KR20090095889A - Flame retardant polyurethane foam and insulation using therof - Google Patents
Flame retardant polyurethane foam and insulation using therof Download PDFInfo
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- KR20090095889A KR20090095889A KR1020080021109A KR20080021109A KR20090095889A KR 20090095889 A KR20090095889 A KR 20090095889A KR 1020080021109 A KR1020080021109 A KR 1020080021109A KR 20080021109 A KR20080021109 A KR 20080021109A KR 20090095889 A KR20090095889 A KR 20090095889A
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- polyurethane foam
- flame retardant
- weight
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- raw material
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 53
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229920005830 Polyurethane Foam Polymers 0.000 title claims abstract description 32
- 239000011496 polyurethane foam Substances 0.000 title claims abstract description 32
- 238000009413 insulation Methods 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000011342 resin composition Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 23
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 22
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 22
- 238000012643 polycondensation polymerization Methods 0.000 claims abstract description 22
- 108010010803 Gelatin Proteins 0.000 claims abstract description 19
- 239000008273 gelatin Substances 0.000 claims abstract description 19
- 229920000159 gelatin Polymers 0.000 claims abstract description 19
- 235000019322 gelatine Nutrition 0.000 claims abstract description 19
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 19
- 229920002635 polyurethane Polymers 0.000 claims abstract description 18
- 239000004814 polyurethane Substances 0.000 claims abstract description 18
- 239000011810 insulating material Substances 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 11
- 150000003077 polyols Chemical class 0.000 claims abstract description 11
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 238000005187 foaming Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 239000004604 Blowing Agent Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011109 contamination Methods 0.000 abstract 1
- 239000004088 foaming agent Substances 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000004566 building material Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 239000002341 toxic gas Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011491 glass wool Substances 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011490 mineral wool Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920006328 Styrofoam Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000000539 amino acid group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000008261 styrofoam Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
- E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
- E04B1/78—Heat insulating elements
- E04B1/80—Heat insulating elements slab-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
- E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
- E04C2/10—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of wood, fibres, chips, vegetable stems, or the like; of plastics; of foamed products
- E04C2/20—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of wood, fibres, chips, vegetable stems, or the like; of plastics; of foamed products of plastics
- E04C2/205—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of wood, fibres, chips, vegetable stems, or the like; of plastics; of foamed products of plastics of foamed plastics, or of plastics and foamed plastics, optionally reinforced
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2266/00—Composition of foam
- B32B2266/02—Organic
- B32B2266/0214—Materials belonging to B32B27/00
- B32B2266/0278—Polyurethane
Landscapes
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Acoustics & Sound (AREA)
- Electromagnetism (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
본 발명은 난연성을 갖는 폴리우레탄 폼 및 이를 이용한 단열재에 관한 것으로, 더욱 상세하게는 폴리올과 이소시아네이트를 이용하여 폴리우레탄을 발포할 시에 파라포름알데히드, 젤라틴, 메탄올 등으로 되는 난연성 수지조성물을 혼합하여 발포함으로써, 폴리우레탄의 물성이 저하되지 않으면서도 내화성이 우수하고, 연소시 유독가스의 발생이 적은 폴리우레탄 폼에 관한 것이다.The present invention relates to a polyurethane foam having a flame retardancy and a heat insulating material using the same, and more particularly, by mixing a flame retardant resin composition consisting of paraformaldehyde, gelatin, methanol, etc. when foaming the polyurethane using a polyol and an isocyanate By foaming, it is related with the polyurethane foam which is excellent in fire resistance and does not generate | occur | produce the toxic gas at the time of combustion, without reducing the physical property of a polyurethane.
