KR950006264B1 - Polyvinyl chloride resin composition and its manufacture method for gasket of refrigerator door - Google Patents

Polyvinyl chloride resin composition and its manufacture method for gasket of refrigerator door Download PDF

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KR950006264B1
KR950006264B1 KR1019910015050A KR910015050A KR950006264B1 KR 950006264 B1 KR950006264 B1 KR 950006264B1 KR 1019910015050 A KR1019910015050 A KR 1019910015050A KR 910015050 A KR910015050 A KR 910015050A KR 950006264 B1 KR950006264 B1 KR 950006264B1
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polyvinyl chloride
chloride resin
resin composition
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KR930004431A (en
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강호철
남충우
임정택
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한화종합화학주식회사
박원배
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02—Inorganic compounds
    • C09K2200/0239—Oxides, hydroxides, carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0635—Halogen-containing polymers, e.g. PVC
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
    • C09K2200/0655—Polyesters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Sealing Material Composition (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The resin is composed of 100 wt% PVC resin, 30-80 wt% polyester adipate, 10-50 wt% epoxidated soybean oil and 5-50 wt% calcium chloride as a filler, other additives including 0.5-2.0 wt% Ba-Zn based solid state organic composite as a thermal stabilizer, 0.2-1.0 wt% phosphite, 0.1-0.8 wt% barium stearate, 0.08-0.7 wt% calcium stearate, 0.08-0.8 wt% stearic acid, 0.2-1.0 wt% polyethylene oxide, 0.5-4.0 wt% methyl metacrylate-alkyl acrylate copolymer as a processing aid, 0.05-0.5 wt% 10,10'-oxybisphenoxazine as an antifungal agent, 0.6-5.0 wt% titania as a flame retardant and some amount of pigment. The PVC resin is prepared by (a) mixing resin and additives at low stirring speed at 60-120 deg.C for 1-2 min., (b) mixing this mixture and polyester adipate, epoxidated soybean oil at 50-100 deg.C and adding calcium carbonate to the mixture.

Description

냉장고 도어의 가스킷용 폴리염화비닐수지조성물과 그의 제조방법Polyvinyl chloride resin composition for gasket of refrigerator door and its manufacturing method

본 발명은 냉장고 도어의 가스킷용 폴리염화비닐수지조성물과 그의 제조방법에 관한 것이다. 더욱 상세하게는, 폴리염화비닐수지에 폴리에스테르계 고분자 가소제와 에폭시화된 콩기름이 혼용되어 이루어진 가소제 내이행성, 내용제성, 가공성, 내곰팡이성 및 기계적강도도 우수한 냉장고 도어의 가스킷용 폴리염화비닐수지조성물과 그 제조방법에 관한 것이다.The present invention relates to a polyvinyl chloride resin composition for a gasket of a refrigerator door and a manufacturing method thereof. More specifically, a polyvinyl chloride resin for a gasket of a refrigerator door having excellent plasticity resistance, solvent resistance, processability, mold resistance, and mechanical strength, in which a polyvinyl chloride resin is mixed with a polyester polymer plasticizer and epoxidized soybean oil. A composition and a method for producing the same.

종래의 냉장고 가스킷용 폴리염화비닐수지조성물은 프탈레이트 가소제등을 사용하기 때문에 냉장고 내상의 소재인 ABS 수지 또는 HIPS 수지에 가소제이행이 심하여 접촉부위가 쉽게 오염되고, 장기간 사용시 기계적 물성이 저하하였으며, 내곰팡이성이나 밀폐성등에 문제가 있을 뿐만 아니라 냉장고 청소등에 사용하는 용제에 대해 내용제성이 불량한 단점도 있었다.Since polyvinyl chloride resin composition for refrigerator gaskets uses phthalate plasticizers and the like, plasticizers are severely adhered to ABS resin or HIPS resin, which is a material on the inside of the refrigerator, and contaminated contact parts are easily contaminated. As well as problems in the properties such as castle or airtightness, there was also a disadvantage that the solvent resistance is poor for the solvent used for cleaning the refrigerator.

