KR970009392B1 - The process for the preparation of waterproof polyurethane rubber sheet from polyurethane foam - Google Patents

The process for the preparation of waterproof polyurethane rubber sheet from polyurethane foam Download PDF

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KR970009392B1
KR970009392B1 KR1019920012402A KR920012402A KR970009392B1 KR 970009392 B1 KR970009392 B1 KR 970009392B1 KR 1019920012402 A KR1019920012402 A KR 1019920012402A KR 920012402 A KR920012402 A KR 920012402A KR 970009392 B1 KR970009392 B1 KR 970009392B1
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rubber sheet
polyurethane
polyurethane foam
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KR940002319A (en
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차국승
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

Waterproof polyurethane rubber sheet is produced by (1) To 100wt% of grinded polyurethane foam, adding palletizing composite that has 2~3wt% of chlorination polyethylene, 2~3wt% of ethylene glycol or buthylene glycol and 2~3wt% of sulfuric barium. (2) pelletizing above mixture by extruding within temperature range of 130~170deg.C . (3) By adding polyurethane rubber sheet composite with 2~4wt% of chlorination polyethylene, 1~3wt% of sulfuric barium, 0.5~2.5wt% of stearin acid zinc, 2.5wt% of clay and 2.5wt% of talcum to the above pallet 100wt%, extruding within temperature range of 130~160deg.C. (4) By injecting above extruded substance between two geared cooling drums, passing through cooling drum.

Description

폴리우레탄 포옴으로부터 방수용 폴리우레탄 고무쉬트를 제조하는 방법Method for manufacturing waterproof polyurethane rubber sheet from polyurethane foam

본 발명은 폴리우레탄 포옴(polyurethane form)으로부터 방수용 폴리우레탄 고무쉬트를 제조하는 방법에 관한 것으로서, 상세하게는 열경화성 폴리우레탄 수지제품인 폴리우레탄 포옴에 소정의 조성물을 첨가하고 물성을 변성시키는 것에 의해 방수용 폴리우레탄 고무쉬트를 제조하는 방법에 관한 것이다.The present invention relates to a method for manufacturing a waterproof polyurethane rubber sheet from a polyurethane foam, and more particularly, by adding a predetermined composition to a polyurethane foam, which is a thermosetting polyurethane resin product, and modifying physical properties. It relates to a method for producing a urethane rubber sheet.

폴리우레탄은 주쇄중에 우레탄 결합(-NHCOO)을 갖는 합성고분자로서, 일반적으로 디이소시아네이트와 디올을 반응시켜 얻어진다. 상세하게는 디이소시아네이트에 폴리에스테르폴리올, 폴리에테르폴리올, 아크릴폴리올, 파마자유 유도체, 기타 함수산기 화합물과의 반응에 의해 제조된다. 이때 상기한 디이소시아네이트와 반응물의 종류에 따라 우레탄 고무, 우레탄 도료, 우레탄 접착제, 스판텍스, 폴리우레탄 코티드 합성피혁인 폴리우레탄 코티드레더(coated leather) 등 광범위한 용도의 우레탄 제품이 얻어지게 된다.Polyurethane is a synthetic polymer having a urethane bond (-NHCOO) in the main chain, and is generally obtained by reacting diisocyanate with diol. Specifically, diisocyanate is prepared by reaction with polyester polyol, polyether polyol, acryl polyol, perm oil derivative, and other hydrous acid compound. At this time, according to the type of the diisocyanate and the reactant, a urethane product of a wide range of uses, such as urethane rubber, urethane paint, urethane adhesive, spantex, polyurethane coated synthetic leather, polyurethane coated leather, is obtained.

폴리우레탄 포옴은 디이소시아네이트와 디올의 반응시 디올에 소량의 물을 혼합하여 반응시키면 얻을 수 있다. 이는 물이 디이소시아네이트와 반응하여 디아민과 이산화탄소를 생성하는데, 중합반응이 진행됨에 따라 사슬이 연장되면서 분자가 거대화 됨과 동시에 가교반응이 일어나면서, 상기 이산화탄소 가스가 거품(bubble) 형태로 중합체내에 잡혀서 구형 또는 다각형 세포조직을 갖는 스폰지 형상으로 만들어지는 것이다. 폴리우레탄 포옴은 열경화성 수지로서 쿠션재료, 신발창, 단열재료, 건축재료 등에 사용된다.Polyurethane foams can be obtained by reacting diols with a small amount of water during the reaction of diisocyanates with diols. Water reacts with diisocyanate to produce diamine and carbon dioxide. As the polymerization progresses, the chain is extended, the molecules become larger, and the crosslinking reaction takes place, and the carbon dioxide gas is trapped in the polymer in the form of bubbles to form a sphere. Or it is made of a sponge shape having a polygonal tissue. Polyurethane foam is used in cushioning materials, soles, insulation materials, building materials, etc. as a thermosetting resin.

