KR20240003110A - Eco-friendly polyurethane composition - Google Patents
Eco-friendly polyurethane composition Download PDFInfo
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- KR20240003110A KR20240003110A KR1020220080191A KR20220080191A KR20240003110A KR 20240003110 A KR20240003110 A KR 20240003110A KR 1020220080191 A KR1020220080191 A KR 1020220080191A KR 20220080191 A KR20220080191 A KR 20220080191A KR 20240003110 A KR20240003110 A KR 20240003110A
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- polyisocyanate
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- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 239000004814 polyurethane Substances 0.000 title claims abstract description 36
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 36
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 33
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 33
- 239000002262 Schiff base Substances 0.000 claims abstract description 21
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 150000002148 esters Chemical class 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 14
- 150000003077 polyols Chemical class 0.000 claims abstract description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 5
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 claims description 4
- OFLXLNCGODUUOT-UHFFFAOYSA-N acetohydrazide Chemical compound C\C(O)=N\N OFLXLNCGODUUOT-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 23
- 229920005830 Polyurethane Foam Polymers 0.000 description 7
- 239000011496 polyurethane foam Substances 0.000 description 7
- -1 aldehyde compounds Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000011489 building insulation material Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 208000008842 sick building syndrome Diseases 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 208000011580 syndromic disease Diseases 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- JPIGSMKDJQPHJC-UHFFFAOYSA-N 1-(2-aminoethoxy)ethanol Chemical compound CC(O)OCCN JPIGSMKDJQPHJC-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- JZUFKLXOESDKRF-UHFFFAOYSA-N Chlorothiazide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC2=C1NCNS2(=O)=O JZUFKLXOESDKRF-UHFFFAOYSA-N 0.000 description 1
- 206010014561 Emphysema Diseases 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4054—Mixtures of compounds of group C08G18/60 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/60—Polyamides or polyester-amides
- C08G18/603—Polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/25—Carboxylic acid hydrazides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
본 발명은 친환경 폴리우레탄 조성물에 관한 것으로, 좀더 상세하게 설명하자면, 폴리이소시아네이트 29~90 중량%와, 폴리올 또는 아스파틱 에스테르 수지(aspartic ester resin) 9~70 중량%와, 포름알데히드와 반응하여 시프염기(schiff base)를 형성하는 시프염기 전구체 0.01~1 중량%를 포함하여 구성됨으로써, 포름알데히드의 방출량이 현저하게 낮은 친환경 폴리우레탄 조성물에 관한 것이다.The present invention relates to an eco-friendly polyurethane composition. To be described in more detail, 29 to 90% by weight of polyisocyanate, 9 to 70% by weight of polyol or aspartic ester resin, and formaldehyde react to form Schiff. It relates to an eco-friendly polyurethane composition that contains 0.01 to 1% by weight of a Schiff base precursor forming a base (schiff base), thereby emitting significantly low formaldehyde.
Description
본 발명은 친환경 폴리우레탄 조성물에 관한 것으로, 좀더 상세하게 설명하자면, 폴리이소시아네이트 49~90 중량%와, 폴리올 또는 아스파틱 에스테르 수지(aspartic ester resin) 9~50 중량%와, 포름알데히드와 반응하여 시프염기(schiff base)를 형성하는 시프염기 전구체 0.01~1 중량%를 포함하여 구성됨으로써, 포름알데히드의 방출량이 현저하게 낮은 친환경 폴리우레탄 조성물에 관한 것이다. The present invention relates to an eco-friendly polyurethane composition. To be described in more detail, 49 to 90% by weight of polyisocyanate, 9 to 50% by weight of polyol or aspartic ester resin, and formaldehyde are reacted to form Schiff. It relates to an eco-friendly polyurethane composition that contains 0.01 to 1% by weight of a Schiff base precursor forming a base (schiff base), thereby emitting significantly low formaldehyde.