특히, 종래에 사용한 가소제들은 고분자 가소제들이므로 단가가 고가일뿐만 아니라 점도도 3,000rps의 고점도이므로 조성물제조시 가소제의 완전한 흡수가 곤란하며, 일반적인 헨첼혼합기(Henschel Mixer)작업방식으로는 조성물의 제조가 불가능(가공성 저하)하다는 문제점등이 있었다.In particular, since the plasticizers used in the prior art are polymer plasticizers, they are not only expensive, but also have high viscosity of 3,000 rpm, making it difficult to completely absorb the plasticizer during the preparation of the composition, and in general, the Henschel Mixer working method allows the manufacture of the composition. There were problems such as impossibility (degradability).

본 발명은 상기 문제점을 해결하기 위하여 이루어진 것으로서, 본 발명의 목적은 종래의 ABS 수지와 HIPS 수지에 대한 가소제 이행문제를 포함한 제반물성의 향상을 위해, 폴리염화비닐수지에 대한 가소제로서 폴리에스테르계 고분자 가소제를 사용하고, 에폭시화된 콩기름을 병용시키므로서 가소제의 내이행성과 내용제성, 가공성, 내곰팡이성 및 기계적 강도면에서 뛰어난 냉장고 도어의 가스킷용 폴리염화비닐수지조성물과 이를 제조하는 방법을 제공하는데 있다.The present invention has been made to solve the above problems, an object of the present invention is to improve the overall physical properties, including the problem of the plasticizer for the conventional ABS resin and HIPS resin, a polyester-based polymer as a plasticizer for polyvinyl chloride resin The present invention provides a polyvinyl chloride resin composition for a gasket of a refrigerator door excellent in terms of plasticizer performance, solvent resistance, processability, mold resistance and mechanical strength by using a plasticizer and using epoxidized soybean oil in combination. have.

이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명은 폴리염화비닐수지 100중량부에 대해 아디프산 폴리에스테르 30 내지 80중량부와, 에폭시화된 콩기름 10 내지 50중량부를 주성분으로 하고, 여기에 충진제와 기타 첨가제를 포함하여서 이루어진 냉장고 가스킷용 폴리염화비닐수지조성물인 것이다.The present invention is a refrigerator gasket composed of 30 to 80 parts by weight of adipic acid polyester and 10 to 50 parts by weight of epoxidized soybean oil based on 100 parts by weight of polyvinyl chloride resin, and comprising a filler and other additives. It is a polyvinyl chloride resin composition.

또한, 본 발명에 따른 폴리염화비닐수지조성물은 폴리염화비닐수지와 기타 첨가제를 60℃의 고온에서 1분 내지 2분간 저속으로 교반혼합하고, 이어서 아디프산 폴리에스테르와 에폭시화된 콩기름을 50℃ 내지 100℃의 범위에서 소량씩 투입하여 저속 또는 고속과 혼용으로 교반혼합시키며, 여기에다 충진제를 투입하여 105℃ 내지 110℃로 배합한 후 상기 배합물을 배출시켜 냉각처리하여서 분말 형태로 제조한다.In addition, the polyvinyl chloride resin composition according to the present invention is stir-mixed polyvinyl chloride resin and other additives at a low temperature of 1 to 2 minutes at a high temperature of 60 ℃, then adipic acid polyester and epoxidized soybean oil at 50 ℃ In a small amount in the range of to 100 ℃ to stir-mix the mixture at low or high speed, the filler is added to the mixture at 105 ℃ to 110 ℃ and then the mixture is discharged and cooled to prepare a powder form.

이와같이 구성된 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention configured in this way in more detail as follows.

본 발명에 따르면 폴리염화비닐수지로는 중합도가 1300정도인 폴리염화비닐수지가 사용된다.According to the present invention, polyvinyl chloride resin having a degree of polymerization of about 1300 is used as the polyvinyl chloride resin.