열경화성 수지로서 대표적인 폴리우레탄 수지는 비교적 저렴하고 성형이 용이해서, 이의 발포체는 자동차 부품을 비롯하여, 생활 용품 전반에 걸쳐 널리 사용되고 있다. 그러나, 폴리우레탄 수지는 가연성이며, 일단 착화하면 제어할 수 없이 연소한다. 따라서, 현재 폴리우레탄 수지가 이용되는 분야의 일부에서는, 법률적으로 폴리우레탄 수지 제품의 난연화를 의무화하고 있다. 예를 들면, 자동차내장 부품의 분야에서는 미국의 FMVSS 302, 건축재료의 분야에서는 일본의 JISA 1321,Polyurethane resins, which are representative of thermosetting resins, are relatively inexpensive and easy to mold, and their foams are widely used throughout automobiles and household goods. However, polyurethane resins are combustible and, once ignited, they burn out of control. Therefore, in some of the fields in which polyurethane resins are currently used, legally mandatory flame retardation of polyurethane resin products is required. For example, FMVSS 302 in the US in the field of automotive interior parts, JISA 1321 in Japan in the field of building materials,
가구에 관한 분야에서는 미국의 CAL 117, 영국의 BS 5852 등의 난연규제(難燃規制) 가 마련되어 있다.In the field of furniture, flame retardants such as CAL 117 in the United States and BS 5852 in the United Kingdom are established.
이러한 규제에 의해 정해진 기준을 충족시키기 위해서, 연질 폴리우레탄 폼에 인 함유 유기난연제(phosphorouscontaining organic flame retardant)를 배합하는 방법, 수산화 알루미늄(aluminum hydroxide), 3 산화 안티몬(antimony trioxide) 등의 무기난연제를 배합하는 방법 등이 널리 사용되었다. In order to meet the standards set by these regulations, a method of incorporating phosphorous containing organic flame retardant in a flexible polyurethane foam, inorganic flame retardants such as aluminum hydroxide, antimony trioxide, etc. The compounding method was widely used.
이러한 방법 중, 인 함유 유기난연제를 난연제로 사용하는 방법에서는, 폴리우레탄 발포체 연소시의 용융 적하물이 많아, 난연규제에서 정해진 기준을 만족하기 어렵다. 또한, 무기난연제를 난연제로 사용하는 방법에서는, 다량으로 사용하지 않으면 충분한 난연성을 부여할 수 없어 원료의 점도가 과도하게 상승할 뿐만 아니라, 폴리우레탄 발포체의 기계적물성이 저하되기 쉽다.Among these methods, in the method of using a phosphorus-containing organic flame retardant as a flame retardant, there are many melt drops during the combustion of polyurethane foam, and it is difficult to satisfy the criteria defined in the flame retardant regulation. In addition, in the method of using an inorganic flame retardant as a flame retardant, sufficient flame retardancy cannot be imparted unless it is used in large quantities, and the viscosity of a raw material rises excessively, and the mechanical properties of a polyurethane foam tend to fall easily.
한편, 일반적으로 건축용 조립식 패널은 약 0.5㎜ 정도의 강판 사이에 흡음성이나 단열성이 있는 심재를 넣어 접착시켜 제조되므로 지지성능을 위하여 일정수준 이상의 압축강도가 필요하다. 현재 상기 심재로 주로 폴리우레탄폼, 스티로폼과 같은 유기질 재료와, 유리면, 암면과 같은 무기질 재료가 사용되고 있다. 그러나 유기질 재료의 경우 필요로하는 압축강도는 발현되나 화재발생시 난연성능이 취약하여 점차 활용성이 떨어지고 있다. 반면, 무기질 재료의 경우 난연성능은 우수하나 제조 공정상의 분진발생 및 인체유해성으로 인하여 작업자나 시공자들이 기피하고 있는 실정이다. On the other hand, in general, prefabricated panels are manufactured by putting a sound absorbing or heat insulating core material between the steel plate of about 0.5mm, so that a certain level of compressive strength is required for supporting performance. Currently, as the core material, organic materials such as polyurethane foam and styrofoam, and inorganic materials such as glass wool and rock wool are used. However, in the case of organic materials, the required compressive strength is expressed, but the fire retardant performance is weak in case of fire, and its utility is gradually decreasing. On the other hand, in the case of inorganic materials, the flame retardant performance is excellent, but due to dust generation and human harmfulness in the manufacturing process, workers or builders are avoiding.
최근 건축자재로 많이 사용되고 있는 폴리에스테르 흡음단열재는 타 유기질 재료와는 달리 연소시에 유해가스가 발생하지 않고, 유리면이나 암면과 같은 무기섬유질 재료에 비하여 시공상의 용이성이나 인체무해성, 환경변화에 따른 형태변형이 없는 반영구적인 수명으로 각광받고 있으나, 난연성능의 미흡으로 인하여 용도확대에 많은 장애가 있다.Unlike other organic materials, polyester sound-absorbing insulation materials, which are widely used as building materials, do not generate harmful gases during combustion, and they are easier to construct, harmless to humans, and environmental changes than inorganic fiber materials such as glass wool or rock wool. Although it is spotlighted as a semi-permanent life without shape deformation, there are many obstacles in expanding the use due to the lack of flame retardant performance.