폴리우레탄은 폴리올과 폴리이소시아네이트가 반응하여 생성되는 고분자 화합물로서, 탄성이 풍부하고 접착성 및 내구성이 우수하여 방수성 도료나, 접착제, 탄성 포장재, 건축용 단열재, 자동차 내장재 등의 용도는 광범위하게 사용되고 있다.Polyurethane is a polymer compound produced by the reaction of polyol and polyisocyanate. It is rich in elasticity and has excellent adhesiveness and durability, so it is widely used in waterproof paints, adhesives, elastic packaging materials, building insulation materials, and automobile interior materials.
그런데 이러한 폴리우레탄은 단량체(monomer)가 경화되는 과정에서 포름알데히드, 아세트 알데히드 및 프로피온 알데히드와 같은 알데히드 화합물을 방출하고, 이는 새집증후군이나 새차증후군의 원인이 된다. However, these polyurethanes release aldehyde compounds such as formaldehyde, acetaldehyde, and propionic aldehyde during the curing process of the monomer, which causes sick house syndrome or sick car syndrome.
이 중에서 특히 포름알데히드는 인체에 대한 독성이 매우 강한 휘발성 유기화합물(VOC)로서, 50ppm 이상의 농도에 장시간 노출될 경우 독성 폐기종이 발생할 수 있고, 심하면 사망에 이를 수도 있다. 그래서 종래에도 폴리우레탄에서 포름알데히드를 감소 또는 제거하려는 노력들이 다양하게 시도되어 왔다. Among these, formaldehyde in particular is a volatile organic compound (VOC) that is highly toxic to the human body. If exposed to a concentration of 50 ppm or more for a long time, toxic emphysema may occur, and in severe cases, it may even lead to death. Therefore, various efforts have been made in the past to reduce or remove formaldehyde from polyurethane.
먼저 특허 제10-1075566호(2011년 10월 14일)에는, 휘발성 유기화합물, 특히 포름알데히드의 발생을 최소화 할 수 있는 친환경 뿜칠용 폴리우레탄 발포체용 조성물이 개시되어 있다. 상기 폴리우레탄 발포체 조성물은 레진 프리믹스 45~55 중량%와 폴리이소시아네이트 55~45 중량%로 이루어지고, 상기 레진 프리믹스는 재활용 폴리에테르 폴리올과 폴리에스테르 폴리올, 가교제, 반응형 아민계 우레탄 촉매, 금속계 우레탄 촉매, 실리콘 계면활성제, 물, 난연제 및 발포제로 구성된다. First, Patent No. 10-1075566 (October 14, 2011) discloses an eco-friendly polyurethane foam composition for spray coating that can minimize the generation of volatile organic compounds, especially formaldehyde. The polyurethane foam composition consists of 45 to 55% by weight of resin premix and 55 to 45% by weight of polyisocyanate, and the resin premix includes recycled polyether polyol and polyester polyol, crosslinking agent, reactive amine-based urethane catalyst, and metal-based urethane catalyst. It consists of silicone surfactant, water, flame retardant and foaming agent.
다음으로 특허 제10-1692970호(2016년 12월 29일)에는, 포름알데히드 및 아세트 알데히드의 발생량을 감소시킬 수 있는 액상제거제를 포함하는 폴리우레탄 폼 및 그 제조방법이 개시되어 있다. 상기 액상제거제는, 아민기를 갖는 화합물 5~40 중량%, 산화방지 기능을 갖는 천연화합물 5~30 중량%, 계면활성제 5~20 중량%, 및 잔량의 히드록시기를 갖는 용매로 구성된다.Next, Patent No. 10-1692970 (December 29, 2016) discloses a polyurethane foam containing a liquid remover that can reduce the amount of formaldehyde and acetaldehyde generated, and a method for manufacturing the same. The liquid remover consists of 5 to 40% by weight of a compound having an amine group, 5 to 30% by weight of a natural compound with an antioxidant function, 5 to 20% by weight of a surfactant, and the remaining amount of a solvent having a hydroxy group.