가소제로는 폴리에스테르계의 고분자 가소제인 아디프산 폴리에스테르를 폴리염화비닐수지 100중량부에 대해 30 내지 80중량부가 사용한다.As a plasticizer, 30-80 weight part of adipic acid polyester which is a polyester polymer plasticizer is used with respect to 100 weight part of polyvinyl chloride resins.

만일, 가소제로서 아디프산 폴리에스테르의 양을 30중량부 미만으로 사용할 경우에는 가소제의 내이행성과 내용제성이 떨어지게 되며, 반대로 80중량부를 초과하여 사용할 경우에는 얻고자 하는 내이행성과 내용제성에 비해 가격면에서 바람직하지 못하게 된다. 더욱 바람직하기로는 아디프산 폴리에스테르 가소제를 45 내지 55중량부 사용하는 것이 좋다.If the amount of adipic acid polyester is less than 30 parts by weight as the plasticizer, the plasticizer has poor performance and solvent resistance. On the contrary, when the amount of adipic acid polyester is used in excess of 80 parts by weight, It is not desirable in terms of price. More preferably, 45 to 55 parts by weight of adipic acid polyester plasticizer is used.

한편, 상기 고분자 가소제의 사용에 따른 원가절감과 부수적으로 가공성의 향상을 위해 에폭시화 콩기름을 사용할 수 있으며, 그 사용량은 폴리염화비닐수지 100중량부에 대해 10 내지 50중량부가 좋다. 만일 상기 에폭시화된 콩기름의 양을 10중량부 미만으로 사용할 경우에는 고분자 가소제의 양을 증가시켜야 하므로 비경제적이고, 또 냉장고내에 서식하는 곰팡이에 대한 내곰팡이성도 약하고 반대로 50중량부를 초과하여 사용할 경우에는 가공성을 저하시키는 문제를 일으킨다. 더욱 바람직하기로는 에폭시화 콩기름의 양을 20 내지 40중량부 사용하는 것이 좋다.On the other hand, epoxidized soybean oil may be used for cost reduction and concomitantly improving processability according to the use of the polymer plasticizer, the amount of which is preferably 10 to 50 parts by weight based on 100 parts by weight of polyvinyl chloride resin. If the amount of the epoxidized soybean oil is less than 10 parts by weight, the amount of polymeric plasticizer should be increased, so it is uneconomical and the mold resistance to the mold in the refrigerator is weak. Causes problems to degrade. More preferably, the amount of epoxidized soybean oil is 20 to 40 parts by weight.

본 발명에서 사용하는 충진제로서는 CaCl2계가 바람직하며 그 사용량은 5 내지 50중량부가 좋다.As the filler used in the present invention, CaCl 2 is preferable, and the amount thereof is preferably 5 to 50 parts by weight.

