KR20120090708A - Method for preparing non-shrinking polyurethane foam - Google Patents
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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Abstract
Description
본 발명은 무수축 폴리우레탄 발포체의 제조방법에 관한 것으로, 자동차의 시트 패드에 사용될 수 있는 연질 폴리우레탄 발포체의 제조방법에 관한 것이다.
The present invention relates to a method for producing a non-shrinkable polyurethane foam, and to a method for producing a flexible polyurethane foam that can be used in a seat pad of an automobile.
연질 시트 패드 발포체는 제조 방식에 따르 콜드큐어(cold cure) 몰드 발포체와 하드큐어(hard cure) 몰드 발포체로 구분된다. 하드큐어 몰드 발포체는 몰드 내에서 화학적인 작용에 의해 자연적으로 발포된 셀이 오픈되어 탈형 후에 인위적으로 셀을 오픈시키는 공정이 필요 없지만, 콜드큐어 몰드 발포체는 닫힌 구조의 셀을 형성하기 때문에 탈형 후 인위적인 셀 오픈 작업(크러싱)이 필요하다.Soft seat pad foams are classified into cold cure mold foams and hard cure mold foams according to the manufacturing method. Hard cure mold foam does not require the process of artificially opening the cell after demolding by opening the cell naturally foamed by chemical action in the mold, but since the cold cure mold foam forms a cell of closed structure, it is artificial after demolding. Cell open work (crushing) is required.
자동차용 시트 패드는 대부분 콜드 큐어(cold cure) 연질 우레탄 폼 제조 방식으로 생산되는데, 50~70℃의 비교적 높은 온도의 몰드에 원액을 주입하여 50~70℃의 비교적 낮은 온도에서 발포체를 경화시키는 생산 방식으로 원료의 특성상 탈형된 발포체는 일정량의 닫힌 구조의 셀을 함유하고 이러한 닫힌 구조의 셀은 가스가 빠져 나가면서 발포체의 수축을 야기시킨다. (도 1 참조) 따라서 이러한 수축을 방지하기 위해서는 발포체보다 좁은 간격의 틀 사이에 발포체를 통과시켜 크러싱하는 방법과 발포체에 진공을 걸어 크러싱하는 방법을 사용한다. Most of car seat pads are produced by cold cure soft urethane foam manufacturing method, injecting stock solution into mold of 50 ~ 70 ℃ relatively high temperature to cure foam at relatively low temperature of 50 ~ 70 ℃ The foam demolded in the nature of the raw material in such a manner contains a certain amount of closed structured cells, which cause the shrinkage of the foam as the gas escapes. (See Fig. 1) Therefore, in order to prevent such shrinkage, a method of passing the foam through a narrow spaced frame than the foam and crushing by applying a vacuum to the foam.
이와 같은 통상의 연질 콜드큐어 몰드 발포체는 크러싱 공정을 거쳐야 하기 때문에 작업 시간이 오래 걸리고, 크러싱 머신 작동을 위한 공간, 전력, 인력 등 비용이 과다하게 발생하며, 크러싱 작업 후에 발포체의 찢김 등 불량이 발생하는 문제점이 있었다. (도 2 참조) Since such a normal cold cure mold foam has to go through a crushing process, it takes a long time, excessive space, power, manpower, etc. for operating the crushing machine, and tearing of the foam after crushing. There was a problem that a defect occurs. (See Figure 2)
이러한 문제를 해결하기 위해 본 출원인은 대한민국 등록 특허 제030328호에서 레진 프리믹스와 유기폴리이스시아네이트를 반응시켜 별도의 크러싱 공정을 필요로 하지 않고 몰드 내에서 화학적인 작용에 의해 자연적으로 크러싱된 연질 우레탄 몰드 발포체는 제조할 수 있는 방법을 제시한 바 있다. In order to solve this problem, the applicant reacts with the resin premix and organopolyisocyanate in the Republic of Korea Patent No. 030328, which is naturally crushed by chemical action in the mold without requiring a separate crushing process. Flexible urethane mold foams have been presented a method that can be produced.
그러나 상기 특허에서는 밀도범위 45~55 kg/m3의 시트쿠션에 대해서는 크러시어빌리티(crushability)가 낮아 크러싱이 없이도 제조가 가능하나, 밀도가 낮은 범위인 35~45 kg/m3에 대해서는 크러시어빌리티가 비교적 높아 크러싱 공정을 배제하기 어려웠다. However, in the above patent, the crushability of the seat cushion in the density range of 45 to 55 kg / m 3 can be manufactured without crushing, but the crushability for the low density range of 35 to 45 kg / m 3 can be manufactured. Is relatively high and it is difficult to exclude the crushing process.
또한 기존의 방법으로는 시트 쿠션의 경우는 밀도범위가 높아 생산하는데 큰 불량이 발생하지 않았으나, 시트 백의 경우는 밀도가 낮고 금형 형상이 얇고 복잡하여 상대적으로 불량이 많이 발생하였다. 따라서 낮은 밀도 범위를 갖는 시트 백(seat back)이나 암 레스트(arm rest)에 적용하기에는 한계가 있어 이 부분에 대한 보완 기술이 필요하였다.
In addition, in the conventional method, the seat cushion has a high density range, and thus a large defect does not occur. However, the seat back has a low density, a mold shape is thin and complex, and a relatively large defect occurs. Therefore, there is a limit to apply to a seat back or an arm rest having a low density range, and thus, a complementary technique is required.
이에, 본 발명자들은 저 밀도 범위에서도 크러싱이 필요 없는 기술을 개발하기 위해 노력한 결과, 특정 분자량 및 OH가를 갖는 폴리올을 레진 프리믹스에 포함시켜 사용함으로써 이러한 목적을 달성할 수 있음을 발견하였다.Accordingly, the present inventors have tried to develop a technique that does not require crushing even in the low density range, and found that this object can be achieved by using a polyol having a specific molecular weight and OH number in the resin premix.
따라서 본 발명은 넓은 범위의 밀도 영역에서 크러싱이 필요 없는 무수축 폴리우레탄 발포체의 제조방법을 제공하는 것을 그 목적으로 한다.
