 제조방법.According to claim 1,
Wherein the mixing step includes mixing one or more polymeric binders selected from alkyd polyurethane and polyvinyl butyral.
다이아이소노닐 프탈산(Diisononyl phthalate)을 수소반응(hydrogenation)시킴으로서 얻은 1-2 사이클로헥산 디카르복실산 다이아이소노닐 에스테르를 포함하는 가소제; 및
인산염 화합물을 포함하는 보호제;를 포함하고,
상기 가소제는 밀도 0.944 ~ 0.954 g/cm3, 점도 44 ~ 60 mPa*s인, PVC 조성물.It is prepared by the method of any one of claims 1 to 4,
a plasticizer including 1-2 cyclohexane dicarboxylic acid diisononyl ester obtained by hydrogenation of diisononyl phthalate ; and
A protective agent containing a phosphate compound; including,
The plasticizer has a density of 0.944 to 0.954 g/cm3 and a viscosity of 44 to 60 mPa*s, PVC composition.
상기 보호제는, 하나 이상의 금속 인산염(metal phosphates)을 포함하고, 입자 형태로 평균 크기는 0.5 내지 10μm인 것을 사용하는, PVC 수지 조성물.According to claim 5,
The protective agent includes one or more metal phosphates, and the average particle size is 0.5 to 10 μm in the form of particles, PVC resin composition.
상기 조성물은, 가소제와 보호제를 각각 2:15 내지 15:2, 및 바람직하게는 각각 1:5 내지 5:1, 및 바람직하게는 각각 1:4 내지 4:1, 및 바람직하게는 각각 1:3 내지 3:1의 사용 가능한 중량비 범위로 포함하는, PVC 수지 조성물.According to claim 5,
The composition comprises a plasticizer and a protectant in an amount of 2:15 to 15:2, respectively, and preferably 1:5 to 5:1, respectively, and preferably 1:4 to 4:1, and preferably 1: A PVC resin composition comprising an usable weight ratio range of 3 to 3: 1.
상기 조성물은, 알키드 폴리우레탄(alkyd polyurethane), 또는 폴리비닐 부티랄(polyvinyl butyral) 중 선택되는 하나 이상의 고분자 결합제를 포함하는, PVC 수지 조성물.
According to claim 5,
The composition is a PVC resin composition comprising at least one polymeric binder selected from alkyd polyurethane and polyvinyl butyral.
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