또한, 본 발명에서 사용하는 기타 첨가제로는 무독성의 Ba-Zn계 열안정제와 아인산엽계 열안정제가 있으며, 상기 열안정제로서는 일본의 아데카아르구스(주)에서 제조한 바륨-아연계 고상유기복합체(상표명; Mark Rup-14) 또는 아인산염(상표명; Mark-1500)을 사용할 수 있으며, 그 사용량으로는 폴리염화비닐수지 100중량부에 대해 Ba-Zn계 고상유기복합체 0.4 내지 2.0중량부, 아인산염 0.2 내지 1.0중량부를 사용하는 것이 좋다. 그 이외의 첨가제로서는 스테아린산바륨(Ba-St) 0.1 내지 0.8중량부, 스테아린산칼슘(Ca-St) 0.08 내지 0.7중량부, 스테아린산(H-St) 0.08 내지 0.8중량부, 산화폴리에틸렌(미국 Allied signal사 제품의 상표명 ; AC-629A) 0.2 내지 1.0 중량부, 가공조제로서 메틸메타크릴레이트-알킬아크릴레이트 코폴리머(K-125) 0.5 내지 4.0 중량부, 곰팡이방지제로서 10,10'옥시비스페녹사진(일본 기따고오가가구(주)제품의 상품명 Hokustar-HP) 0.05 내지 0.5중량부, 난연제로서 TiO20.6 내지 5.0중량부, 적당량의 안료가 혼합된 혼합물로 사용할 수 있다.In addition, other additives used in the present invention include non-toxic Ba-Zn-based heat stabilizer and phosphorous phosphate-based heat stabilizer, and the heat stabilizer is a barium-zinc-based solid organic complex manufactured by Adeka Argus Co., Ltd. of Japan. (Trade name; Mark Rup-14) or phosphite (trade name; Mark-1500) may be used, and the amount of the polyvinyl chloride resin is 0.4 to 2.0 parts by weight based on 100 parts by weight of a polyvinyl chloride resin. It is preferable to use 0.2 to 1.0 parts by weight of phosphate. Other additives include barium stearate (Ba-St) 0.1 to 0.8 part by weight, calcium stearate (Ca-St) 0.08 to 0.7 part by weight, stearic acid (H-St) 0.08 to 0.8 part by weight, polyethylene oxide (USA Allied signal) AC-629A) 0.2 to 1.0 parts by weight, methyl methacrylate-alkyl acrylate copolymer (K-125) as processing aid, 10 to 10'oxybisphenoxazine as antifungal agent (Trade name Hokustar-HP manufactured by Nippon Kogyo Furniture Co., Ltd.) 0.05 to 0.5 parts by weight, TiO 2 0.6 to 5.0 parts by weight as a flame retardant, can be used in a mixture of a suitable amount of pigments.

본 발명에 따른 폴리염화비닐수지조성물의 제조시에는 통상적으로 100ℓ 용량의 헨셀혼합기(Henschal Mixer)를 이용하며, 혼합기내에 충전된 오일의 온도를 60내지 120℃의 고온으로 유지하고, 이 혼합기에다 분산성 향상을 위해 폴리염화비닐수지와 상기한 기타 첨가제 및 필요에 따라 안료를 투입하여 1분 내지 2분간 약 400rpm 저속으로 교반혼합한다.In preparing the polyvinyl chloride resin composition according to the present invention, a Henschel Mixer having a capacity of 100 l is generally used, and the oil filled in the mixer is maintained at a high temperature of 60 to 120 ° C. In order to improve the acidity, the polyvinyl chloride resin and the other additives as described above and a pigment are added as necessary, and stirred and mixed at about 400 rpm at a low speed for 1 to 2 minutes.

다음에, 가소제의 점도를 낮추기 위해 가소제 승온장치를 통해 50℃ 내지 100℃의 범위에서 고분자 가소제인 아디프산 폴리에스테르와 에폭시화 콩기름을 분당 200 내지 500g씩 투입하여 저속 또는 저속과 고속을 병행, 바람직하게는 저속으로 이들을 교반혼합시킨다.Next, in order to lower the viscosity of the plasticizer, the adipic acid polyester and the epoxidized soybean oil, which are high molecular plasticizers, were added in a range of 50 ° C. to 100 ° C. in a range of 50 ° C. to 100 ° C., in parallel to low or low speeds and high speeds. Preferably they are stirred and mixed at low speed.

그후, 상기 과정 이후에 배합물에다 충진제를 투입하여 105℃ 내지 110℃로 배합한 후 상기 배합물을 약 125℃의 온도에서 배출시킨 후 냉각혼합기로 이송시켜 약 40℃ 이하로 냉각처리하면, 본 발명에 따른 분말상태의 생성물이 얻어지게 된다.Thereafter, after the above process, the filler is added to the compound, and then blended at 105 ° C to 110 ° C, and then the compound is discharged at a temperature of about 125 ° C, and then transferred to a cooling mixer to cool down to about 40 ° C or less. Accordingly, a powdery product is obtained.