It is therefore an object of the present invention to provide a process for producing a non-shrinkable polyurethane foam which does not require crushing in a wide range of density ranges.
상기 목적을 달성하기 위하여 본 발명은 The present invention to achieve the above object
(1) a. 중량평균분자량이 6,000~10,000이고 OH값이 25~30 mg KOH/g인 폴리에테르폴리올 또는 폴리에스테르폴리올 40~70중량%, (1) a. 40 to 70% by weight of a polyether polyol or polyester polyol having a weight average molecular weight of 6,000 to 10,000 and an OH value of 25 to 30 mg KOH / g,
b. 중량평균분자량이 6,000~10,000이고 OH값이 20~24 mg KOH/g인 폴리에테르폴리올 또는 폴리에스테르폴리올 10~30중량%, b. 10-30 wt% of a polyether polyol or polyester polyol having a weight average molecular weight of 6,000 to 10,000 and an OH value of 20 to 24 mg KOH / g,
c. 중량평균분자량이 3,000~6,000이고 OH값이 30~60 mg KOH/g인 폴리에테르폴리올 또는 폴리에스테르폴리올 0~20중량% 및c. 0-20 wt% of a polyether polyol or polyester polyol having a weight average molecular weight of 3,000 to 6,000 and an OH value of 30 to 60 mg KOH / g and
d. 중량평균분자량이 6,000~10,000이고 OH값이 20~30 mg KOH/g인 폴리에테르폴리올 또는 폴리에스테르폴리올에 아크릴로니트릴, 스티렌 또는 그 혼합물이 분산 또는 그라프트된 폴리머폴리올 10~40중량%d. 10 to 40% by weight of polymer polyol in which acrylonitrile, styrene or a mixture thereof is dispersed or grafted in a polyether polyol or polyester polyol having a weight average molecular weight of 6,000 to 10,000 and an OH value of 20 to 30 mg KOH / g
를 포함하는 폴리올 레진 프리믹스 100 중량부; 100 parts by weight of a polyol resin premix comprising;
(2) 이소시아네이트 30 ~ 70 중량부; 및 (2) 30 to 70 parts by weight of isocyanate; And
(3) 발포제 1~10 중량부(3) 1 to 10 parts by weight of blowing agent
를 혼합한 조성물을 반응시켜 제조하는 것을 특징으로 하는 폴리우레탄 발포체의 제조방법을 제공한다.
It provides a method for producing a polyurethane foam, characterized in that to produce a mixture by reacting the mixture.
기존 넌크러싱(Non-crushing) 시스템은 밀도 45~55 kg/m3에서 국한되어 있었으며 시트 쿠션 부분에 한정이 되어 생산되고 있었으나, 본 발명에 따른 방법은 넓은 밀도 범위에서 사용이 가능하므로 시트 쿠션, 시트 백 생산라인을 통합함으로 원료관리를 효율적으로 할 수 있으며 생산불량을 감소시켜 기존 시트 패드 대비 생산성을 향상할 수 있다. 본 발명의 특수한 효과를 자세히 설명하면 하기와 같다.Existing non-crushing system (Non-crushing) system was limited to a density of 45 ~ 55 kg / m 3 and was produced to be limited to the seat cushion portion, but the method according to the present invention can be used in a wide density range seat cushion, By integrating the sheet back production line, raw material can be managed efficiently and productivity can be improved compared to existing sheet pads by reducing production defects. The special effects of the present invention will be described in detail as follows.
첫째로, 원료관리에 대한 효율화를 통하여 설비보수 및 품질 불량발생으로 인한 비용을 절감 할 수 있다. 자동차 업체의 시트 쿠션과 시트 백을 생산하는 데 있어서 여러 종류의 원료를 업체마다 사용하고 있으며 이로 인한 저장탱크, 배합탱크 등의 설비관리, 원료에 대한 입고, 품질관리의 문제 등이 수시로 발생하게 된다. 이를 개선하기 위하여 본 발명은 원료를 아이소시아네이트 1종류, 레진프리믹스 1종류를 사용하여 밀도분포가 30 ~ 55 kg/m3까지 다양한 시트 쿠션, 시트 백을 1개의 생산 라인에서 동시에 생산할 수 있다. First, the cost of maintenance and quality defects can be reduced through efficient management of raw materials. In producing seat cushions and seat backs of automobile companies, various types of raw materials are used by each company, which causes problems such as management of storage tanks, mixing tanks, receipt of raw materials, and quality control. . In order to improve this, the present invention can produce a variety of seat cushions, seat bags up to 30 ~ 55 kg / m 3 at the same time in one production line by using one type of isocyanate, one type of resin premix.
둘째로, 원료투입량을 임의로 조절 할 수 있어 생산비용을 절감 할 수 있다. 동일한 경도를 유지하면서 원료투입량(충진량 및 주입비(Packing Ratio))을 생산자가 자유롭게 생산 조건에 맞게 조절할 수 있다. 이로 인해 클로즈드 셀(Closed Cell) 과다로 인한 수축, 찢김, 주름, 보이드(Void) 등의 불량을 개선할 수 있는 장점이 있어 생산성 향상에 따른 원가 절감을 할 수 있다. Second, raw material input can be adjusted arbitrarily, which can reduce production costs. While maintaining the same hardness, the raw material input amount (filling amount and packing ratio) can be freely adjusted by the producer to the production conditions. As a result, there is an advantage of improving defects such as shrinkage, tearing, wrinkles, voids, etc. due to excessive closed cells, thereby reducing the cost of productivity.
셋째로, 설비보수 및 유지비용 절감 및 계절변화에 따른 품질 트러블을 줄일 수 있다. 본 발명에 따른 방법은 시트패드 생산 시 자연적으로 발생되는 수축을 처리하고자 사용하는 설비(Crushing and Vacuum Roller)를 사용하지 않고 생산할 수 있는 강점이 있으며 Crushing and Vacuum Roller를 사용하지 않으므로 생산 작업공간을 최대한 활용할 수 있고 설비보수 및 유지비용도 절감할 수 있으며 시트패드 생산 시 생산 리드 타임(Lead Time(탈형공정→사상공정))도 단축시킬 수 있다.