상기한 문제점을 해결하기 위하여, 수용성 난연제를 개발하여 건축자재의 표면에 수용성 난연제를 도포하거나 스프레이하는 기술들이 선출원되었으나, 표면도포만으로는 난연성이 충분히 발휘될 수 없고, 화재가 조기 진화되지 않을 경우는 난연제의 도포가 전혀 화재를 지연시키지 못하는 등의 문제점이 있었다.In order to solve the above problems, technologies for applying a water-soluble flame retardant to the surface of building materials by developing a water-soluble flame retardant have been applied for, but the surface coating alone can not be sufficiently flame retardant, if the fire does not extinguish prematurely flame retardant There was a problem such that the application of does not delay the fire at all.
따라서 본 발명의 목적은, 폴리올과 이소시아네이트을 이용하여 폴리우레탄을 발포할 시에 파라포름알데히드, 젤라틴, 메탄올 등으로 되는 난연성 수지조성물을 혼합하여 발포함으로써, 난연성을 갖는 폴리우레탄폼을 제공하도록 하는 것이다.Accordingly, an object of the present invention is to provide a flame-retardant polyurethane foam by mixing and foaming a flame-retardant resin composition of paraformaldehyde, gelatin, methanol and the like when foaming a polyurethane by using a polyol and an isocyanate.
또한 난연성 수지조성물을 혼합하여 발포하여도 폴리우레탄의 기본물성이 전혀 저하되지 않도록 하고, 연소시 유독가스의 발생이 적어 화재발생시 인명과 재산상의 손실을 최소화하며, 폐기시에도 환경 오염이 최소화되도록 하는 것이다.In addition, even when foamed with a flame-retardant resin composition, foaming does not reduce the basic physical properties of polyurethane at all, and there is little generation of toxic gases during combustion, thereby minimizing the loss of life and property in the event of fire and minimizing environmental pollution during disposal. will be.
또한 상기 난연성을 갖는 폴리우레탄 폼의 양면에 금속판을 접합하여 단열재로의 사용이 가능하도록 하는 것이다.In addition, by bonding a metal plate on both sides of the flame-retardant polyurethane foam to be used as a heat insulating material.
상기와 같은 목적을 달성하기 위한 본 발명의 난연성을 갖는 폴리우레탄 폼은 폴리올, 이소시아네이트 및 발포제를 포함하여 되는 폴리우레탄의 주재에 난연성 수지조성물을 혼합하고, 발포하여서 되는 것을 특징으로 한다.Polyurethane foam having a flame retardancy of the present invention for achieving the above object is characterized by mixing and foaming a flame-retardant resin composition to the main body of polyurethane comprising a polyol, isocyanate and a blowing agent.
또한 상기 난연성 수지조성물은 파라포름알데히드, 젤라틴, 메탄올, 축합중합형 열경화성수지의 원료 및 물을 준비하는 단계와,In addition, the flame-retardant resin composition is preparing a raw material and water of paraformaldehyde, gelatin, methanol, condensation polymerization type thermosetting resin,
상기 준비된 원료에 수산화나트륨을 가하여 pH가 8∼9가 되도록 하는 단계와,Adding sodium hydroxide to the prepared raw material to have a pH of 8 to 9;
상기 pH가 조절된 원료를 혼합하여 반응시키는 단계와,Reacting by mixing the pH-adjusted raw material;
상기 반응된 반응물에 산을 첨가하여 pH가 4∼5가 되도록 하는 단계를 포함하여 제조되는 것을 특징으로 한다.It characterized in that it comprises the step of adding an acid to the reacted reactant to have a pH of 4 to 5.
그리고 상기 발포된 폴리우레탄 폼의 상, 하부에 금속판이 추가로 압착되어 단열재를 구성하는 것을 특징으로 한다.And the upper and lower parts of the foamed polyurethane foam is characterized in that the metal plate is further compressed to constitute a heat insulating material.