상기와 같이 본 발명에 따른 폴리염화비닐수지조성물은 냉장고 도어의 가스킷용으로 사용하기에 적합하여, 특히 가소제 이행문제를 포함한 제반물성의 향상을 위해, 폴리염화비닐수지에 대한 가소제로서 폴리에스테르계 고분자 가소제를 사용하고, 에폭시화된 콩기름을 병용시키므로서 가소제의 내이행성과 내용제성, 가공성, 내곰팡이성 및 기계적 강도면에서 뛰어난 효과가 있다.As described above, the polyvinyl chloride resin composition according to the present invention is suitable for use as a gasket for a refrigerator door, and in particular, a polyester-based polymer as a plasticizer for polyvinyl chloride resin, in order to improve various properties including plasticizer migration problems. By using a plasticizer and using epoxidized soybean oil together, the plasticizer has an excellent effect on the plasticizer's performance, solvent resistance, processability, mold resistance and mechanical strength.

이하, 본 발명을 실시예를 통해 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.

[실시예]EXAMPLE

100ℓ용량의 헨첼혼합기의 오일자켓의 온도를 80℃로 유지해주고 이 혼합기에다 중합도가 1300인 폴리염화비닐수지 100중량부에 대해 첨가제로서 열안정제로 바륨-아연계 고상유기복합체와 아인산염을 각각 1.0중량부와 0.5중량부, 스테아린산바륨 0.4중량부, 스테아린산칼슘 0.3중량부, 스테아린산 0.3중량부, 산화폴리에틸렌 0.5중량부, 가공조제로서 메틸메타크릴레이트-알킬아크릴레이트 코폴리머 2.0중량부, 곰팡이방지제로서 10,10'옥시비스페녹사진(Oxybisphenoxarsine) 0.1중량부, 난연제로서 TiO22.0중량부, 안료 적당량을 투입하여 2분간 400rpm저속으로 교반혼합한다. 다음에, 가소제 승온장치를 통해 80℃에서 아디프산 폴리에스테르와 에폭시화 콩기름을 분당 500g씩 투입하여 500rpm의 속도로 이들을 교반혼합시켰다.Maintain the temperature of the oil jacket of 100l Henschel mixer at 80 ℃ and add 1.0 barium-zinc solid organic complex and phosphite as heat stabilizer to 100 parts by weight of polyvinyl chloride resin with a polymerization degree of 1300. Parts by weight and 0.5 parts by weight, barium stearate 0.4 parts by weight, calcium stearate 0.3 parts by weight, stearic acid 0.3 parts by weight, polyethylene oxide 0.5 parts by weight, methyl methacrylate-alkyl acrylate copolymer 2.0 parts by weight as a processing aid, as a mold inhibitor 0.1 parts by weight of 10,10'Oxybisphenoxarsine, 2.0 parts by weight of TiO 2 as a flame retardant, and an appropriate amount of pigment are added and stirred and mixed at a low speed of 400 rpm for 2 minutes. Next, adipic acid polyester and epoxidized soybean oil were added 500 g per minute at 80 ° C. through a plasticizer heating apparatus, and these were stirred and mixed at a speed of 500 rpm.

다음에, 상기 배합물에다 CaCO3계 충진제를 투입하여 110℃에서 배합하고, 상기 배합물을 125℃의 온도에서 배출시킨 후, 냉각혼합기로 이송시켜 40℃ 이하로 냉각처리하여 분말상의 생성물을 얻는다.Next, CaCO 3 -based filler was added to the compound and blended at 110 ° C., the compound was discharged at a temperature of 125 ° C., then transferred to a cooling mixer, and cooled to 40 ° C. or less to obtain a powdery product.

[비교실시예 1]Comparative Example 1

상기 실시예 1에서 가소제로서 ABS 수지와 HIPS 수지를 사용하는 것 이외에는 상기 실시예 1과 동일하게 하여 폴리염화비닐수지조성물을 얻었다.A polyvinyl chloride resin composition was obtained in the same manner as in Example 1 except that ABS resin and HIPS resin were used as the plasticizer in Example 1.

상기 실시예와 비교실시예에서 얻어진 생성물의 물성측정결과는 다음 표 1과 같다.The physical property measurement results of the products obtained in Examples and Comparative Examples are shown in Table 1 below.

