KR101867064B1 - Polyurethane form - Google Patents
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- KR101867064B1 KR101867064B1 KR1020170157822A KR20170157822A KR101867064B1 KR 101867064 B1 KR101867064 B1 KR 101867064B1 KR 1020170157822 A KR1020170157822 A KR 1020170157822A KR 20170157822 A KR20170157822 A KR 20170157822A KR 101867064 B1 KR101867064 B1 KR 101867064B1
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
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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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J9/12—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 by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
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- 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
- 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
- C08J9/12—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 by a physical blowing agent
- C08J9/127—Mixtures of organic and inorganic blowing agents
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- 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
- 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
- C08J9/12—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 by a physical blowing agent
- C08J9/14—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 by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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- 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
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- 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
- C08L75/08—Polyurethanes from polyethers
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- C08G2101/0025—
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
Description
본 발명은 열전도율의 낮고, 치수안정성이 개선된 친환경 발포 폴리우레탄 폼 및 이를 제조하기 위한 경화 조성물에 관한 것이다.The present invention relates to an environmentally friendly expanded polyurethane foam having a low thermal conductivity and improved dimensional stability, and a curing composition for producing the same.
우레탄폼은 단열 부재로서 건축용 내외벽재나 패널 또는 가전제품의 단열품으로서, 또한 건축물의 결로방지나 단열등에서 많이 사용하는 소재이다. Urethane foam is a heat insulating material, which is widely used as insulation material for building interior and exterior wall materials, panels or household appliances, and also for prevention of condensation and insulation of buildings.
이러한 폴리우레탄은 통상 폴리이소시아네이트와 폴리올에 발포제, 촉매, 정포제 등의 다양한 첨가제를 투입하여 경화하고 발포함으로써 제조된다. Such a polyurethane is usually prepared by adding various additives such as a foaming agent, a catalyst and a foaming agent to a polyisocyanate and a polyol, followed by curing and foaming.
종래의 폴리우레탄의 발포제로 물이나 유기발포제로서 HFC계나, 기상의 탄화수소계열을 주로 사용하고 있지만, 여전히 충분히 등방성의 발포가 부족하여 단열효과의 개선이 필요하다. As a foaming agent for conventional polyurethanes, water or an organic foaming agent such as HFC or gas phase hydrocarbons are mainly used. However, sufficient isotropic foaming is still insufficient to improve the heat insulating effect.
본 발명에서는 이러한 발포특성의 저하는 발포제와 발포제에 따른 폴리우레탄폼의 주제(폴리올함유 조성물)과 경화제(폴리이소시아네이트등)의 조합과 발포제의 종류에 따라 많은 차이가 발생함을 알게 되었으며, 상기 효과를 가지는 새로운 폴리우레탄 발포시스템을 개발함으로서, 본 발명을 완성하였다. In the present invention, it has been found that such deterioration of the foaming properties is caused by a large difference depending on the combination of the foaming agent and the foaming agent, the combination of the subject (polyol-containing composition) of the polyurethane foam with the curing agent (polyisocyanate or the like) The present invention has been accomplished by developing a novel polyurethane foam system.
일본특허공개공보 2011-208051호에서는 발포제로서 물 , 하이드로플루오로카본(HFC), 하이드로카본(HC) 또는 이산화탄소를 이용하여 우수한 발포특성과 치수안정성이 높은 우레탄폼을 제조하는 것으로 기재하고 있지만, 여전히 발포크기가 균일하지 않아 방열기능이 개선되어야 하는 문제점을 가지고 있다.Japanese Patent Laid-Open Publication No. 2011-208051 discloses that urethane foam having excellent foam properties and dimensional stability is produced by using water, hydrofluorocarbon (HFC), hydrocarbon (HC), or carbon dioxide as a blowing agent, There is a problem that the heat spreading function must be improved because the foam size is not uniform.
본 발명의 목적은 상기와 같이 균일한 발포형태를 가지는 폴리우레탄발포 구조체를 제조함으로써, 방열특성이나 내열특성이 더욱 우수하고, 치수안정성이 좋은 새로운 폴리우레탄 경질폼을 제조하기 위한 폴리우레탄시스템을 제공하는 것이다. An object of the present invention is to provide a polyurethane system for producing a new polyurethane hard foam having excellent heat radiation property and heat resistance property and good dimensional stability by producing a polyurethane foam structure having a uniform foam shape as described above .