본 발명은 폴리올과 이소시아네이트을 이용하여 폴리우레탄을 발포할 시에 파라포름알데히드, 젤라틴, 메탄올 등으로 되는 난연성 수지조성물을 혼합하여 발포함으로써, 내화성을 갖는 단열재를 손쉽게 생산할 수 있도록 하고, 난연성 수지조성물을 혼합하여 발포하여도 폴리우레탄의 기본물성이 전혀 저하되지 않도록 하며, 폴리우레탄 폼의 연소시 유독가스의 발생이 적어 화재발생시 인명과 재산상의 손실을 최소화할 뿐만 아니라, 폐기시에도 환경 오염이 최소화되도록 하는 등의 유용한 효과를 제공한다.The present invention mixes and foams a flame retardant resin composition made of paraformaldehyde, gelatin, methanol and the like when foaming a polyurethane by using a polyol and an isocyanate, thereby easily producing a fire-resisting heat insulating material, and mixing a flame retardant resin composition. Even if it foams, the basic physical properties of polyurethane are not lowered at all, and the generation of toxic gas is less when burning the polyurethane foam, which not only minimizes loss of life and property in the event of fire, but also minimizes environmental pollution during disposal. To provide useful effects.
또한 상기 폴리우레탄 폼의 양면에 금속판을 접합시켜 단열재로 사용할 수 있도록 하는 등의 유용한 효과를 제공한다.In addition, by bonding a metal plate on both sides of the polyurethane foam to provide a useful effect, such as to be used as a heat insulating material.
이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 난연성을 갖는 폴리우레탄 폼은 폴리올(polyol)과 이소시아 네이트를 반응시켜 발포하여서 이루어지되, 발포시 난연성 수지조성물을 더 혼합하여 발포함으로써 되는 것이다.Polyurethane foam having a flame retardancy according to the present invention is made by foaming by reacting a polyol (iso) and isocyanate, by foaming by further mixing the flame-retardant resin composition when foaming.
그리고 상기 폴리올로는 폴리에스테르와 에테르를 이용할 수 있는 바, 종래 단열재를 구성하는 폴리올은 모두 사용할 수 있는 것으로, 그 종류를 제한하지 않는다. 이때 상기 폴리에스테르와 에테르는 폴리에스테르 70∼90중량%와 에테르 10∼30중량%로 혼합하는 것이 단열재로서의 물성이 우수하게 된다.And as the polyol can be used polyester and ether, the polyol constituting the conventional heat insulating material can be used all, and the kind is not limited. At this time, the polyester and the ether is mixed with 70 to 90% by weight of polyester and 10 to 30% by weight of the ether is excellent in physical properties as a heat insulating material.
그리고 상기 이소시아네이트로는 디페닐메탄-4,4-디이소시아네이트(MDI)를 사용할 수 있는 데, 이는 우레탄 반응 시 강도면에서 뛰어나고 표면경화성이 우수하기 때문이다.In addition, diphenylmethane-4,4-diisocyanate (MDI) may be used as the isocyanate because it is excellent in strength during urethane reaction and has excellent surface hardenability.
그리고 상기 폴리우레탄의 주재로는 상기 폴리올과 이소시아네이트 외에도 발포제가 추가되는 바, 상기 발포제는 폴리올과 이소시아네이트의 발포를 위한 것으로, 이 기술이 속하는 분야에서는 이미 공지된 물질이므로 그에 대한 상세한 설명은 생략하며, 종래 사용되는 물, HCFC-141B와 같은 모든 종류의 발포제를 사용할 수 있는 것다.And as the main material of the polyurethane is added to the blowing agent in addition to the polyol and isocyanate, the blowing agent is for the foaming of the polyol and isocyanate, it is already known in the art belongs to this technology, so a detailed description thereof will be omitted, It is possible to use all kinds of blowing agents such as conventionally used water, HCFC-141B.
또한 발포속도를 빠르게 하기 위하여 촉매를 추가할 수도 있으며, 우레탄의 원료성분을 균일하게 분산시켜 빠르게 안정화시키는 정포제를 추가로 포함할 수도 있다.In addition, a catalyst may be added to increase the foaming speed, and may further include a foam stabilizer which stabilizes rapidly by uniformly dispersing a raw material of the urethane.