또한 특허 제10-2084745호(2020년 02월 27일)에는, 알데히드 저감제 조성물 및 이를 이용한 연질 폴리우레탄 폼의 제조방법이 개시되어 있다. 상기 알데히드 저감제 조성물은, 하이드록실기와 아민기를 가진 화합물 5~20 중량%, 알칼리 금속 또는 알칼리 토금속의 황산염 화합물 1~10 중량%, 산화방지 기능을 가진 화합물 0.1~ 5 중량%, HLB가 4~16인 비이온계 계면활성제 또는 pH 5~10인 이온성 계면활성제 3~20 중량%, 및 잔량의 히드록실기를 갖는 용매로 구성된다.Additionally, Patent No. 10-2084745 (February 27, 2020) discloses an aldehyde reducing agent composition and a method of manufacturing flexible polyurethane foam using the same. The aldehyde reducing agent composition contains 5 to 20% by weight of a compound having a hydroxyl group and an amine group, 1 to 10% by weight of a sulfate compound of an alkali metal or alkaline earth metal, 0.1 to 5% by weight of a compound with an antioxidant function, and an HLB of 4. It consists of 3 to 20% by weight of a nonionic surfactant with a pH of ~16 or an ionic surfactant with a pH of 5 to 10, and the balance of a solvent having a hydroxyl group.
마지막으로 공개특허 제10-2021-0040096호(2021년 04월 12일)에는, 폴리우레탄 폼에서 알데히드의 방출을 감소시키는 방법이 개시되어 있다. 상기 방법은, 방향족 폴리이소시아네이트, 적어도 2개의 평균 관능기 및 이소시아네이트 반응성 기당 적어도 200의 당량을 갖는 이소시아네이트 반응성 물질, 발포제, 계면활성제 및 촉매, 환형 1,3-디케톤 및 적어도 하나의 아미노알코올 또는 알킬하이드록실아민을 함유하는 반응혼합물을 경화시켜서 폴리우레탄 폼을 제조한다.Lastly, Publication Patent No. 10-2021-0040096 (April 12, 2021) discloses a method for reducing the emission of aldehyde from polyurethane foam. The method comprises an aromatic polyisocyanate, an isocyanate-reactive material having at least two average functional groups and an equivalent weight of at least 200 per isocyanate-reactive group, a blowing agent, a surfactant and a catalyst, a cyclic 1,3-diketone and at least one aminoalcohol or alkylhyde. Polyurethane foam is prepared by curing the reaction mixture containing roxylamine.
본 발명의 목적은 인체에 유해한 포름알데히드의 발생량을 최소화 할 수 있는 새로운 친환경 폴리우레탄 조성물을 제공하는 것이다. The purpose of the present invention is to provide a new eco-friendly polyurethane composition that can minimize the amount of formaldehyde harmful to the human body.
본 발명에 따른 친환경 폴리우레탄 조성물은, 점도가 1200cp~3000cp인 폴리이소시아네이트 49~90 중량%와, 폴리올 또는 아스파틱 에스테르 수지(aspartic ester resin) 9~50 중량%와, 포름알데히드와 반응하여 시프염기(schiff base)를 형성하는 시프염기 전구체 0.01~1 중량%를 포함하여 구성되는 것을 특징으로 한다.The eco-friendly polyurethane composition according to the present invention reacts with 49 to 90 wt% of polyisocyanate having a viscosity of 1200 cp to 3000 cp, 9 to 50 wt% of polyol or aspartic ester resin, and formaldehyde to form Schiff base. It is characterized in that it contains 0.01 to 1% by weight of a Schiff base precursor forming a Schiff base.
상기 시프염기 전구체는 하이드라지드(hydrazide) 화합물, 바람직하기로는 아세트산 하이드라지드, 말론산 디하이드라지드, 쑥신산 디하이드라지드, 아디프산 디하이드라지드 중 어느 하나 이상인 것을 특징으로 한다. The Schiff base precursor is a hydrazide compound, preferably at least one of acetic acid hydrazide, malonic acid dihydrazide, succinic acid dihydrazide, and adipic acid dihydrazide. .