본 발명의 발명자는 상기의 과제를 달성하기 위하여 많은 연구를 한 결과, 폴리에테르폴리올과 트리에탄올아민계폴리에테르폴리올의 혼합 폴리올과 폴리머릭 MDI(polymeric MDI)를 기본 원료로하는 폴리우레탄을 제조할 때, 발포제로 HFC와 초임계 이산화탄소의 혼합발포제를 사용하는 경우, 본 발명에서 목적으로 하는 균일한 발포셀을 가지는 발포구조체가 얻어지고, 또한 그로부터 방열특성과 수치안정성이 우수한 경질 폴리우레탄폼이 제조됨을 확인하였다.The inventors of the present invention have conducted extensive research in order to achieve the above-mentioned object. As a result, the inventors of the present invention have found that when polyurethanes based on a mixed polyol of a polyether polyol and a triethanolamine-based polyether polyol and a polymeric MDI When a mixed foaming agent of HFC and supercritical carbon dioxide is used as a foaming agent, a foaming structure having a uniform foaming cell of the present invention is obtained, and a rigid polyurethane foam excellent in heat radiation characteristics and numerical stability is produced therefrom Respectively.
구체적으로 본 발명은 폴리에테르계폴리올 100중량부에 대하여, 트리에탄올아민계 폴리에테르폴리올 1 내지 50중량부의 혼합 폴리에테르 폴리올을 주제로하고, 여기에 아민계 촉매, 인계난연제를 포함하는 주제혼합물을 중합성MDI와 반응시켜 제조한다.Specifically, the present invention relates to a method for producing a polyether polyol, which comprises subjecting a mixed polyether polyol of 1 to 50 parts by weight of a triethanolamine-based polyether polyol to 100 parts by weight of a polyether polyol, subjecting the mixture to an amine catalyst and a phosphorus- Gt; MDI < / RTI >
또한 본 발명은 상기 주제와 경화제의 조합에서 발포제로 HFCs와 이산화탄소를 혼합한 발포제를 채택한 것을 또한 본 발명의 특징이라 할 수 있다. 상기와 같은, 발포제들의 조합과 상기 주제조성물과 경화제의 조합에 의해 물성이 우수하고, 발포셀의 형태가 원형의 고른 형태를 가지며, 따라서 방열특성이 우수하고 또한 치수안정성이 우수하게 된다.It is also a feature of the present invention that the present invention adopts a foaming agent in which HFCs and carbon dioxide are mixed as a foaming agent in the combination of the subject and the curing agent. By the combination of the foaming agents and the combination of the base composition and the curing agent as described above, the physical properties are excellent and the shape of the foamed cells has a uniform shape of the circular shape, so that the heat radiation property is excellent and the dimensional stability is excellent.
본 발명에서 사이 폴리올 주제 100중량부에 대하여, 상기 혼합발포제는 1 내지 40중량부를 사용할 수 있으며, 상기 혼합발포제에서 HFCs계 발포제와 이산화탄소 발포제의 비율은 HFCs 100중량부에 대하여 제한하지 않지만 좋게는 1 내지 30중량부의 비율로 사용하는 것이 발포셀을 안정화에 더욱 좋지만 이에 한정하는 것은 아니다.In the present invention, the mixed foaming agent may be used in an amount of 1 to 40 parts by weight based on 100 parts by weight of the polyphenol resin. In the mixed foaming agent, the ratio of the HFCs-based blowing agent to the carbon dioxide blowing agent is not limited to 100 parts by weight, To 30 parts by weight is more preferable for stabilizing the foamed cell but is not limited thereto.
또한 본 발명에서 혼합폴리올 주제 100중량부에 대하여 0.05 내지 5중량부의 아민계 촉매를 함유하며, 상기 발포제 중 이산화탄소는 상기 폴리올 주제중에 또는 경화제 중에 또는 2가지 조성물 중에 초임계, 아임계 또는 액상 이산화탄소를 함유하도록 하여 폴리우레탄 폼을 제조할 수 있다. In the present invention, 0.05 to 5 parts by weight, based on 100 parts by weight of the mixed polyol subject, of an amine-based catalyst is contained. The carbon dioxide in the blowing agent may be added to the polyol subject or the curing agent, or into two compositions by using supercritical, subcritical or liquid carbon dioxide To prepare a polyurethane foam.