Third, it is possible to reduce equipment maintenance and maintenance costs and to reduce quality problems caused by seasonal changes. The method according to the present invention has advantages in that it can be produced without the use of a facility (Crushing and Vacuum Roller) used to handle shrinkage that occurs naturally in sheet pad production, and does not use a Crushing and Vacuum Roller to maximize the production workspace. In addition, it can reduce equipment maintenance and maintenance costs and shorten the production lead time (dead process → ideological process) in sheet pad production.
도 1은 종래의 제조방법에 따라 제조된 폴리우레탄 발포체가 성형 후 수축하여 변형을 일으키는 모습과 본 발명에 따른 폴리우레탄 발포체가 성형 후에도 수축에 따른 변형이 없는 것을 비교하여 나타낸 사진이다.
도 2는 종래의 제조방법에 따라 제조된 폴리우레탄 발포체가 크러싱 작업 후에 발포체의 찢김 등 불량이 발생하는 모습과 본 발명에 따른 폴리우레탄 발포체가 크러싱 작업이 필요 없어 불량이 없는 모습을 비교하여 나타낸 사진이다.
도 3은 종래의 방법에 따라 제조된 폴리우레탄 발포체가 크러싱 작업 후에 폴리우레탄 셀이 찢겨 깨진 것을 나타내는 SEM 사진과 본 발명에 따라 제조된 폴리우레탄 발포체의 셀이 유지되고 있음을 비교하여 나타낸 SEM 사진이다.1 is a photograph showing that the polyurethane foam prepared according to the conventional manufacturing method shrinks after molding to cause deformation and that the polyurethane foam according to the present invention does not have deformation due to shrinkage even after molding.
Figure 2 is a polyurethane foam prepared according to the conventional manufacturing method compared to the appearance that the defects such as tearing of the foam after the crushing operation and the polyurethane foam according to the present invention does not need the crushing operation there is no defect The picture shown.
3 is a SEM photograph showing that the polyurethane foam prepared according to the conventional method is torn and broken polyurethane cells after the crushing operation and the SEM photograph showing that the cells of the polyurethane foam prepared according to the present invention are maintained. to be.
이와 같은 본 발명을 상세하게 설명을 하면 다음과 같다.The present invention will be described in detail as follows.
본 발명의 무수축 폴리우레탄 발포체의 제조방법은The manufacturing method of the non-shrinkable polyurethane foam of the present invention
(1) a. 중량평균분자량이 6,000~10,000이고 OH값이 25~30 mg KOH/g인 폴리에테르폴리올 또는 폴리에스테르폴리올 40~70중량%, (1) a. 40 to 70% by weight of a polyether polyol or polyester polyol having a weight average molecular weight of 6,000 to 10,000 and an OH value of 25 to 30 mg KOH / g,
b. 중량평균분자량이 6,000~10,000이고 OH값이 20~24 mg KOH/g인 폴리에테르폴리올 또는 폴리에스테르폴리올 10~30중량%, b. 10-30 wt% of a polyether polyol or polyester polyol having a weight average molecular weight of 6,000 to 10,000 and an OH value of 20 to 24 mg KOH / g,
c. 중량평균분자량이 3,000~6,000이고 OH값이 30~60 mg KOH/g인 폴리에테르폴리올 또는 폴리에스테르폴리올 0~20중량% 및c. 0-20 wt% of a polyether polyol or polyester polyol having a weight average molecular weight of 3,000 to 6,000 and an OH value of 30 to 60 mg KOH / g and
d. 중량평균분자량이 6,000~10,000이고 OH값이 20~30 mg KOH/g인 폴리에테르폴리올 또는 폴리에스테르폴리올에 아크릴로니트릴, 스티렌 또는 그 혼합물이 분산 또는 그라프트된 폴리머폴리올 10~40중량%d. 10 to 40% by weight of polymer polyol in which acrylonitrile, styrene or a mixture thereof is dispersed or grafted in a polyether polyol or polyester polyol having a weight average molecular weight of 6,000 to 10,000 and an OH value of 20 to 30 mg KOH / g
를 포함하는 폴리올 레진 프리믹스 100 중량부; 100 parts by weight of a polyol resin premix comprising;
(2) 이소시아네이트 30 ~ 70 중량부; 및 (2) 30 to 70 parts by weight of isocyanate; And
(3) 발포제 1~10 중량부(3) 1 to 10 parts by weight of blowing agent
를 혼합한 조성물을 반응시켜 제조하는 것을 그 특징으로 한다.
It is characterized by producing by reacting the mixed composition.
폴리우레탄 수지는 기본적으로 폴리올 화합물과 이소시아네이트 화합물을 반응시켜 우레탄 결합을 형성함에 의해 제조한다. Polyurethane resins are basically prepared by reacting a polyol compound with an isocyanate compound to form a urethane bond.
본 발명의 구성성분은 상기 (1) 폴리올 레진 프리믹스, (2) 이소시아네이트 및 (3) 발포제로 구성된다. The component of this invention consists of said (1) polyol resin premix, (2) isocyanate, and (3) blowing agent.