[표 1]TABLE 1

(1) 65℃ ×150시간에서 측정.(1) Measured at 65 ° C. × 150 hours.

(2) 인장속도를 500mm/분으로 하여 측정.(2) Measured at a tensile speed of 500 mm / min.

(3) 120℃×120시간 방치후에 측정(3) Measured after 120 ℃ × 120 hours

(4) 25℃ 물에 72시간 침적후에 우유를 바르고 25℃×120시간 동안 방치한 후에 측정함. 측정시의 습도는 95%.(4) After 72 hours of immersion in water at 25 ° C, milk is applied and measured after standing at 25 ° C for 120 hours. Humidity at the time of measurement is 95%.

(5) 버터+물에 시료를 밀봉하고 4±2.8℃에서 16 내지 72시간동안 방치한 후에 측정.(5) Measured after sealing the sample in butter + water and standing at 4 ± 2.8 ° C. for 16-72 hours.

(6) -20℃×48시간동안 방치후에 측정.(6) Measured after standing at −20 ° C. for 48 hours.

(7) n-헥산에 72시간동안 침적시킨 후에 측정.(7) Measured after immersion in n-hexane for 72 hours.

(8) H2S에 5분간 방지한 후에 측정.(8) Measured after preventing for 5 minutes in H 2 S.

(9) 쇼아 A경도.(9) Shore A hardness.

(10) 비중계로 측정.(10) Measured with hydrometer.

Claims (4)