또한 본 발명은 난연제로서 인계난연제를 폴리에테르폴리올 100중량부에 대하여 5 내지 40 중량부, 좋게는 10 내지 30 중량부 사용하는 것이 방열특성과 더불어 난연특성을 더욱 증가시키고, 또한 실리콘계 활제를 폴리에테르 폴리올 주제 100중량부에 대하여 0.1 내지 5중량부를 채택함으로써, 본 발명의 효과를 더욱 증진할 수 있다.In addition, the use of the phosphorus-based flame retardant as a flame retardant in an amount of 5 to 40 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the polyether polyol further increases the flame retardancy, The effect of the present invention can be further enhanced by employing 0.1 to 5 parts by weight based on 100 parts by weight of the polyol subject.
본 발명의 상기 수단에 의해 달성되는 폴리우레탄 폼은 폴리우레탄 폼의 강도를 확보하면서, 폼의 발포를 효과적으로 발생시키고, 압축 강도가 우수하며, 방열특성이 우수하고, 발포셀의 형태가 구형으로 균일하게 분포되는 셀이 생성되며, 치수 변화율이 작게 할 수 있는 장점이 있다. The polyurethane foam attained by the means of the present invention can effectively foam foam while securing the strength of the polyurethane foam, has excellent compressive strength, is excellent in heat radiation characteristics, And the dimensional change rate can be made small.
도 1은 실시예에서 제조된 발포우레탄 폼의 주사전자현미경(Scanning Electron Microscope, SEM) 사진이다.1 is a Scanning Electron Microscope (SEM) photograph of the foamed urethane foam produced in the Example.
이하, 본 발명에 대하여 구체적으로 설명한다. Hereinafter, the present invention will be described in detail.
본명에서 주제로서 폴리올 성분은 폴리에테르폴리올과 트리에탄올아민계폴리에테르폴리올의 혼합 폴리올을 채택하고, 경화제로서는 폴리머릭 MDI(polymeric MDI, 중합성 MDI라고도 함)를 사용하여 양자를 반응시킴으로써, 본 발명의 폴리우레탄을 제조한다. 본 발명에서 발포제로는 상기 주제와 경화제의 혼합물에 HFCs와 이산화탄소의 혼합발포제를 사용하는데, 이 경우 균일한 발포셀을 가지는 발포구조체가 얻어지고, 또한 그로부터 방열특성과 수치안정성이 우수한 경질 폴리우레탄폼이 제조된다.The polyol component as a subject in the real name is a mixed polyol of a polyether polyol and a triethanolamine-based polyether polyol, and a polymeric MDI (polymeric MDI, also referred to as a polymerizable MDI) as a curing agent, Polyurethane is produced. As the foaming agent in the present invention, a mixed foaming agent of HFCs and carbon dioxide is used as a mixture of the above-mentioned subject and the curing agent. In this case, a foaming structure having uniform foaming cells is obtained, and a rigid polyurethane foam .
본 발명의 상기 주제로서 폴리에테르계폴리올과 트리에탄올아민계 폴리에테르 폴리올의 조성비는 폴리에테르계폴리올 100중량부에 대하여, 트리에탄올아민계 폴리에테르폴리올 1 내지 50중량부의 혼합 폴리에테르 폴리올을 주제로 사용하는 것이, 발포셀을 균일하고 원형의 형태를 유지하는 것에서 좋다. As the subject of the present invention, the composition ratio of the polyether polyol and the triethanolamine-based polyether polyol is such that the mixed polyether polyol of 1 to 50 parts by weight of the triethanolamine-based polyether polyol is used per 100 parts by weight of the polyether- It is preferable that the foam cell maintains a uniform and circular shape.
상기 본 발명의 폴리에테르계폴리올은 다가 알코올을 개시제에 알킬렌 옥사이드를 반응시켜 얻어지는 것이 통상적이며, 이러한 다가 알콜로는 글리세린, 에틸렌글리콜, 프로필렌 글리콜, 디에틸렌 글리콜, 펜타에리트리톨, 디프로필렌글리콜, 트리메티롤프로판 등을 사용할 수 있다. 또한 본 발명에서 트리에탄올아민계폴리에테르폴리올의 경우는 트리에탄올아민 등을 상기의 알킬렌글리콜 등의 다가 알콜과 축합반응시켜 제조할 수 있고 상업적으로는 WANOL R3304A 등의 다양한 그레이드가 상품화 되어 있으므로, 본 발명에서는 더 이상 설명을 생략한다.The polyether polyol of the present invention is usually obtained by reacting a polyhydric alcohol with an initiator and an alkylene oxide. Examples of the polyhydric alcohol include glycerin, ethylene glycol, propylene glycol, diethylene glycol, pentaerythritol, Trimethylol propane and the like can be used. Further, in the case of the triethanolamine-based polyether polyol in the present invention, triethanolamine or the like can be produced by a condensation reaction with a polyhydric alcohol such as alkylene glycol, etc., and various grades such as WANOL R3304A are commercialized, The description will be omitted.