이 중에서 상기 폴리올 레진 프리믹스는 본 발명에서는 4성분의 혼합물 형태로 사용하는 것이 특징이다. 즉, a~d 성분을 특정 함량으로 혼합 사용한다. 이 때 상기 폴리에테르폴리올과 폴리에스테르폴리올은 폴리올 프리믹스를 구성하는 성분으로서 균등하게 사용될 수 있으며, 단독 또는 혼합물 형태로 사용될 수 있다. 이 중 폴리에테르폴리올은 에틸렌글리콜, 글리세린, 트리에탄올아민, 펜타에리스리톨, 톨루엔디아민, 에틸렌디아민, 디아미노디페닐메탄, 솔비톨 및 설탕으로 이루어진 군에서 선택된 1종 이상의 개시제를 사용하여 프로필렌옥사이드와 에틸렌옥사이드를 부가중합시켜 얻어진 폴리에테르폴리올을 사용하는 것이 바람직하고, 상기 폴리에스테르폴리올은 테레프탈산, 에틸렌아디프산, 부틸렌아디프산, 1,6-헥산다이프산, 디에틸렌아디프산 및 프탈산으로 이루어진 군에서 선택된 1종 이상과 1,4-부탄디올 및 에틸렌글리콜로 이루어진 군에서 선택된 1종 이상을 탈수 축합하여 얻어진 폴리에스테르폴리올을 사용하는 것이 바람직하나, 반드시 이에 한정하는 것은 아니고 본 발명이 속하는 기술분야에서 사용가능한 폴리에테르폴리올 및 폴리에스테르폴리올은 다양하게 이용될 수 있다. Among these, the polyol resin premix is characterized in that it is used in the form of a mixture of four components in the present invention. That is, the a to d components are mixed and used in a specific content. At this time, the polyether polyol and polyester polyol may be used as a component constituting the polyol premix, and may be used alone or in a mixture form. Among these, the polyether polyol may be selected from propylene oxide and ethylene oxide using at least one initiator selected from the group consisting of ethylene glycol, glycerin, triethanolamine, pentaerythritol, toluenediamine, ethylenediamine, diaminodiphenylmethane, sorbitol, and sugar. It is preferable to use the polyether polyol obtained by addition polymerization, and the polyester polyol is a group consisting of terephthalic acid, ethylene adipic acid, butylene adipic acid, 1,6-hexanedipic acid, diethylene adipic acid and phthalic acid. It is preferable to use a polyester polyol obtained by dehydrating one or more selected from the group consisting of one or more selected from 1,4-butanediol and ethylene glycol, but is not necessarily limited thereto. Polyetherpolyols and polyesterpolys available It can be widely used.
본 발명에 있어서, 상기 혼합 조성물에는 가교제, 촉매 및 계면활성제로 이루어진 군에서 선택된 1종 이상의 첨가제가 더 포함될 수 있다. 상기 첨가제는 주로 폴리올 레진 프리믹스에 포함되어 있다가 혼합시 조성물에 포함되는 것이 일반적이나, 이소시아네이트 또는 발포제에 포함되어 있다가 혼합되는 것도 본 발명의 범위에서 배제되지 않는다. In the present invention, the mixed composition may further include at least one additive selected from the group consisting of a crosslinking agent, a catalyst and a surfactant. The additives are generally included in the polyol resin premix and then included in the composition upon mixing, but the additives included in the isocyanate or blowing agent and then mixed are not excluded from the scope of the present invention.
본 발명에서 상기 가교제는 글리콜계 또는 아민계를 사용할 수 있으며, 에틸렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 디프뢸렌글리콜, 1,4-부탄디올, 1,6-헥산디올, 펜타에리트리톨, 디에탄올아민, 트링탄올아민, 에틸렌디아민, 트리에틸렌테트라아민, 메틸렌오르토클로로아닐린, 4,4-디페닐메탄디아민, 2,6-디클로로-4,4-디페닐메탄디아민, 2,4-톨루엔디아민 및 2,6-톨루엔디아민 중에서 선택될 수 있으나, 반드시 이에 한정하는 것은 아니다. 상기 가교제는 전체 혼합 조성물에 대하여 0.001~10 중량%로 사용되는 것이 바람직하고, 더욱 바람직하게는 0.01~5 중량%이다. In the present invention, the crosslinking agent may use a glycol-based or amine-based, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, pentaerythritol, diethanol Amines, tritanolamines, ethylenediamine, triethylenetetraamine, methyleneorthochloroaniline, 4,4-diphenylmethanediamine, 2,6-dichloro-4,4-diphenylmethanediamine, 2,4-toluenediamine and It may be selected from 2,6-toluenediamine, but is not necessarily limited thereto. The crosslinking agent is preferably used at 0.001 to 10% by weight, more preferably 0.01 to 5% by weight, based on the total mixed composition.
본 발명에 있어서, 상기 촉매는 폴리우레탄 발포체의 제조에 통상적으로 사용되는 것을 이용하는 것이 가능하고, 특별히 한정하지는 않으나, 예를 들어 아민 촉매로 트리에틸렌디아민, 비스디에틸아미노에틸에테르, 트리프로필아민, 트리이소프로판올아민, 트리부틸아민, 트리에틸아민, N-메틸모폴린, 디에틸렌트리아민비스 (2-(N,N-디에틸아미노)에틸)에테르 및 이들의 염 중에서 선택될 수 있으나, 반드시 이에 한정하는 것은 아니다. 상기 촉매는 전체 혼합 조성물에 대하여 0.001~10 중량%로 사용되는 것이 바람직하며, 더욱 바람직하게는 0.01~5중량%이다.In the present invention, the catalyst can be used that is commonly used in the production of polyurethane foam, and is not particularly limited, for example, triethylenediamine, bisdiethylaminoethyl ether, tripropylamine, Triisopropanolamine, tributylamine, triethylamine, N-methylmorpholine, diethylenetriaminebis (2- (N, N-diethylamino) ethyl) ether and salts thereof, but not necessarily It is not limited. The catalyst is preferably used in 0.001 to 10% by weight, more preferably 0.01 to 5% by weight based on the total mixture composition.
본 발명에 있어서, 상기 계면활성제는 폴리우레탄 발포체의 제조에 통상적으로 사용되는 것을 이용하는 것이 가능하고, 특별히 한정하지는 않으나, 유기규소 계면활성제를 사용할 수 있다. 상기 계면활성제는 전체 혼합 조성물에 대하여 0.001~10 중량%로 사용되는 것이 바람직하고, 더욱 바람직하게는 0.01~5 중량%이다. In the present invention, the surfactant can be used that is commonly used in the production of polyurethane foam, and is not particularly limited, an organosilicon surfactant can be used. The surfactant is preferably used in 0.001 to 10% by weight, more preferably 0.01 to 5% by weight based on the total mixture composition.
본 발명에 있어서, 상기 (1). d의 폴리머폴리올에 분산 또는 그라프트된 아크릴로니트릴, 스티렌 또는 그 혼합물의 양은 40중량% 이하의 범위에서 사용될 수 있고, 바람직하게는 0.1~40중량%이다. In the present invention, the above (1). The amount of acrylonitrile, styrene or mixture thereof dispersed or grafted in the polymer polyol of d may be used in the range of 40% by weight or less, preferably 0.1 to 40% by weight.