일반적인 폴리우레탄 수지는 열가소성 수지이므로 열용융이 가능하나 유동성이 매우 크기 때문에 PVC(polyvinyl chloride), PE(polyethylene), PP(polypropylene ), PS(polystyrene) 등과 같은 중합체와는 달리 상온에서 압출 성형이나 다이스 성형이 거의 불가능하다. 이에 따라 대부분 유기 경화제 또는 무기 경화제를 사용하거나 열 또는 대기에 의한 경화로 응고시키거나 큰 점도를 갖게 하여 성형하게 된다. 따라서 시간이 경과되면 성형물의 성질이 변성된다는 문제가 있다. 따라서 고무로서의 특성을 유지하면서 PVC, PE, PP, PS 등과 같이 쉬트 성형성을 갖는 폴리우레탄 고무쉬트의 제조방법이 요구되어 왔다.Since general polyurethane resin is thermoplastic resin, it can be hot melted, but because of its high fluidity, unlike polymers such as PVC (polyvinyl chloride), PE (polyethylene), PP (polypropylene), and PS (polystyrene), extrusion molding or dies at room temperature Molding is almost impossible. Accordingly, most of them may be formed by using an organic curing agent or an inorganic curing agent or by solidifying by heat or air curing or having a large viscosity. Therefore, there is a problem that the property of the molded product is denatured over time. Therefore, there has been a need for a method for producing a polyurethane rubber sheet having sheet formability such as PVC, PE, PP, PS, etc. while maintaining its properties as rubber.

본 발명의 목적은 상기한 요구에 부응하여 상기한 열경화성 폴리우레탄 포옴을 이용하여 용이하게 성형하는 것으로 방수용 폴리우레탄 고무쉬트를 제조할 수 있는 방법을 제공하고자 하는 것이다.It is an object of the present invention to provide a method for producing a waterproof polyurethane rubber sheet by easily molding using the above-mentioned thermosetting polyurethane foam in response to the above requirements.

상기 목적을 달성하기 위하여 본 발명에서는 폴리우레탄 포옴 분쇄물 100중량부에, 염소화 폴리에틸렌 2-3중량부, 에틸렌글리콜 또는 부틸렌글리콜 2-3중량부 및 황상바륨(BaSO4) 2-3중량부의 조성을 갖는 펠렛트화 조성물을 첨가하여 조성물을 첨가하여 혼합하는 단계; 상기 혼합물을 130-170℃ 온도 범위에서 입출함으로서 펠렛트화 하는 단계; 얻어지는 펠렛트에, 상기 펠렛트에, 상기 펠렛트 100중량부에 대하여 염소화 폴리에틸렌 2-4중량부, 황산바륨 1-3중량부, 스테아린산 아연 0.5-2.5중량부, 점토 2.5중량부 및 활석분 2.5중량부의 조성비를 갖는 폴리우레탄 고무쉬트 조성물을 첨가하여 혼합하고 130-160℃ 온도 범위에서 압출하는 단계; 및 상기 압출물을 두개의 맞물린 냉각드럼 사이로 주입하여 냉각드럼을 통과시키는 단계를 포함하는 방수용 폴리우레탄 고무쉬트의 제조방법을 제공한다.In order to achieve the above object, in the present invention, 100 parts by weight of a polyurethane foam pulverized product, 2-3 parts by weight of chlorinated polyethylene, 2-3 parts by weight of ethylene glycol or butylene glycol and 2-3 parts by weight of barium sulfate (BaSO 4 ) Adding and mixing the composition by adding a pelletized composition having a composition; Pelletizing the mixture by extracting at a temperature in the range of 130-170 ° C .; To the obtained pellet, 2 to 4 parts by weight of chlorinated polyethylene, 1-3 parts by weight of barium sulfate, 0.5 to 2.5 parts by weight of zinc stearate, 2.5 parts by weight of clay, and talc powder 2.5 to 100 parts by weight of the pellets. Adding and mixing a polyurethane rubber sheet composition having a composition part by weight and extruding at a temperature range of 130 to 160 ° C .; And injecting the extrudate between two interlocking cooling drums to pass the cooling drums.