또한 본 발명은 상기 주제와 경화제의 조합에서 발포제로 HFCs와 이산화탄소를 혼합한 발포제를 채택한 것을 또한 본 발명의 특징이라 할 수 있다. 상기와 같은, 발포제들의 조합과 상기 주제조성물과 경화제의 조합에 의해 물성이 우수하고, 발포셀의 형태가 원형의 고른 형태를 가지며, 따라서 방열특성이 우수하고 또한 치수안정성이 우수하게 된다.It is also a feature of the present invention that the present invention adopts a foaming agent in which HFCs and carbon dioxide are mixed as a foaming agent in the combination of the subject and the curing agent. By the combination of the foaming agents and the combination of the base composition and the curing agent as described above, the physical properties are excellent and the shape of the foamed cells has a uniform shape of the circular shape, so that the heat radiation property is excellent and the dimensional stability is excellent.
본 발명에서 HFCs로는 디플루오로메탄(HFC32), 1,1,1,2,2-펜타플루오로에탄(HFC125), 1,1,1-트리플루오로에탄(HFC143a), 1,1,2,2-테트라플루오로에탄(HFC134), 1,1,1,2-테트라플루오로에탄(HFC134a), 1,1-디플루오로에탄(HFC152a), 1,1,1,2,3,3,3-펜타플루오로프로판(HFC227ea), 1,1,1,3,3-펜타플루오로프로판(HFC245fa), 1,1,1,3,3-펜타플루오로부탄(HFC365mfc) 및 1,1,1,2,2,3,4,5,5,5-데카 플루오로펜탄(HFC4310mee) 등을 들 수 있다.In the present invention, HFCs include, for example, difluoromethane (HFC32), 1,1,1,2,2-pentafluoroethane (HFC125), 1,1,1-trifluoroethane (HFC143a) , 2-tetrafluoroethane (HFC134), 1,1,1,2-tetrafluoroethane (HFC134a), 1,1-difluoroethane (HFC152a), 1,1,1,2,3,3 , 3-pentafluoropropane (HFC227ea), 1,1,1,3,3-pentafluoropropane (HFC245fa), 1,1,1,3,3-pentafluorobutane (HFC365mfc) , 1,2,2,3,4,5,5,5-decafluoropentane (HFC4310mee), and the like.
또한 본 발명에 있어서는 상기한 유기의 발포제와 함께 초임계, 아임계, 또는 액상 이산화탄소(이하, 액상 CO2로 약칭한다)가 HFCs와 혼합되어 투입된다. 상기 이산화탄소는 액화된 상태로 혼합되어 투입되며, 액상 이산화탄소는 이산화탄소 기체를 소정의 온도에서 압력을 가하여 초임계 상태, 아임계 상태, 또는 액체 상태로 투입된다. 본 발명의 액상 CO2는 이산화탄소 공급 장치에 의해 폴리올 조성물의 유로 또는 폴리이소시아네이트의 유로에 공급되어 혼합시킬 수 있어 이들 폴리올 조성물 중의 폴리올과 폴리이소시아네이트와의 반응에 의해 발생하는 폴리우레탄의 발포에 기여한다. 이러한 액상 CO2는 그 배합에 의해 발포 초기에 있어서의 유효한 발포 작용을 실현할 수 있어서 좋다.In the present invention, supercritical, subcritical, or liquid carbon dioxide (hereinafter abbreviated as liquid CO 2 ) together with the above-mentioned organic foaming agent is mixed with HFCs. The carbon dioxide is mixed in a liquefied state, and the liquid carbon dioxide is put into a supercritical state, a subcritical state, or a liquid state by applying a pressure of a carbon dioxide gas at a predetermined temperature. The liquid CO 2 of the present invention can be supplied to the flow path of the polyol composition or the polyisocyanate flow path by the carbon dioxide supply device and mixed therewith and contributes to the foaming of the polyurethane generated by the reaction of the polyol and the polyisocyanate in the polyol composition . The liquid CO 2 may be realized in the effective foaming action in the initial foaming by the formulation.