본 발명에 있어서, 상기 (2) 이소시아네이트는 폴리우레탄 발포체의 제조에 통상적으로 사용되는 것을 이용하는 것이 가능하고, 특별히 한정하지는 않으나, 예를 들어, 폴리머릭 디페닐메탄디이소시아네이트, 모노머릭 디페닐메탄디이소시아네이트, 변성 디페닐메탄디이소시아네이트, 톨루엔디이소시아네이트 및 변성 톨루엔디이소시아네이트로 이루어진 군에서 선택된 1종 이상이 사용될 수 있다.In the present invention, the (2) isocyanate can be used that is commonly used for the production of polyurethane foam, and is not particularly limited, for example, polymeric diphenylmethane diisocyanate, monomeric diphenylmethane di At least one selected from the group consisting of isocyanate, modified diphenylmethane diisocyanate, toluene diisocyanate and modified toluene diisocyanate may be used.
본 발명에 있어서 발포제는 물을 사용하는 것이 바람직하나, 일반적인 물리적 발포제인 프레온류(CFC, HCFC, HFC 등), 펜탄류(시클로펜탄 등) 등을 사용하는 것을 배제하지는 않는다. 다만, 상기 프레온류는 오존층을 파괴하는 성질이 있어 전 세계적으로 사용이 규제되고 있고, 상기 펜탄류는 공기 중 소량만 존재해도 폭발하는 특성이 있어 폭발 방지를 위한 막대한 설비 투자가 필요하므로 바람직하지는 않다.In the present invention, it is preferable to use water as the blowing agent, but the use of freons (CFC, HCFC, HFC, etc.), pentanes (cyclopentane, etc.), which are general physical blowing agents, is not excluded. However, since the freon has a property of destroying the ozone layer, its use is regulated worldwide, and the pentane is explosive even when only a small amount is present in the air. .
본 발명에는 필요에 따라 각종 안정제, 충진제, 착색제, 난연제, 항균제 등의 첨가제를 추가로 포함시키는 것도 가능하다. If necessary, additives such as various stabilizers, fillers, colorants, flame retardants, and antibacterial agents may be further included in the present invention.
통상적인 폴리우레탄 발포체의 제조 공정에는 폴리올과 이소시아네이트의 반응 과정에서 생성된 클로즈드 셀(closed cell)을 개방시켜 통기성을 확보하기 위하여 기포개환제가 사용되는 것이 일반적이나, 본 발명에서는 자체로 통기성이 확보되기 때문에 이러한 기포개환제를 사용하지 않고서도 생산이 가능하다. In a conventional polyurethane foam manufacturing process, a bubble opening agent is generally used to open a closed cell generated during the reaction of a polyol and an isocyanate to secure air permeability, but in the present invention, air permeability is ensured by itself. As a result, it is possible to produce the product without using such a bubble opener.
본 발명에서는 상기와 같은 폴리올 레진 프리믹스와 이소시아네이트, 발포제 및 각종 첨가제가 혼합된 혼합 조성물을 40~100℃로 가열된 몰드에 주입하여 반응시킴에 의해 제조한다. 반응시간은 약 1~10분 정도 소요되며, 몰드에는 필요에 따라 프레임(frame), 이형 필름 등을 넣고 성형할 수도 있다. 이 때 더욱 바람직한 몰드의 온도는 40~80℃이고 더욱 바람직한 반응시간은 3~8분이다. In the present invention, the polyol resin premix and the isocyanate, blowing agent, and various additives are prepared by injecting a mixed composition into a mold heated at 40 to 100 ° C and reacting. The reaction time is about 1 to 10 minutes, and may be molded into a mold (frame), a release film, etc., if necessary. At this time, the temperature of a more preferable mold is 40-80 degreeC, and more preferable reaction time is 3-8 minutes.
발포체를 제조하는데 통상적으로 인덱스라는 용어를 사용하는데 여기서 인덱스란 레진 프리믹스 중에 함유된 활성수소기를 가진 화합물의 당량과 이 활성수소와 반응하는 이소시아네이트의 화학양론적량에 대한 지수이다. 이는 폴리올, 가교제 등이 아이소시아네이트(NCO기)와 반응하여 얻은 활성수소기의 양에 필요한 아이소시아네이트기의 량(화학양론적 양)에 대한 지수이다. 예를 들면, 활성수소기의 량에 상당하는 아이소시아네이트가 사용된 경우의 아이소시아네이트 인덱스는 1.00이고 아이소시아네이트량이 95%중량%이면 0.95이다. The term index is commonly used to prepare foams, where the index is an index of the equivalent of the compound with active hydrogen groups contained in the resin premix and the stoichiometric amount of isocyanate reacting with the active hydrogen. This is an index for the amount (stoichiometric amount) of isocyanate groups required for the amount of active hydrogen groups obtained by reaction of polyols, crosslinkers and the like with isocyanates (NCO groups). For example, the isocyanate index when an isocyanate corresponding to the amount of the active hydrogen group is used is 1.00 and 0.95 if the amount of isocyanate is 95% by weight.
이러한 이소시아네이트 인덱스는 다음 식에 의하여 계산된다. This isocyanate index is calculated by the following formula.
<식 1><Formula 1>
레진 프리믹스 중에 활성수소기를 가지고 있는 각각의 물질에 대한 당량을 산출하여 전체 당량을 구하고 반응에 필요한 이소시아네이트량을 산출한다. The equivalents for each substance containing active hydrogen groups in the resin premix are calculated to determine the total equivalents and the amount of isocyanates required for the reaction.
<식 2><Formula 2>
상기 식에서 OHv는 OH값(OH Value)이다. In the above formula, OHv is an OH value.