본 발명의 바람직한 실시예에 따른 친환경 폴리우레탄 조성물은, 점도가 1200cp~3000cp인 폴리이소시아네이트 60 중량%와, 다음 [화학식 I]으로 표시되는 아스파틱 에스테르 수지 39.9 중량%와, 아디프산 디하이드라지드 0.1 중량%를 포함하여 구성되는 것을 특징으로 한다. The eco-friendly polyurethane composition according to a preferred embodiment of the present invention includes 60% by weight of polyisocyanate having a viscosity of 1200 cp to 3000 cp, 39.9% by weight of aspartic ester resin represented by the following [Chemical Formula I], and adipic acid dihydra. It is characterized in that it contains 0.1% by weight of Zide.
[ 화학식 I ][Formula I]
(상기 화학식 I 에서, R1과 R2는 탄소수 1~10의 알킬기로서 서로 같을 수도 있고, 다를 수도 있다.)(In the above formula (I), R 1 and R 2 are alkyl groups having 1 to 10 carbon atoms and may be the same or different from each other.)
본 발명에 따른 친환경 폴리우레탄 조성물은 경화 과정에서 인체에 유해한 포름알데히드가 거의 발생하지 않기 때문에 방수성 도료나, 접착제, 탄성 포장재, 건축용 단열재, 자동차 내장재 등으로 사용할 경우 새집 증후군이나 새차 증후군을 개선하는데 기여할 수 있을 것으로 기대된다. Since the eco-friendly polyurethane composition according to the present invention generates almost no formaldehyde harmful to the human body during the curing process, it contributes to improving sick house syndrome or new car syndrome when used as a waterproof paint, adhesive, elastic packaging material, building insulation material, automobile interior material, etc. It is expected that it will be possible.
이하, 본 발명을 상세하게 설명한다. 다만, 본 발명을 실시하는데 꼭 필요한 구성이라 하더라도 종래기술에 소개되어 있거나, 통상의 기술자가 공지기술로부터 용이하게 실시할 수 있는 사항에 대해서는 구체적인 설명을 생략한다.Hereinafter, the present invention will be described in detail. However, even if the configuration is essential for carrying out the present invention, detailed description will be omitted for matters that are introduced in the prior art or that can be easily implemented by a person skilled in the art from the known technology.
그리고 본 발명에서 어떤 구성요소를 ‘포함’ 한다는 것은, 명시된 구성요소에 더하여 필요에 따라 다른 구성요소를 더 포함할 수 있다는 것을 의미한다.And in the present invention, ‘including’ a certain component means that in addition to the specified component, other components may be further included as needed.
본 발명에 따른 친환경 폴리우레탄 조성물은 3종의 필수적 구성성분, 즉 폴리이소시아네이트와, 폴리올 또는 아스파틱 에스테르 수지(aspartic ester resin), 그리고 시프염기(schiff base) 전구체를 포함하여 구성된다.The eco-friendly polyurethane composition according to the present invention is composed of three essential components, namely polyisocyanate, polyol or aspartic ester resin, and Schiff base precursor.
먼저 폴리이소시아네이트는 주제인 폴리올 또는 아스파틱 에스테르 수지와 반응하여 폴리우레탄을 형성하는 경화제로서, 점도가 1200cp~3000cp 인 것이 바람직하고, 그 함량은 조성물 전체에 대하여 49~90 중량%를 포함한다.First, polyisocyanate is a curing agent that reacts with the main polyol or aspartic ester resin to form polyurethane. It preferably has a viscosity of 1200 cp to 3000 cp, and its content is 49 to 90% by weight based on the total composition.
만일 폴리이소시아네이트의 점도가 1200cp 미만이거나 그 함량이 49 중량% 미만이면 주제와의 반응성이 낮아져서 경화속도가 너무 늦고 점도가 감소하여 균일한 시공이 어려워지는 문제가 있다.If the viscosity of the polyisocyanate is less than 1200 cp or its content is less than 49% by weight, the reactivity with the base material is lowered, so the curing speed is too slow and the viscosity decreases, making uniform construction difficult.