본 발명에서 상기 폴리올 주제 100중량부에 대하여, 상기 혼합발포제는 1 내지 40중량부를 사용할 수 있으며, 상기 혼합발포제에서 HFCs계 발포제와 이산화탄소 발포제의 비율은 이산화탄소를 HFCs 100중량부에 대하여 제한하지 않지만 좋게는 1 내지 30중량부의 비율로 사용하는 것이 발포셀을 안정화에 더욱 좋지만 이에 한정하는 것은 아니다.In the present invention, 1 to 40 parts by weight of the mixed foaming agent may be used per 100 parts by weight of the polyol subject. In the mixed foaming agent, the ratio of the HFC-based foaming agent to the carbon dioxide foaming agent is not limited to 100 parts by weight of HFCs, Is preferably used in a proportion of 1 to 30 parts by weight for stabilizing the foamed cell, but is not limited thereto.
또한 본 발명에서 혼합폴리올 주제 100중량부에 대하여 0.05 내지 5중량부의 아민계 촉매를 함유하며, 상기 발포제 중 이산화탄소는 상기 폴리올 주제중에 또는 경화제 중에 또는 2가지 조성물 중에 초임계, 아임계 또는 액상 이산화탄소를 함유하도록 하여 폴리우레탄 폼을 제조할 수 있다. In the present invention, 0.05 to 5 parts by weight, based on 100 parts by weight of the mixed polyol subject, of an amine-based catalyst is contained. The carbon dioxide in the blowing agent may be added to the polyol subject or the curing agent, or into two compositions by using supercritical, subcritical or liquid carbon dioxide To prepare a polyurethane foam.
본 발명에서 아민계 촉매는 상기 폴리올 주제와 경화제를 반응시키는 역할을 하는 것으로, 본 발명에서는 하나의 아민계 촉매 또는 복수의 아민계촉매를 사용할 수 있다. 예를들면 본 발명에서 사용하는 촉매로는 2,4,6-트리(디메틸아미노메틸) 페놀, 테트라메틸 구아니딘, N,N-디메틸아미노에탄올, N,N-디메틸아미노에톡시 에탄올, 에톡시화 하이드록실아민, N,N,N',N'-테트라메틸-1,3-디아미노2-프로판올, N,N,N'-트리메틸 아미노에틸 에탄올아민, 1,4-비스(2-하이드록시프로필),2-메틸 피페라진,1-(2-하이드록시프로필) 이미다졸, 3,3-디아미노 N-메틸 디프로필 아민, N-메틸-N'-하이드록시에틸 피페라진 등을 들 수 있다. 또한 고리식 아민 화합물로서는 트리에틸렌 디아민, N,N'-디메틸사이클로헥실 아민, N,N-디사이클로헥실 메틸아민, 메틸렌비스(디메틸사이클로헥실) 아민, N,N-디메틸벤질 아민, 모르폴린, N-메틸 모르폴린, N-에틸 모르폴린, N-(2-디메틸아미노에틸) 모르폴린, 4,4'-옥시디에틸렌 디모르포린, N,N'-디에틸 피페라진, N,N'-디메틸피페라진, N-메틸-N'-디메틸아미노에틸 피페라진, 1,8-디아조비사이클로(5,4,0)-운데센-7 등을 들 수 있으며, 상기 아민 촉매가 본 발명의 상기 범주를 사용하는 경우, 외관이 더욱 좋고, 발포셀의 형태가 균일하므로, 선호되지만, 반드시 이에 한정하는 것은 아니다. In the present invention, the amine-based catalyst serves to react the polyol subject with the curing agent. In the present invention, one amine-based catalyst or a plurality of amine-based catalysts can be used. Examples of the catalyst used in the present invention include 2,4,6-tri (dimethylaminomethyl) phenol, tetramethylguanidine, N, N-dimethylaminoethanol, N, N-dimethylaminoethoxyethanol, ethoxylated N, N, N'-trimethylaminoethylethanolamine, 1,4-bis (2-hydroxypropyl) ), 2-methylpiperazine, 1- (2-hydroxypropyl) imidazole, 3,3-diamino N-methyldipropylamine and N-methyl-N'-hydroxyethylpiperazine . Examples of the cyclic amine compound include triethylenediamine, N, N'-dimethylcyclohexylamine, N, N-dicyclohexylmethylamine, methylenebis (dimethylcyclohexyl) amine, N, N-dimethylbenzylamine, N, N'-diethylpiperazine, N, N'-diethylpiperazine, N, N'-dimethylmorpholine, N- - dimethylpiperazine, N-methyl-N'-dimethylaminoethylpiperazine, 1,8-diazobicyclo (5,4,0) -undecene-7, and the like. When the above category is used, the appearance is better and the shape of the foamed cells is uniform, which is preferable, but not always limited thereto.