본 발명에서 원료로서 사용하는 폴리우레탄 포옴은 기존 제품의 폐품을 사용하는 것이 가능한데, 바람직하게는 신발공장에서 버려지는 신발창 불량품이 적용될 수 있다. 그런데 이는 열경화성 수지이므로 열에 의해 용융되지 않는다. 따라서 적절한 크기로 분쇄하여 몇가지 화학물질로 이루어진 펠렛트화 조성물을 가하고 열을 가하여 1차적으로 펠렛트화한 다음, 이 펠렛트에 다시 몇가지 화학물질로 이루어진 폴리우레탄 고무쉬트 조성물을 가하고 열을 가하여 고무쉬트를 제조하도록 한 것이다.Polyurethane foam used as a raw material in the present invention is possible to use the waste products of the existing product, preferably the defective soles discarded in the shoe factory can be applied. However, since it is a thermosetting resin, it is not melted by heat. Therefore, it is pulverized to an appropriate size, and a pelletized composition composed of several chemicals is added, and the pellets are primarily pelletized by applying heat. Then, the polyurethane rubber sheet composition composed of several chemicals is added to the pellet and heated to apply a rubber sheet. It was made to manufacture.

펠렛트화 조성물은 폴리우레탄 포옴 분쇄물 100중량부에 대하여 염소화 폴리에틸렌 2-3중량부, 에틸렌 글리콜 또는 부틸렌 글리콜 2-3중량부 및 황산바륨 2-3중량부를 포함하여 이루어지며, 폴리우레탄 고무쉬트 조성물은 펠렛트 100중량부에 대하여 염소화 폴리에틸렌 2-4중량부, 황산바륨 1-3중량부, 스테아린산 아연 0.5-2.5중량부, 점토 2.5중량부를 포함하여 이루어진다.The pelletized composition comprises 2-3 parts by weight of chlorinated polyethylene, 2-3 parts by weight of ethylene glycol or butylene glycol and 2-3 parts by weight of barium sulfate based on 100 parts by weight of the polyurethane foam pulverized product, and a polyurethane rubber sheet. The composition comprises 2-4 parts by weight of chlorinated polyethylene, 1-3 parts by weight of barium sulfate, 0.5-2.5 parts by weight of zinc stearate, and 2.5 parts by weight of clay, based on 100 parts by weight of pellets.

상기 폴리우레탄 포옴은 적절한 크기로 분쇄하되, 잘게 분쇄할수록 우수한 물성을 갖는 고무쉬트가 얻어지게 된다.The polyurethane foam is ground to an appropriate size, but finely pulverized, a rubber sheet having excellent physical properties is obtained.

상기한 본 발명에 따른 방법에서 펠렛트화 조성물과 폴리우레탄 고무쉬트 조성물로서 첨가되는 염소화 폴리에틸렌은 폴리우레탄 포옴과 상용성이 좋고 내후성 즉, 내일광성, 내오존성, 내산화성이 우수하며 특히 열화에 의한 폴리우레탄 수지의 황변 방지에 도움을 주는 성분이다.The chlorinated polyethylene added as a pelletized composition and polyurethane rubber sheet composition in the process according to the present invention described above has good compatibility with the polyurethane foam and is excellent in weather resistance, namely, sun resistance, ozone resistance, and oxidation resistance, and particularly poly by deterioration. A component that helps prevent yellowing of urethane resins.

또한 황산바륨은 폴리우레탄 포옴으로부터 제조되는 고무쉬트에 열안정성을 부여함과 동시에 고무 특성을 갖도록 하는 가황기능을 갖는다.In addition, barium sulfate has a vulcanizing function to impart thermal stability to the rubber sheet made from the polyurethane foam and to have rubber properties.

에틸렌글리콜 또는 부틸렌글리콜은 열화된 우레탄 포옴을 재가교시키는 가교제로서 우레탄 본래의 특성을 보강시키고 스테아린산 아연은 안정제로서의 역할은 물론 접착성이 큰 폴리우레탄의 성형가공에 이형성을 부여하여 작업성을 향상시키는 역할을 한다.Ethylene glycol or butylene glycol is a crosslinking agent that re-crosslinks the deteriorated urethane foam, reinforcing the inherent properties of urethane, and zinc stearate not only serves as a stabilizer, but also provides mold release properties for highly adhesive polyurethanes to improve workability. It plays a role.

점토와 활석분은 화합물의 첨가로 열용융에 의해 유동성이 커진 폴리우레탄 수지의 유동성을 감소시켜 판상의 고무쉬트로의 성형가공을 용이하게 해준다.The clay and the talc powder reduce the fluidity of the polyurethane resin, which has become more fluidized by thermal melting due to the addition of the compound, thereby facilitating the molding process into the plate-like rubber sheet.