반대로 폴리이소시아네이트의 점도가 3000cp를 초과하거나 그 함량이 90 중량%를 초과하면 경화속도가 너무 빠르고 점도가 증가하여 폴리우레탄을 시공할 때 작업성이 저하되는 문제가 있다.Conversely, if the viscosity of polyisocyanate exceeds 3000 cp or its content exceeds 90% by weight, the curing speed is too fast and the viscosity increases, which reduces workability when constructing polyurethane.
다음으로 폴리올 또는 아스파틱 에스테르 수지는 경화제인 폴리이소시아네이트와 반응하여 폴리우레탄을 형성하는 주제로서, 그 함량은 조성물 전체에 대하여 9~50 중량%를 포함한다.Next, polyol or aspartic ester resin reacts with polyisocyanate, a curing agent, to form polyurethane, and its content is 9 to 50% by weight based on the total composition.
상기 폴리올은 에틸렌 글리콜 또는 폴리에틸렌글리콜 인 것이 바람직하다. 그리고 상기 아스파틱 에스테르 수지(aspartic ester resin)는 다음 [화학식 I]으로 표시될 수 있다. The polyol is preferably ethylene glycol or polyethylene glycol. And the aspartic ester resin may be represented by the following [Chemical Formula I].
[ 화학식 I ][Formula I]
(상기 화학식 I 에서, R1과 R2는 탄소수 1~10의 알킬기로서 서로 같을 수도 있고, 다를 수도 있다.)(In the above formula (I), R 1 and R 2 are alkyl groups having 1 to 10 carbon atoms and may be the same or different from each other.)
상기 아스파틱 에스테르 수지는 N-H 작용기가 폴리이소시아네이트의 NCO 작용기와 반응하여 우레아 결합을 함으로써 경화가 진행된다.The aspartic ester resin is cured as the N-H functional group reacts with the NCO functional group of polyisocyanate to form a urea bond.
상기 폴리올 또는 아스파틱 에스테르 수지의 함량이 9 중량% 미만이면 우레아 반응이 충분히 진행되지 않아서 균일한 폴리우레탄 중합체를 형성하지 못할 우려가 있다.If the content of the polyol or aspartic ester resin is less than 9% by weight, there is a risk that the urea reaction will not proceed sufficiently and a uniform polyurethane polymer may not be formed.
반대로 상기 폴리올 또는 아스파틱 에스테르 수지의 함량이 50 중량%를 초과하면 우레탄 단량체와 폴리올 또는 아스파틱 에스테르 수지 일부가 잔류하여 경화가 충분히 진행되지 않고 층 분리가 발생할 수 있다.On the other hand, if the content of the polyol or aspartic ester resin exceeds 50% by weight, some of the urethane monomer and polyol or aspartic ester resin may remain, and curing may not proceed sufficiently and layer separation may occur.
상기 경화제와 주제는 중량비로 6 : 4의 비율로 사용하는 것이 바람직하다.It is preferable to use the hardener and base material in a weight ratio of 6:4.
마지막으로 상기 시프염기 전구체는 폴리우레탄의 경화 과정에서 발생하는 포름알데히드와 반응하여 시프염기를 형성하는 것으로, 이를 반응식으로 표시하면 다음과 같다.Lastly, the Schiff base precursor reacts with formaldehyde generated during the curing process of polyurethane to form a Schiff base, which is expressed in the reaction equation as follows.
상기 시프염기 전구체는 하이드라지드(hydrazide) 화합물, 구체적으로 아세트산 하이드라지드, 말론산 다이하이드라지드, 쑥신산 다이하이드라지드, 아디프산 다이하이드라지드 중 어느 하나 이상인 것이 바람직하다.The Schiff base precursor is preferably a hydrazide compound, specifically, at least one of acetic acid hydrazide, malonic acid dihydrazide, succinic acid dihydrazide, and adipic acid dihydrazide.