또한 본 발명에서는 상기 아민계 촉매와 함께 폴리올과 폴리이소시아네이트와의 반응을 촉진시키기 위해, 이부틸 주석 디라우레이트, 옥틸산 비스무트(2-에틸헥실산 비스무트), 네오데칸산 비스무트, 네오 도데칸산 비스무트, 나프텐산 비스무트 등의 지방산 비스머스염, 나프텐산 납 등의 우레탄 중합형 촉매를 더 추가할 수 있다. In the present invention, in order to promote the reaction between the polyol and the polyisocyanate together with the amine-based catalyst, it is preferable to use butyltin dilaurate, bismuth octylate (bismethyl 2-ethylhexylate), bismuth neodecanoate, bismuth neododecane , Fatty acid bismuth salts such as bismuth naphthenate, lead naphthenate, and the like can be further added.
본 발명에서 경화제로는 중합성MDI를 사용하는 것이 발포셀의 균일성과 치수안정성 및 표면의 평활성을 위해서 사용하는 것이 좋다. 중합성 MDI로는 본 발명에서 특별히 제한하지 않지만, 예를 들면, 하기 화학식의 것으로서, 상온에서는 액체이며, 평균관능기 수가 2.5 내지 2.9개이며, 점도는 25℃에서 100~3,000cps의 것이 본 발명의 발포셀의 균일성을 위해서 더욱 좋아서 선호되며, 예를 들면 금호미쓰이화학의 COSMONATE M-100, SR-500등의 시리즈가 있으므로 본 발명에서는 더 이상 설명하지 않는다..In the present invention, it is preferable to use a polymerizable MDI as the curing agent for uniformity of the foamed cell, dimensional stability and surface smoothness. The polymerizable MDI is not particularly limited in the present invention but may be, for example, those having the following formula: liquid at room temperature, average number of functional groups of 2.5 to 2.9, viscosity of 100 to 3,000 cps at 25 占 폚, For example, COSMONATE M-100, SR-500 by KUMHO MITSUI CHEMICAL CO., LTD., So that it is not described in the present invention.
본 발명에서 상기 주제와 경화제의 함량은 이소시아네이트기(NCO)와 폴리올 수산기(OH)의 당량비로서, NCO/OH당량비로서 0.8 내지 2,0으로 반응시키는 것이 좋지만, 본 발명에서는 이를 반드시 한정하는 것은 아니다. In the present invention, the content of the subject and the curing agent is preferably an equivalent ratio of an isocyanate group (NCO) to a polyol hydroxyl group (OH) in terms of NCO / OH equivalent ratios of 0.8 to 2.0, but the present invention is not limited thereto .
또한 본 발명은 난연제로서 인계난연제를 폴리에테르폴리올 100중량부에 대하여 5 내지 40 중량부, 좋게는 10 내지 30 중량부 사용하는 것이 방열특성과 더불어 난연특성을 더욱 증가시키고, 또한 실리콘계 활제를 폴리에테르 폴리올 주제 100중량부에 대하여 0.1 내지 5중량부를 채택함으로써, 본 발명의 효과를 더욱 증진할 수 있다.In addition, the use of the phosphorus-based flame retardant as a flame retardant in an amount of 5 to 40 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the polyether polyol further increases the flame retardancy, The effect of the present invention can be further enhanced by employing 0.1 to 5 parts by weight based on 100 parts by weight of the polyol subject.
또한 본 발명에서는 필요에 의해, 추가로 정포제 등의 종래부터 알려져 있는 각종 조제를 적당하게 선택하고, 배합시키는 것도 가능하다. In the present invention, it is also possible to suitably select and formulate various conventional additives known in the art such as foaming agents, if necessary.
이하는 본 발명의 발포공정에 대하여 설명한다.Hereinafter, the foaming process of the present invention will be described.
본 발명의 발포경화는 폴리올주제와 경화제인 중합성MDI와 촉매의 존재 하에 반응시켜 발포 경화시키는데, 발포공정에 적용하는 방법은 종래의 방법이라면 특별히 한정하지 않고 사용할 수 있다.The foaming curing of the present invention is performed by foaming and curing by reacting in the presence of a polyol subject and a polymerizable MDI which is a curing agent and a catalyst, and the method of applying the foaming process is not particularly limited as long as it is a conventional method.
예를 들면, 라미네이트 연속 발포법, 주입 발포법, 혹은 사(스프레이) 발포법 등에 의해 발포 경화시킬 수 있으며, 필요에 의해서 적절히 선택할 수 있으므로, 본 발명에서는 구체적으로 설명하지 않는다. For example, it can be foamed and cured by a continuous lamination foaming method, an injection foaming method, a sagging (spraying) foaming method or the like, and can be appropriately selected according to necessity.