상기 식에서 계산한 이소시아네이트와 레진 프리믹스 액비를 토대로 폼의 밀도는 50~70℃로 가열 조작된 400X400X100mm의 알루미늄 몰드에 계산하여 주입한다. 예를 들어, 레진 프리믹스와 이소시아네이트 액비가 식 1과 식 2에 의해 계산되어진 것이 100g:50g이고, 밀도 40kg/m3의 폼을 제조한다면 밀도는 질량/부피이므로 640g을 주입해야 몰드 부피상 밀도 40kg/m3의 폼을 제조할 수 있다.(몰드크기:400X400X100mm, 부피:0.016m3) 이것을 레진 프리믹스와 이소시아네이트 액비로 계산하여 주입량을 계산하면 426.66: 213.34g을 주입하여 제조할 수 있다. 그리고, 이 몰드에 아이소시아네이트와 레진 프리믹스를 교반을 통한 혼합반응으로 몰드에 주입하여 제조함으로써 원하는 밀도를 갖는 폴리우레탄 발포체의 제조가 가능하다.
Based on the isocyanate and resin premix liquid ratio calculated in the above formula, the density of the foam is calculated and injected into a 400 × 400 × 100 mm aluminum mold heated to 50 to 70 ° C. For example, if the resin premix and isocyanate liquor were calculated by Equation 1 and Equation 100g: 50g, and a foam having a density of 40kg / m 3 is produced, the density is mass / volume, so 640g must be injected, so that the mold volume density is 40kg. A foam of / m 3 can be prepared (mold size: 400 × 400 × 100 mm, volume: 0.016 m 3 ). It can be prepared by injecting 426.66: 213.34 g by calculating the injection amount based on the resin premix and isocyanate liquid ratio. In addition, it is possible to prepare a polyurethane foam having a desired density by injecting an isocyanate and a resin premix into the mold and preparing the mixture by stirring.
본 발명에 따른 제조방법에 의해 제조된 상기 폴리우레탄 발포체는 밀도가 밀도가 30~55 kg/m3까지 조절될 수 있으며, 특히 저밀도 영역인 30~45 kg/m3에서도 크러시어빌리티가 우수하여 성형 후 크러싱 작업이 필요 없다. The polyurethane foam produced by the manufacturing method according to the invention the density can be controlled up to 30 ~ 55 kg / m 3 in density, especially in the low density region 30 ~ 45 kg / m 3 is excellent in crushability molding There is no need for post crushing work.
이렇게 제조된 폴리우레탄 발포체는 자동차의 시트쿠션, 시트백 또는 암 레스트 등에 사용될 수 있으며, 오픈 셀을 형성하고 있어 별도의 기체를 빼내기 위한 공정(크러싱 공정) 및 진공 공정이 필요 없어, 별도의 장비 설치를 위한 작업 공간을 필요로 하지 않고 생산 속도를 빠르게 할 수 있는 등 생산성 면에서 매우 우수하다. 또한, 기존 방법으로는 시트 쿠션을 제외한 시트 백을 제조하기 위해서는 크러싱 공정이 필요 했으나, 본 발명에 따를 경우에는 시트 백 제조시에도 크러싱 공정을 배제할 수 있어 작업 효율을 현저히 향상시킬 수 있다.
The polyurethane foam thus manufactured can be used for seat cushions, seatbacks or arm rests of automobiles, and since it forms an open cell, it does not require a separate process (crushing process) and a vacuum process to separate gas, so that separate equipment is installed. It is very productive in terms of speeding up production without the need for a working space. In addition, the conventional method required a crushing process in order to manufacture a seat back except the seat cushion, according to the present invention can eliminate the crushing process even when manufacturing the seat back can significantly improve the work efficiency .
이하, 본 발명은 다음 실시예에 의거하여 구체적으로 설명하겠으나, 본 발명이 이에 한정되는 것은 아니다.
Hereinafter, the present invention will be described in detail based on the following examples, but the present invention is not limited thereto.
실시예Example
실시예Example 1~5 1-5
표 1에 나타낸 기존 조성에 의하여 폴리우레탄 발포체를 제조하였다. Polyurethane foams were prepared according to the existing compositions shown in Table 1.
표 1과 같이 이소시아네이트는 전체 이소시아네이트 100중량%에 대하여 이소시아네이트기 함량이 35.0-45.0 중량%인 것을 사용하였으며, 레진 프리믹스의 성분들을 표 1에 기재한 양만큼 혼합하여 레진 프리믹스를 만들고 <식 2>로 조절된 레진 프리믹스와 <식 1>로 조절된 이소시아네이트를 표 1에 기재한 만큼 취하여 혼합한 후 심하게 교반한 후 50~70℃로 가열 조작된 400X400X100 mm의 알루미늄 몰드에 주입하여 뚜껑을 닫았다. 몰드에서 성형된 폼은 레진 프리믹스와 이소시아네이트 조성물의 교반 개시로부터 5분 후에 몰드 내에서 꺼낸 직후 밀도 30~55Kg/m3에 따라 유니버셜 테스트 머신으로 1차 50%압축하여 걸리는 힘과 2차 50% 압축하여 걸리는 힘의 차이를 측정하여 크러시어빌리티를 평가하였다. 표 2에 기재된 결과와 같이 밀도 30~55kg/m3에서 크러싱이 없이 불량 없는 폴리우레탄 발포체를 제조할 수 있었다.
As shown in Table 1, an isocyanate group having an isocyanate group content of 35.0-45.0% by weight based on 100% by weight of total isocyanate was used, and the components of the resin premix were mixed in the amounts shown in Table 1 to make a resin premix. The adjusted resin premix and the isocyanate controlled by <Formula 1> were taken as shown in Table 1, mixed, mixed with vigorous stirring, and then injected into a 400 × 400 × 100 mm aluminum mold heated to 50 ° C. to 70 ° C. to close the lid. The foam formed in the mold is first 50% compressed by the universal test machine and the second 50% compressed according to the density 30-55Kg / m 3 immediately after taking out of the mold 5 minutes after the start of stirring of the resin premix and isocyanate composition. The crushability was evaluated by measuring the difference in force. As shown in Table 2, it was possible to produce a polyurethane foam without defects without crushing at a density of 30 ~ 55kg / m 3 .