상기 촉매와 정포제는 각각 포함될 수도 있으며, 동시에 포함될 수도 있는 것이며, 정포제로서는 많이 사용되고 있는 실리콘계 정포제를 사용할 수 있다.The catalyst and the foam stabilizer may be included, respectively, may be included at the same time, as the foam stabilizer can be used a silicon-based foam stabilizer.
상기 난연성 수지조성물은 폴리우레탄과 함께 발포되어 폴리우레탄에 난연성, 내화성을 부여하는 것으로서, 상세한 설명은 이하에서 다시 설명한다.The flame retardant resin composition is foamed together with the polyurethane to impart flame retardancy and fire resistance to the polyurethane, which will be described later.
그리고 상기 폴리우레탄의 주재와 난연성 수지조성물은, 폴리우레탄의 주재 50∼70중량%와 난연성 수지조성물 30∼50중량%로 혼합되는 것이 바람직한 바, 이는 난연성 수지조성물이 30중량% 미만이되면 난연성의 효과가 충분히 발휘되지 못하고 50중량%를 초과하면 과량이되어 폴리우레탄의 물성이 저하될 우려가 있기 때문이다.And the main material of the polyurethane and the flame retardant resin composition is preferably mixed with 50 to 70% by weight of the main material of the polyurethane and 30 to 50% by weight of the flame retardant resin composition, which is when the flame retardant resin composition is less than 30% by weight This is because if the effect is not sufficiently exerted and exceeds 50% by weight, the amount of excess may be excessive and the physical properties of the polyurethane may be lowered.
상기와 같이 폴리우레탄의 주재와 난연성 수지조성물은 혼합, 발포되어 신규한 난연성을 갖는 폴리우레탄 폼을 구성하는 것이다.As described above, the main body of polyurethane and the flame retardant resin composition are mixed and foamed to form a polyurethane foam having novel flame retardancy.
상기와 같이 구성된 본 발명에 따른 난연성을 갖는 폴리우레탄 폼은 열방출량 4.3∼4.7MJ/㎡(건교고시 제2006-476기준 8MJ/㎡ 이하)와 가스유해성시험 13:23∼13:35/min(건교고시 제2006-476기준 9min 이상)으로 한국건자재시험연구원의 준불연재료에 적합한 우수한 품질을 갖는 것이다.The flame-retardant polyurethane foam according to the present invention configured as described above has a heat release rate of 4.3 ~ 4.7MJ / ㎡ (8MJ / ㎡ or less as of 2006-476 of the cross-linking) and the gas hazard test 13:23 ~ 13: 35 / min ( It is of high quality suitable for semi-combustible materials of Korea Building Materials Testing & Research Institute.
상기한 난연성을 갖는 폴리우레탄 폼은 단독으로 단열재로 유용하게 사용될 수 있다.Polyurethane foam having the above flame retardancy can be usefully used alone as a heat insulating material.
또한 종래의 폴리우레탄 폼과 같이, 상기 난연성을 갖는 폴리우레탄 폼의 상, 하부에 금속판을 추가로 압착시켜 단열재로 사용할 수도 있는 것이다. In addition, as in the conventional polyurethane foam, a metal plate may be further compressed on the upper and lower portions of the flame retardant polyurethane foam and used as a heat insulating material.
이때 상기 금속판의 압착은 성형기의 내부온도를 60∼80℃ 정도로 상승시켜 압착하는 것으로, 그 방법을 제한하지 않는다.At this time, the pressing of the metal plate is carried out by raising the internal temperature of the molding machine to about 60 to 80 ° C., and the method is not limited.
이하 본 발명에 따른 난연성 수지조성물에 대해 설명하면 다음과 같다.Hereinafter, the flame retardant resin composition according to the present invention will be described.
본 발명에 따른 난연성 수지조성물은, 파라포름알데히드, 젤라틴, 메탄올 및 축합중합형 열경화성수지의 원료를 포함하여 이루어지는 것을 특징으로 한다.The flame retardant resin composition according to the present invention is characterized by comprising a raw material of paraformaldehyde, gelatin, methanol and a condensation polymerization type thermosetting resin.