이하, 본 발명의 실시예를 통하여 본 발명을 구체적으로 설명한다. 이하의 실시예는 본 발명의 특징을 밝히는 것으로 것으로서, 하기의 실시예에 한정되지 않고 당업자에 의해서 용이하게 변형 실시할 수 있음은 당업자의 수준에서 당연히 실시할 수 있는 범위까지도 포함한다. Hereinafter, the present invention will be described in detail with reference to examples of the present invention. The following examples illustrate the features of the present invention and are not intended to limit the scope of the present invention. It is to be understood that those skilled in the art can easily modify the present invention to the extent practicable at the level of those skilled in the art.
[[ 실시예Example 1] One]
폴리에테르폴리올 주제로서 수크로스/글리세롤기반 폴리알킬렌폴리올로서 JEFFOL SG-360을 80중량부와 20중량부의 트리에탄올아민계폴리알킬렌폴리올로서 WANOL R3004부의 혼합 폴리올 주제 100중량부에 대하여, 실리콘계 정포제 1.5중량부(테고스타브 B8450, 에보닉크 데그사 제품), 난연제로서 트리스(1-클로로-2-프로필) 포스페이트 20중량부, 촉매로서 N, N-디메틸아미노에톡시 에탄올 2중량부, 및 HFCs 발포제로서 1,1,1,3,3-펜타플루오로프로판, 1,1,1,4,4,4-헥사플루오로-2-부텐 및1-클로로-3,3,3-트리플루오로프로펜을 동량으로 전체 18 중량부를 혼합하였다. 80 parts by weight of JEFFOL SG-360 as a sucrose / glycerol-based polyalkylene polyol as a polyether polyol subject, and 100 parts by weight of a mixed polyol subject of WANOL R3004 part as a triethanolamine-based polyalkylene polyol as 20 parts by weight, 20 parts by weight of tris (1-chloro-2-propyl) phosphate as a flame retardant, 2 parts by weight of N, N-dimethylaminoethoxyethanol as a catalyst, and 2 parts by weight of HFCs As foaming agents, 1,1,1,3,3-pentafluoropropane, 1,1,1,4,4,4-hexafluoro-2-butene and 1-chloro-3,3,3-trifluoro An equal amount of propene was mixed in a total of 18 parts by weight.
경화제로서, 폴리머릭MDI로서, 금호미쓰이화학의 COSMONATE SR-500을 NCO/OH 당량이 1.3이 되도록 하여 투입하였다.As polymeric MDI, COSMONATE SR-500 from KUMHO MITSUI CHEMICAL CO., LTD. Was added as the curing agent so that the NCO / OH equivalent was 1.3.
상기에서 제조한 폴리올 주제 조성물과 경화제를 이용해 액화 이산화탄소 공급 장치를 구비한, 발포 분사 장치에 의해 상기 폴리올 주제 조성물에 이산화탄소를 2.8중량부를 초임계 상태로 공급하여 혼합시킨 후, 경화제를 접촉 혼합시켜 JIS-A-9526에 준하여 23±5℃, 상대습도80% 의 조건 하에서 2m x 2m x 1.5 m의 부스 내에서 분사를 하고, 발포 경화시킴으로써, 경질 폴리우레탄 폼을 제조하였다. 2.8 parts by weight of carbon dioxide was supplied to the polyol subject composition in a supercritical state by a foaming spraying device equipped with a liquefied carbon dioxide supplying device using the polyol subject composition and the curing agent prepared above, A hard polyurethane foam was prepared by spraying in a booth of 2 m x 2 m x 1.5 m under the conditions of 23 占 폚 and 80% relative humidity according to A-9526, followed by foaming and curing.
상기 제조한 폴리우레탄 폼의 발포셀을 관찰한 경과, 매우 균일한 원형의 발포셀이 조밀하게 형성되어 있음을 알 수 있었다. (도 1)As a result of observing the foamed cell of the polyurethane foam prepared above, it was found that a very uniform circular foam cell was densely formed. (Fig. 1)
치수안정성은 100 mm x 100 mm x 25 mm의 사이즈로 잘라서 온도 70℃, 습도95%로 유지된, 항온 항습조에 48 시간 정치시킨 후의 치수 변화를 측정하였다. 그 결과 변화율이 1% 미만의 치수안정을 나타 내었다.Dimensional stability was measured by measuring the dimensional stability after it was cut into a size of 100 mm x 100 mm x 25 mm and allowed to stand in a constant temperature and humidity chamber maintained at a temperature of 70 DEG C and a humidity of 95% for 48 hours. As a result, the change rate showed dimensional stability of less than 1%.