#2) 글리세린을 개시제로 하고 프로필렌옥사이드와 에틸렌 옥사이드를 부가중합 시켜서 얻어진 폴리에테르 폴리올(중량평균분자량 7500), OHV 22 mg KOH/g
#3) 글리세린을 개시제로하고 프로필렌옥사이드와 에틸렌옥사이드를 부가중합시켜서 얻어진 폴리에테르폴리올에 아크릴로니트릴과 스타이렌 모노머를 분산시켜 제조한 폴리머폴리올(중량평균분자량 6500), OHV 26 mg KOH/g
#4) 글리세린을 개시제로 하고 프로필렌 옥사이드와 에틸렌 옥사이드를 부가중합시켜서 얻어진 폴리에테르폴리올(중량평균분자량 3,500), OHV 52 mg KOH/g
#5) 증류수 또는 이온교환수
#6) 유기규소 계면활성제(MOMENTIVE사 제품)
#7) 아민촉매 or 촉매의 조합(에어프로덕트사, TOSOH, 또는 KAO 제품)
#8) 아민촉매(에어프로덕트사 제품)
#9) 디에탄올 아민(한국포리올사 제품)
#10) NCO% 37.5, 금호미쓰이화학㈜ 제품(상품명: COSMONATE CG-3701S)# 1) Polyether polyol (weight average molecular weight 6000) obtained by addition polymerization of propylene oxide and ethylene oxide with glycerin as initiator, OHV 28 mg KOH / g
# 2) Polyether polyol (weight average molecular weight 7500) obtained by addition polymerization of propylene oxide and ethylene oxide with glycerin as initiator, OHV 22 mg KOH / g
# 3) Polymer polyol (weight average molecular weight 6500) prepared by dispersing acrylonitrile and styrene monomer in polyether polyol obtained by addition polymerization of propylene oxide and ethylene oxide as glycerin as initiator, OHV 26 mg KOH / g
# 4) Polyether polyol (weight average molecular weight 3,500) obtained by addition polymerization of propylene oxide and ethylene oxide with glycerin as an initiator, OHV 52 mg KOH / g
# 5) distilled or ion-exchanged water
# 6) organosilicon surfactant (product of MOMENTIVE company)
# 7) Combination of Amine Catalysts or Catalysts (Air Products, TOSOH, or KAO)
# 8) Amine Catalyst (Air Products)
# 9) diethanol amine (Korea Polyol Co., Ltd.)
# 10) NCO% 37.5, Kumho Mitsui Chemicals Co., Ltd. (Product Name: COSMONATE CG-3701S)
표 1의 구성으로 제조한 발포체에 대한 물성을 표 2에 나타내었다. 용도는 시트 쿠션, 시트 백, 암 레스트이며 30~55 kg/m3 밀도에서의 모든 발포체가 불량 없이 제조되었다.(크러시어빌리티 = 0)
Physical properties of the foam prepared in the configuration of Table 1 are shown in Table 2. Applications include seat cushions, seat backs, arm rests and all foams at densities of 30-55 kg / m 3 were produced without defects (crushability = 0).
(50% 압축,50℃,95% RH,22hr)Permanent compression set,% (high temperature, high humidity)
(50% compression, 50 ° C, 95% RH, 22hr)
(75% 압축,80℃,22hr)Compressive strain,% (high temperature)
(75% compression, 80 ℃, 22hr)
도 3은 종래의 방법에 따라 폴리우레탄 발포체가 크러싱된 후에 폴리우레탄 셀의 모습과 본 발명에 따라 제조된 폴리우레탄 발포체의 셀의 모습을 비교하여 나타낸 SEM사진이다. 좌측의 종래 방법에 의할 경우 필연적으로 크러싱 공정을 거쳐야 하기 때문에 물리적 파손이 발생하는데 비하여, 본 발명에 따를 경우에는 이와 같은 물리적 크러싱 과정이 필요 없으므로 셀의 파손이 발생하지 않는다. Figure 3 is a SEM photograph showing the appearance of the polyurethane cell and the appearance of the cell of the polyurethane foam prepared according to the invention after the polyurethane foam is crushed according to the conventional method. According to the conventional method on the left side, since the physical damage is inevitably required to go through the crushing process, the physical crushing process is not necessary in accordance with the present invention, so that no cell breakage occurs.
본 발명의 조성물로 제조된 폴리우레탄 발포체는 한가지 원료(이소시아네이트 1종류, 레진 프리믹스 1종류)로 밀도범위를 30~55 kg/m3 범위에서 생산할 수 있으며 동시에 기계적인 셀 오픈 공정(크러싱 공정) 없이도 생산 할 수 있어 생산성 향상 및 원료 취급 관리를 용이할 수 있는 효과가 있다.Polyurethane foam made of the composition of the present invention can produce a density range of 30 ~ 55 kg / m 3 with one raw material (one isocyanate, one resin premix) and at the same time a mechanical cell open process (crushing process) It can be produced without it, which has the effect of improving productivity and managing raw material handling.
Claims (13)
b. 중량평균분자량이 6,000~10,000이고 OH값이 20~24 mg KOH/g인 폴리에테르폴리올 또는 폴리에스테르폴리올 10~30중량%,
c. 중량평균분자량이 3,000~6,000이고 OH값이 30~60 mg KOH/g인 폴리에테르폴리올 또는 폴리에스테르폴리올 0~20중량% 및
d. 중량평균분자량이 6,000~10,000이고 OH값이 20~30 mg KOH/g인 폴리에테르폴리올 또는 폴리에스테르폴리올에 아크릴로니트릴, 스티렌 또는 그 혼합물이 분산 또는 그라프트된 폴리머폴리올 10~40중량%
를 포함하는 폴리올 레진 프리믹스 100 중량부;
(2) 이소시아네이트 30 ~ 70 중량부; 및
(3) 발포제 1~10 중량부
를 혼합한 조성물을 반응시켜 제조하는 것을 특징으로 하는 폴리우레탄 발포체의 제조방법.