이상과 같은 본 발명의 방법은 펠렛트화를 거쳐 평판의 고무쉬트를 성형하는 2단계 공정으로 이루어져 있기 때문에 가황 및 가교가 충분히 이루어지게 되어 얻어지는 제품이 균질하고 제품의 물성이 우수하다. 즉, 열화된 폴리우레탄 포옴을 재가교시킴으로써 폴리우레탄 본래의 특성을 보강시켜 주어 물성이 우수한 제품을 얻을 수 있는 것이다.Since the method of the present invention as described above consists of a two-step process of molding the rubber sheet of the plate through pelletization, the product obtained by being fully vulcanized and crosslinked is homogeneous and has excellent physical properties of the product. In other words, by re-crosslinking the deteriorated polyurethane foam to reinforce the original characteristics of the polyurethane to obtain a product excellent in physical properties.

이상과 같이 2단계 공정을 거쳐 성형된 폴리우레탄 고무쉬트는 폴리우레탄의 특성인 내약품성, 내마모성, 우수한 인열, 인장강도, 신장율 등을 보유하고, 영하의 기온에서도 150% 이상의 신장율을 유지한다.The polyurethane rubber sheet molded through the two-step process as described above possesses the characteristics of polyurethane, such as chemical resistance, abrasion resistance, excellent tear, tensile strength, elongation, and maintains elongation of 150% or more even at temperatures below zero.

폴리우레탄 고무쉬트의 물리, 화학적 특성은 KSF 4911(합성 고분자 루핑 쉬트)의 시험 규정에 명시되어 있는 바, 시험결과에 따르면 모든 시험항목에서 KSF 4911의 규정치보다 2~5배 정도 우수한 성능을 보유하고 있음을 나타내고 있다. 시험결과 하기 표 1에 나타낸다.The physical and chemical properties of polyurethane rubber sheets are specified in the test regulations of KSF 4911 (synthetic polymer roofing sheets), and according to the test results, they have 2 to 5 times better performance than those of KSF 4911 in all test items. It is present. The test results are shown in Table 1 below.

특히 원료로서 폴리우레탄 포옴을 사용하기 때문에, 이는 폐기되는 물품을 재활용한다는 차원에서 자원을 재창출하는 효과를 가져와 환경적인 면이나 경제적인 면에서 매우 유리한 것이다. 더욱이 본 발명의 방법에 따라 얻어지는 폴리우레탄 고무쉬트는 기존의 방수용 재료에 비해 물성이 우수하기 때문에 특히 건축재료로서 용이하게 사용할 수 있는 것이다.In particular, since polyurethane foam is used as a raw material, this has the effect of re-creating resources in terms of recycling the discarded goods, which is very advantageous in terms of environment and economy. Moreover, the polyurethane rubber sheet obtained according to the method of the present invention can be easily used especially as a building material because it has superior physical properties compared to existing waterproofing materials.

Claims (1)

폴리우레탄 포옴 분쇄물 100중량부에, 염소화 폴리에틸렌 2-3중량부, 에틸렌글리콜 또는 부틸렌 글리콜 2-3중량부 및 황상바륨 2-3중량부의 조성을 갖는 펠렛트화 조성물을 첨가하여 혼합하는 단계; 상기 혼합물을 130-170℃ 온도 범위에서 압출함으로써 펠레트화 하는 단계; 얻어지는 펠레트에, 상기 펠레트 100중량부에 대하여 염소화 폴리에틸렌 2-4중량부, 황산바륨 1-3중량부, 스테아린산 아연 0.5-2.5중량부, 점토 2.5중량부 및 활석분 2.5중량부의 조성비를 갖는 폴리우레탄 고무쉬트 조성물을 첨가하여 혼합하고 130-160℃ 온도 범위에서 압출하는 단계; 및 상기 압출물을 두개의 맞물린 냉각드럼 사이로 주입하여 냉각드럼을 통과시키는 단계를 포함하는 방수용 폴리우레탄 고무쉬트의 제조방법.Adding and mixing a pelletizing composition having a composition of 2-3 parts by weight of chlorinated polyethylene, 2-3 parts by weight of ethylene glycol or butylene glycol, and 2-3 parts by weight of barium sulfate, to 100 parts by weight of the polyurethane foam pulverized product; Pelletizing the mixture by extruding in a temperature range of 130-170 ° C .; The resulting pellets have a composition ratio of 2-4 parts by weight of chlorinated polyethylene, 1-3 parts by weight of barium sulfate, 0.5-2.5 parts by weight of zinc stearate, 2.5 parts by weight of clay and 2.5 parts by weight of talc, based on 100 parts by weight of the pellets. Adding and mixing the polyurethane rubber sheet composition and extruding in a temperature range of 130-160 ° C .; And injecting the extrudate between two interlocking cooling drums to pass the cooling drums.
KR1019920012402A 1992-07-13 1992-07-13 The process for the preparation of waterproof polyurethane rubber sheet from polyurethane foam KR970009392B1 (en)

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KR1019920012402A KR970009392B1 (en) 1992-07-13 1992-07-13 The process for the preparation of waterproof polyurethane rubber sheet from polyurethane foam

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