또한 폼의 밀도는 910 mm x 910 mm의 합판상으로 분사해 형성한, 폴리우레탄 폼의 두께를 가로세로에 약 등거리에 위치하는 13의 지점에서 측정하고 그 13점에 있어서의 두께의 평균에서 폴리우레탄 폼의 체적을 구하는 한편, 추가로 폴리우레탄 폼을 분사한 합판의 질량을 측정하고 미리 측정해 둔 합판의 질량을 뺌으로써, 폴리우레탄 폼의 질량을 구함으로써,밀도를 산출하였다. 그 결과 밀도가 41.0kg/㎥로서 발포된 기공의 크기가 커서 잘 발포되었음을 알 수있다. Also, the density of the foam was measured by measuring the thickness of the polyurethane foam, which was formed by spraying in the form of a plywood of 910 mm x 910 mm, at 13 points located approximately equidistant from the lateral and longitudinal sides, The volume of the urethane foam was determined, and the mass of the polyurethane foam was measured, and the mass of the polyurethane foam was determined by subtracting the mass of the plywood which had been measured in advance. The density was calculated. As a result, the density was 41.0 kg / m < 3 >
[[ 비교예Comparative Example 1] One]
상기 실시예 1에서 액상 이산화탄소를 투입하지 않고, HFCs를 각각 21중량부로 변경하여 투입한 것을 제외하고는 동일한 실험을 실시하였다. 그 결과 발포셀의 크기가 서로 상이한 크기들이 관측되어 기포의 크기의 균일성이 열세를 나타내는 것을 알 수 있었다.The same experiment was carried out except that the liquid carbon dioxide was not added in the above Example 1 but HFCs were changed to 21 parts by weight each. As a result, it was found that the sizes of the foamed cells were different from each other.
[[ 비교예Comparative Example 2] 2]
상기 실시예 1에서 주제로서 트리에탄올아민계폴리에테르폴리올을 사용하지 않고, 수크로스/글리세롤기반 폴리에테르폴리올 만을 100중량부로 사용한 것을 제외하고는 동일하게 실시하였다. 그 결과 표면의 발포셀의 파괴되기도 하고, 전체적으로 셀의 형태가 찌그러진 형태가 관찰되었다.Except that triethanolamine-based polyether polyol was not used as a subject in Example 1 and 100 parts by weight of sucrose / glycerol-based polyether polyol alone was used. As a result, the foam cell on the surface was broken, and the shape of the cell was distorted as a whole.
Claims (4)
상기 혼합 발포제는 상기 폴리올 주제 100중량부에 대하여 1 내지 40중량부 사용되고,
상기 혼합 발포제에서 상기 이산화탄소는 상기 HFCs 100중량부에 대하여 1 내지 30중량부 포함되는, 경질폴리우레탄 폼.
Based on 100 parts by weight of polyether-based polyol, 1 to 50 parts by weight of a mixed polyether polyol subject of triethanolamine-based polyether polyol, an amine-based catalyst, a curing agent containing a polymerizable MDI having an NCO functional group number of 2.5 to 2.9, Carbon dioxide mixed blowing agent of the present invention,
The mixed foaming agent is used in an amount of 1 to 40 parts by weight based on 100 parts by weight of the polyol subject,
Wherein the carbon dioxide in the mixed blowing agent is contained in an amount of 1 to 30 parts by weight based on 100 parts by weight of the HFCs.
상기 주제의 OH기의 당량 기준, NCO/OH 당량비가 0.8 내지 2.0의 중합형 MDI 경화제, 및 0.05 내지 5중량부의 아민계촉매를 사용하여 제조되는 경질 폴리우레탄 폼.
The method according to claim 1,
Rigid polyurethane foam prepared using an equivalent of OH groups of the subject, a polymerized MDI curing agent having an NCO / OH equivalent ratio of 0.8 to 2.0, and 0.05 to 5 parts by weight of an amine-based catalyst.
상기 우레탄 폼은 인계난연제를 상기 주제 100중량부에 대하여 5 내지 40중량부를 더 포함하여 제조되는 것인 경질 폴리우레탄 폼.
3. The method of claim 2,
Wherein the urethane foam is produced by further comprising 5 to 40 parts by weight of a phosphorus-based flame retardant per 100 parts by weight of the subject.
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