이때 상기 파라포름알데히드(paraformaldehyde)는 포름알데히드 중합체들의 혼합물로서, 흰 무정형 가루로 되고, 수산화나트륨 용액에 쉽게 녹는다. 상기 파라포름알데히드는 난연성 수지조성물 내에서 축합중합형 열경화성수지의 원료와 반응하여 난연성을 부여하는 역할을 하는 것이다.The formaldehyde (paraformaldehyde) is a mixture of formaldehyde polymers, a white amorphous powder, easily soluble in sodium hydroxide solution. The paraformaldehyde serves to impart flame retardancy by reacting with a raw material of a condensation polymerization type thermosetting resin in a flame retardant resin composition.
그리고 상기 젤라틴은 화학적으로 아미노산 기를 띠고 있는 알라닌(Alanine), 그리신(Glycine), 프롤린(Proline) 및 글루타민(Glutamic)을 기본 작용기로 갖고 있으며, 사슬이 탄소 원자로 연결되어 있어(즉 탄화 사슬이 많이 존재) 젤라틴이 연소물질에 흡착된다면 화재시 불연성 가스인 암모니아(NH3)를 다량 방출 할 것이므로, 가연성 물질 주위의 혼합 기체의 농도를 가연한계에 이르지 않도록 하여 난연 및 방염효과를 증대시킨다. 또한 이미 존재하는 탄화막의 존재에 기인하여 산소의 접근을 저지함으로써 난연 효과에 지대한 영향을 미치며, 젤라틴 내에 존재하는 탄화사슬은 연소에 필요한 열량을 공급하는 산화반응이나 열전달을 위축, 저하시킬 뿐만 아니라, 불꽃 전파의 주요원인인 기화를 저지하는 역할을 하는것이다.In addition, the gelatin has alanine, glycine, proline, and glutamine, which are chemically amino acid groups, as basic functional groups, and the chains are connected to carbon atoms (that is, a lot of carbonized chains). Presence) If gelatin is adsorbed on combustion materials, it will release a large amount of incombustible ammonia (NH 3 ) in case of fire, so that the concentration of mixed gas around the combustible materials does not reach the flammable limit, thereby increasing the flame retardant and flame retardant effect. In addition, due to the presence of the existing carbide film, by blocking the access of oxygen has a profound effect on the flame retardant effect, the carbon chain present in the gelatin not only attenuates and lowers the oxidation reaction or heat transfer that supplies the heat required for combustion, It is to prevent vaporization, which is the main cause of flame propagation.
상기 메탄올은 상기 파라포름알데히드가 축합중합형 열경화성수지의 원료와 반응한 후 유리된 파라포름알데히드를 제거하기 위한 것으로, 난연성 수지조성물이 포름알데히드를 방출하는 것을 방지함은 물론, 난연성 수지조성물의 기계적 물성을 우수하게 하는 역할 또한 하는 것이다.The methanol is to remove the free paraformaldehyde after the paraformaldehyde reacts with the raw material of the condensation polymerization thermosetting resin, and the flame retardant resin composition prevents the release of formaldehyde, as well as the mechanical properties of the flame retardant resin composition. It also plays a role in improving physical properties.
상기 축합중합형 열경화성수지의 원료는 멜라민, 페놀, 우레아 중 선택된 1종 또는 2종 이상의 혼합물로 되는 것으로, 단독으로 사용하거나 혼합하여 사용할 수 있다.The raw material of the condensation polymerization type thermosetting resin is one selected from melamine, phenol, urea, or a mixture of two or more kinds, and may be used alone or in combination.
상기 축합중합형 열경화성수지의 원료는 연소시 유독한 가스가 발생되지 않으며, 연기의 발생 또한 적은 것이 특징이다. 상기 축합중합형 열경화성수지의 원료는 파라포름알데히드와 반응하여 수지조성물 내에서 난연성을 부여하는 것으로서, 가장 바람직하게는 멜라민을 사용하는 것이다. The raw material of the condensation polymerization type thermosetting resin is characterized in that no toxic gas is generated during combustion, and smoke is also less generated. The raw material of the condensation polymerization type thermosetting resin reacts with paraformaldehyde to impart flame retardancy in the resin composition, and most preferably, melamine is used.