(1) a. 40 to 70% by weight of a polyether polyol or polyester polyol having a weight average molecular weight of 6,000 to 10,000 and an OH value of 25 to 30 mg KOH / g,
b. 10-30 wt% of a polyether polyol or polyester polyol having a weight average molecular weight of 6,000 to 10,000 and an OH value of 20 to 24 mg KOH / g,
c. 0-20 wt% of a polyether polyol or polyester polyol having a weight average molecular weight of 3,000 to 6,000 and an OH value of 30 to 60 mg KOH / g and
d. 10 to 40% by weight of polymer polyol in which acrylonitrile, styrene or a mixture thereof is dispersed or grafted in a polyether polyol or polyester polyol having a weight average molecular weight of 6,000 to 10,000 and an OH value of 20 to 30 mg KOH / g
100 parts by weight of a polyol resin premix comprising;
(2) 30 to 70 parts by weight of isocyanate; And
(3) 1 to 10 parts by weight of blowing agent
Method for producing a polyurethane foam, characterized in that to produce a mixture by reacting the mixture.
The method of claim 1, wherein the polyether polyol is propylene oxide using at least one initiator selected from the group consisting of ethylene glycol, glycerin, triethanolamine, pentaerythritol, toluenediamine, ethylenediamine, diaminodiphenylmethane, sorbitol and sugar And a polyether polyol obtained by addition polymerization of ethylene oxide and the like.
The method according to claim 1, wherein the polyester polyol is at least one selected from the group consisting of terephthalic acid, ethylene adipic acid, butylene adipic acid, 1,6-hexanedipic acid, diethylene adipic acid and phthalic acid 1,4 A process for producing a polyurethane foam, characterized by using a polyester polyol obtained by dehydrating and condensing at least one selected from the group consisting of butanediol and ethylene glycol.
The method of claim 1, wherein the composition further comprises at least one additive selected from the group consisting of a crosslinking agent, a catalyst and a surfactant.
The method of claim 4, wherein the crosslinking agent is ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, pentaerythritol, diethanolamine, tritanolamine, ethylenediamine , Triethylenetetraamine, methyleneorthochloroaniline, 4,4-diphenylmethanediamine, 2,6-dichloro-4,4-diphenylmethanediamine, 2,4-toluenediamine and 2,6-toluenediamine Method for producing a polyurethane foam, characterized in that used in 0.001 to 10% by weight based on the total composition.
The method of claim 4, wherein the catalyst is triethylenediamine, bisdiethylaminoethyl ether, tripropylamine, triisopropanolamine, tributylamine, triethylamine, N-methylmorpholine, diethylenetriaminebis (2- ( N, N-diethylamino) ethyl) ether and salts thereof, the method for producing a polyurethane foam, characterized in that used in 0.001 to 10% by weight based on the total composition.
The method according to claim 4, wherein the surfactant is an organosilicon surfactant, the method of producing a polyurethane foam, characterized in that used in 0.001 to 10% by weight based on the total composition.
The method according to claim 1, wherein (1). A method for producing a polyurethane foam, characterized in that the amount of acrylonitrile, styrene or mixtures dispersed or grafted in the polymer polyol of d is 0.1 to 40% by weight.
The method according to claim 1, wherein the (2) isocyanate is at least one selected from the group consisting of polymeric diphenylmethane diisocyanate, monomeric diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, toluene diisocyanate and modified toluene diisocyanate. Method for producing a polyurethane foam, characterized in that used.
The method of claim 1, wherein the blowing agent is water.
The method according to claim 1, wherein the density of the polyurethane foam is adjusted to 30 ~ 55kg / m 3 method of producing a polyurethane foam.
The method of claim 1, wherein the polyurethane foam is used for a seat cushion, a seat back, or an arm rest of an automobile.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927020A (en) * | 2014-03-21 | 2015-09-23 | 现代自动车株式会社 | Flame retarded slabstock polyurethane foam composition for flame lamination |
| US10189966B2 (en) | 2016-04-07 | 2019-01-29 | Hyundai Motor Company | Composition for manufacturing polyurethane foam and molded article thereof |
| CN111072890A (en) * | 2019-12-25 | 2020-04-28 | 万华化学（北京）有限公司 | Semi-rigid polyurethane foam, preparation method thereof, polyurethane foam sandwich component and application |
| CN111116854A (en) * | 2019-12-25 | 2020-05-08 | 万华化学（北京）有限公司 | Semi-rigid polyurethane foam, preparation method thereof, sandwich component, preparation method and application thereof |
| KR20210056679A (en) * | 2019-11-11 | 2021-05-20 | 에스케이씨솔믹스 주식회사 | Polishing pad, preparation method thereof, and preparation method of semiconductor device using same |
| CN116253853A (en) * | 2023-01-02 | 2023-06-13 | 黎明化工研究设计院有限责任公司 | High-adhesion quick-release polyurethane composition, and method and application for preparing polyurethane product |
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2011
- 2011-02-08 KR KR1020110011276A patent/KR20120090708A/en active Search and Examination
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104927020A (en) * | 2014-03-21 | 2015-09-23 | 现代自动车株式会社 | Flame retarded slabstock polyurethane foam composition for flame lamination |
| US10189966B2 (en) | 2016-04-07 | 2019-01-29 | Hyundai Motor Company | Composition for manufacturing polyurethane foam and molded article thereof |
| KR20210056679A (en) * | 2019-11-11 | 2021-05-20 | 에스케이씨솔믹스 주식회사 | Polishing pad, preparation method thereof, and preparation method of semiconductor device using same |
| CN111072890A (en) * | 2019-12-25 | 2020-04-28 | 万华化学（北京）有限公司 | Semi-rigid polyurethane foam, preparation method thereof, polyurethane foam sandwich component and application |
| CN111116854A (en) * | 2019-12-25 | 2020-05-08 | 万华化学（北京）有限公司 | Semi-rigid polyurethane foam, preparation method thereof, sandwich component, preparation method and application thereof |
| CN111072890B (en) * | 2019-12-25 | 2022-04-22 | 万华化学（北京）有限公司 | Semi-rigid polyurethane foam, preparation method thereof, polyurethane foam sandwich component and application |
| CN116253853A (en) * | 2023-01-02 | 2023-06-13 | 黎明化工研究设计院有限责任公司 | High-adhesion quick-release polyurethane composition, and method and application for preparing polyurethane product |
| CN116253853B (en) * | 2023-01-02 | 2024-06-04 | 黎明化工研究设计院有限责任公司 | High-adhesion quick-release polyurethane composition, and method and application for preparing polyurethane product |
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