폴리염화비닐수지조성물에 있어서, 폴리염화비닐수지 100중량부에 대해 아디프산 폴리에스테르 30내지 80중량부와, 에폭시화된 콩기름 10 내지 50중량부를 주성분으로 하고, 여기에 충진제와 기타 첨가제를 포함하여서 이루어진 냉장고 가스킷용 폴리염화비닐수지조성물.Polyvinyl chloride resin composition, comprising 30 to 80 parts by weight of adipic acid polyester and 10 to 50 parts by weight of epoxidized soybean oil based on 100 parts by weight of polyvinyl chloride resin, and include fillers and other additives. Polyvinyl chloride resin composition for refrigerator gasket made by. 제1항에 있어서, 상기 폴리염화비닐수지 100중량부에 대해 Ba-Zn계 고상유기 복합체 0.5 내지 2.0중량부, 아인산염 0.2 내지 1.0중량부, 스테아린산바륨 0.1 내지 0.8중량부, 스테아린산칼슘 0.08 내지 0.7 중량부, 스테아린산 0.008 내지 0.7중량부, 스테아린산 0.08 내지 0.8중량부, 산화폴리에틸렌 0.2 내지 1.0중량부, 메틸메타크릴레이트-알킬아크릴레이트, 코폴리머 0.5 내지 4.0 중량부, 10,10'옥시비스페녹사진 0.05 내지 0.5중량부, TiO20.6 내지 5.0중량부 및 안료를 적당량으로 함유하는 것을 특징으로 하는 냉장고 가스킷용 폴리염화비닐수지조성물.According to claim 1, 0.5 to 2.0 parts by weight of Ba-Zn-based solid organic composite, 0.2 to 1.0 part by weight of phosphite, 0.1 to 0.8 part by weight of barium stearate, 0.08 to 0.7 by weight of calcium stearate relative to 100 parts by weight of the polyvinyl chloride resin Parts by weight, stearic acid 0.008 to 0.7 parts by weight, stearic acid 0.08 to 0.8 parts by weight, polyethylene oxide 0.2 to 1.0 parts by weight, methyl methacrylate-alkyl acrylate, copolymer 0.5 to 4.0 parts by weight, 10,10'oxybisphenoxy A polyvinyl chloride resin composition for refrigerator gaskets containing 0.05 to 0.5 parts by weight, 0.6 to 5.0 parts by weight of TiO 2 , and a pigment in an appropriate amount. 폴리염화비닐수지조성물을 제조하는데 있어서, 폴리염화비닐수지와 첨가제를 60℃ 내지 120℃의 고온에서 1분 내지 2분간 저속으로 교반혼합하고, 이어서 상기 혼합물 100중량부에 대해 아디프산 폴리에스테르 30 내지 80중량부와 에폭시화된 콩기름 10 내지 50중량부를 50℃ 내지 100℃의 범위에서 소량씩 투입하여 저속 또는 고속과 혼용으로 교반혼합시키며, 여기에다 CaCO35 내지 50중량부를 투입하여 105℃ 내지 110℃로 배합한 후, 상기 배합물을 배출시켜 냉각처리한 것을 특징으로 하는 냉장고 가스킷용 폴리염화비닐 수지조성물의 제조방법.In preparing the polyvinyl chloride resin composition, the polyvinyl chloride resin and the additive are stirred and mixed at a low speed for 1 to 2 minutes at a high temperature of 60 ° C to 120 ° C, followed by adipic acid polyester 30 to 100 parts by weight of the mixture. To 80 parts by weight and 10 to 50 parts by weight of epoxidized soybean oil are added in small amounts in the range of 50 ° C. to 100 ° C. and stirred and mixed for mixing with low speed or high speed, and 5 to 50 parts by weight of CaCO 3 is added to 105 ° C. to 110 °. A method of producing a polyvinyl chloride resin composition for a refrigerator gasket, wherein the compound is discharged and cooled after blending at a temperature of about 0 ° C. 제3항에 있어서, 상기 첨가제는 폴리염화비닐수지 100중량부에 대해 Ba-Zn계 고상유기 복합체 0.5내지 2.0중량부, 아인산염 0.2내지 1.0중량부, 스테아린산바륨 0.1 내지 0.8중량부, 스테아린산칼슘 0.08내지 0.7중량부, 스테아린산 0.08 내지 0.8중량부, 산화폴리에틸렌 0.2 내지 1.0중량부, 메틸메타크릴레이트-알킬아크릴레이트 코폴리머 0.5 내지 4.0중량부, 곰팡이방지제로서 10,10'옥시비스페녹사진 곰팡이방지제 0.05 내지 0.5중량부, CaCO35 내지 50중량부, TiO20.6 내지 5.0중량부 및 안료 적당량을 혼합시키는 것을 특징으로 하는 냉장고 가스킷용 폴리염화비닐수지조성물의 제조방법.According to claim 3, wherein the additive is 0.5 to 2.0 parts by weight of Ba-Zn-based organic-based organic complex, 0.2 to 1.0 parts by weight of phosphite, 0.1 to 0.8 parts by weight of barium stearate, and 0.08 parts of calcium stearate based on 100 parts by weight of polyvinyl chloride resin. To 0.7 parts by weight, stearic acid 0.08 to 0.8 parts by weight, polyethylene oxide 0.2 to 1.0 parts by weight, methyl methacrylate-alkyl acrylate copolymer 0.5 to 4.0 parts by weight, 10,10 'oxybisphenoxazine mold inhibitor as antifungal agent A method for producing a polyvinyl chloride resin composition for a refrigerator gasket, comprising 0.05 to 0.5 parts by weight, CaCO 3 5 to 50 parts by weight, TiO 2 0.6 to 5.0 parts by weight, and an appropriate amount of pigment.
KR1019910015050A 1991-08-29 1991-08-29 Polyvinyl chloride resin composition and its manufacture method for gasket of refrigerator door KR950006264B1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009138314A1 (en) * 2008-05-16 2009-11-19 Henkel Ag & Co. Kgaa Composition for the production of a sealing web
WO2019086259A1 (en) 2017-11-06 2019-05-09 Arcelik Anonim Sirketi A door gasket

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009138314A1 (en) * 2008-05-16 2009-11-19 Henkel Ag & Co. Kgaa Composition for the production of a sealing web
WO2019086259A1 (en) 2017-11-06 2019-05-09 Arcelik Anonim Sirketi A door gasket

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