이때 상기 조성물들은 파라포름알데히드 100중량부를 기준으로, 젤라틴 1∼5중량부, 메탄올 10∼20중량부, 축합중합형 열경화성수지의 원료 90∼110중량부를 포함하는 바, 상기 젤라틴이 1중량부 미만이 되면 그 효과가 미만이되고 5중량%를 초과하면 축합중합형 열경화성수지의 원료의 물성을 저하시킬 우려가 있으며, 상기 메탄올이 10중량부 미만이되면 유기된 파라포름알데히드의 제거효과가 떨어지고 20중량부를 초과하면 과량이되어 축합중합형 열경화성수지의 원료의 물성을 저하시킬 우려가 있으며, 축합중합형 열경화성수지의 원료가 90중량부 미만이면 안정성이 좋지 못하고 110 중량부를 초과하면 과량이 되어 경제적이지 못하기 때문이다.At this time, the compositions are based on 100 parts by weight of paraformaldehyde, 1 to 5 parts by weight of gelatin, 10 to 20 parts by weight of methanol, 90 to 110 parts by weight of the raw material of the condensation polymerization type thermosetting resin, the gelatin is less than 1 part by weight When the effect is less than 5% by weight, the physical property of the raw material of the condensation polymerization type thermosetting resin may be lowered. When the methanol is less than 10 parts by weight, the effect of removing the organic paraformaldehyde is deteriorated. If it exceeds the weight part, it may be excessive, which may lower the physical properties of the raw material of the condensation polymerization type thermosetting resin.If the material of the condensation polymerization type thermosetting resin is less than 90 parts by weight, the stability is not good. Because you can not.
상기에서 설명된 바와 같이, 파라포름알데히드, 젤라틴, 메탄올 및 축합중합형 열경화성수지의 원료를 포함하는 난연성 수지조성물은 단독으로 폴리우레탄과 함께 발포되어 단열재로서 사용될 수 있는 것으로, 내화성, 난연성이 우수한 특성이 있다.As described above, the flame-retardant resin composition containing a raw material of paraformaldehyde, gelatin, methanol and a condensation polymerization type thermosetting resin can be used alone as a foam to be used as a heat insulating material, foamed with polyurethane, it is excellent in fire resistance and flame resistance There is this.
이하 본 발명에 따른 난연성 수지조성물의 제조방법에 대해 상세히 설명하면 다음과 같다.Hereinafter, a method for preparing a flame retardant resin composition according to the present invention will be described in detail.
먼저 파라포름알데히드, 젤라틴, 메탄올, 축합중합형 열경화성수지의 원료 및 물을 각각 준비한다. First, raw materials and water of paraformaldehyde, gelatin, methanol, and a condensation polymerization thermosetting resin are prepared.
원료를 준비할 시, 파라포름알데히드 100중량부, 젤라틴 1∼5중량부, 메탄올 10∼20중량부, 축합중합형 열경화성수지의 원료 90∼110중량부 및 물 120∼140중량부가 되도록 준비하는 바, 각 배합비에 대한 설명은 상기에서 충분히 이루어졌으므로, 그에 대한 상세한 설명은 생략한다.When preparing a raw material, prepare 100 parts by weight of paraformaldehyde, 1 to 5 parts by weight of gelatin, 10 to 20 parts by weight of methanol, 90 to 110 parts by weight of the raw material of the condensation polymerization thermosetting resin, and 120 to 140 parts by weight of water. Since the description of each compounding ratio was made enough above, detailed description is abbreviate | omitted.
상기 물은 젤라틴을 녹이고, 수지조성물의 반응을 돕게하기 위한 것으로,상기 물이 120중량부 미만이 되면 소량이 되어 젤라틴의 용해가 어렵고 각 조성물의 혼합이 어렵게 등의 문제가 있고, 140중량부를 초과하면 과량이 되어 후공정인 농축시 제조비용이 상승하는 문제점이 있기 때문이다.The water is to dissolve the gelatin, and to help the reaction of the resin composition, when the water is less than 120 parts by weight is a small amount is difficult to dissolve the gelatin and difficult to mix the composition, and more than 140 parts by weight This is because there is a problem that the manufacturing cost increases when the concentration becomes excessive when it is concentrated.
그리고 앞서 설명한 바와 같이, 상기 축합중합형 열경화성수지의 원료는 멜라민, 페놀, 우레아 중 선택된 1종이 단독으로 사용되거나 선택된 2종 이상의 혼합물로 사용되는 것이 모두 가능하다. And as described above, the raw material of the condensation polymerization type thermosetting resin may be used either one selected from melamine, phenol, urea alone or used as a mixture of two or more selected.
상기와 같이 준비가 완료되면, 상기 준비한 원료에 수산화나트륨(NaOH)을 가하여 pH가 8∼9가 되도록 조절한다. 이때 상기 수산화나트륨은 파라포름알데히드의 용매로서 작용하여, 파라포름알데히드와 축합중합형 열경화성수지의 원료의 반응을 돕는 것이다. 이때 상기 pH를 8∼9가 되도록 조절하는 이유는 파라포름알데히드와 축합중합형 열경화성수지의 원료의 반응이 용이하게 이루어지게 하기 위해서는 8∼9의 pH가 적정하기 때문이다.When the preparation is completed as described above, the sodium hydroxide (NaOH) is added to the prepared raw material to adjust the pH to 8-9. At this time, the sodium hydroxide acts as a solvent of paraformaldehyde, to help the reaction of the paraformaldehyde and the raw material of the condensation polymerization thermosetting resin. At this time, the pH is adjusted to 8-9 because the pH of 8-9 is appropriate to facilitate the reaction of the raw material of the paraformaldehyde and the condensation polymerization type thermosetting resin.
상기 pH가 조절되면, 상기 pH가 조절된 원료를 혼합하여 반응시킨다. 이때 상기 반응 온도는 80∼90℃가 되도록 하는 것이 바람직한 바, 상기 반응 온도를 80∼90℃로 하는 이유는 상기한 온도 범위 내에서 반응이 용이하게 일어나기 때문이며, 그 반응시간을 약 40∼60분으로 하여 충분한 반응이 유도되도록 한다.When the pH is adjusted, the pH-adjusted raw materials are mixed and reacted. At this time, the reaction temperature is preferably 80 to 90 ° C. The reason for the reaction temperature to 80 to 90 ° C. is that the reaction occurs easily within the above temperature range, and the reaction time is about 40 to 60 minutes. Sufficient reaction is induced.
반응이 완료되면, 상기 반응된 반응물을 산을 이용하여 pH가 4∼5가 되도록 중화한다. 이때 상기 pH를 4∼5가 되도록 하는 이유는 상기 반응된 반응물의 중합 도를 높이기 위함이다.When the reaction is complete, the reacted reactant is neutralized to pH 4-5 using an acid. In this case, the reason for setting the pH to 4 to 5 is to increase the degree of polymerization of the reacted reactants.
그리고 상기 산으로는, 질산(HNO3)을 이용할 수 있는 바, 이를 반드시 제한하는 것은 아니며, 수지조성물의 물성을 저하시키지 않는다면 다양한 산을 사용할 수 있음은 물론이다.In addition, as the acid, nitric acid (HNO 3 ) may be used. However, the acid is not necessarily limited, and various acids may be used unless the physical properties of the resin composition are lowered.
상기와 같이 산을 첨가하고 약 60∼90분 후에는, 이를 농축하여 과량의 수분을 제거한다. After about 60 to 90 minutes of adding the acid as above, it is concentrated to remove excess moisture.
이상에서와 같이 본 발명은 상기한 실시예에 한하여 설명되었지만 이를 반드시 제한하는 것은 아닌 것으로, 본 발명의 범주와 사상을 벗어나지 않는 범위 내에서 다양한 변형 실시가 가능함은 물론이다.As described above, the present invention has been described with reference to the above embodiments, but it is not necessarily limited thereto, and various modifications may be made without departing from the scope and spirit of the present invention.
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| KR20210022315A (en) | 2019-08-20 | 2021-03-03 | 롯데케미칼 주식회사 | Polyester polyol, manufacturing method thereof and manufacturing method polyurethane using the same |
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| US11111364B2 (en) | 2016-03-11 | 2021-09-07 | Case Western Reserve University | Flame retardant polymer composite materials and methods of making the same |
| KR20210022315A (en) | 2019-08-20 | 2021-03-03 | 롯데케미칼 주식회사 | Polyester polyol, manufacturing method thereof and manufacturing method polyurethane using the same |
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