상기 시프염기 전구체의 함량은 조성물 전체에 대하여 0.01~1 중량%를 포함한다. 상기 시프염기 전구체의 함량이 0.01 중량% 미만이면 포름알데히드가 충분히 제거되지 않는 문제가 있고, 반대로 1 중량%를 초과하면, 폴리우레탄 중합체의 외관이 혼탁해지고 물성이 저하되는 문제점이 있다.The content of the Schiff base precursor is 0.01 to 1% by weight based on the total composition. If the content of the Schiff base precursor is less than 0.01% by weight, formaldehyde is not sufficiently removed. Conversely, if it exceeds 1% by weight, the appearance of the polyurethane polymer becomes cloudy and physical properties are deteriorated.
본 발명에 따른 친환경 폴리우레탄 조성물은 1액형으로 사용될 수도 있고, 2액형으로 사용될 수도 있다. 2액형으로 사용될 경우, 상기 경화제와 주제가 별도로 제공되고, 시프염기 전구체는 상기 주제와 함께 제공될 수 있다.The eco-friendly polyurethane composition according to the present invention may be used as a one-component type or a two-component type. When used in a two-component form, the curing agent and base may be provided separately, and the Schiff base precursor may be provided together with the base.
또한 본 발명에 따른 친환경 폴리우레탄 조성물은 방수성 도료나, 접착제, 탄성 포장재 등으로 사용될 수도 있고, 필요에 따라 발포제 등을 첨가하여 건축물 또는 자동차 내장용 폴리우레탄 폼 등으로 사용될 수도 있다. In addition, the eco-friendly polyurethane composition according to the present invention can be used as a waterproof paint, adhesive, elastic packaging material, etc., and can be used as polyurethane foam for buildings or automobile interiors by adding a foaming agent, etc., if necessary.
[실시예][Example]
다음 [ 표 1 ]의 구성성분 및 함량 비율에 따라 본 발명의 실시예 1~10에 해당하는 친환경 폴리우레탄 조성물을 제조하였다.Eco-friendly polyurethane compositions corresponding to Examples 1 to 10 of the present invention were prepared according to the components and content ratios shown in Table 1 below.
상기 [ 표 1 ]에서 주제 및 시프염기 전구체로 사용된 약자의 정의는 다음과 같다.The definitions of the abbreviations used as the motif and Schiff base precursor in [Table 1] are as follows.
- EG ; 에틸렌글리콜(ethylene glycol)-EG; ethylene glycol
- PEG ; 폴리에틸렌 글리콜(polyethylene glycol)-PEG; polyethylene glycol
- AER ; 아스파틱 에스테르 수지(aspartic ester resin)-AER; aspartic ester resin
- AH ; 아세트산 하이드라지드(acetic acid hydrazide)-AH; Acetic acid hydrazide
- ADH ; 아디프산 디하이드라지드(adipic acid dihydrazide)-ADH; adipic acid dihydrazide
- MDH ; 말론산 디하이드라지드(malonic acid dihydrazide) -MDH; malonic acid dihydrazide
[비교예][Comparative example]
다음 [ 표 2 ]의 구성성분 및 함량 비율에 따라 비교예의 폴리우레탄 조성물을 제조하였다. 비교예 1~4에서는 경화제와 주제 이외에 알데히드 제거제를 사용하지 않았고, 비교에 5~8에서는 알데히드 제거제로서 아민화합물을 사용하였다.The polyurethane composition of the comparative example was prepared according to the components and content ratios shown in Table 2 below. In Comparative Examples 1 to 4, no aldehyde remover was used other than the curing agent and base material, and in Comparative Examples 5 to 8, an amine compound was used as an aldehyde remover.
상기 아민화합물은 마니히 반응(Mannich reaction)을 통해서 포름알데히드와 반응하여 이민(Immine) 화합물을 형성하는 것으로 알려져 있다. The amine compound is known to react with formaldehyde through the Mannich reaction to form an imine compound.
상기 [ 표 2 ]에서 경화 개시제로 사용된 약자의 정의는 상기 [표 1 ]과 같고, 아민화합물로 사용된 약자의 정의는 다음과 같다.The definitions of the abbreviations used as curing initiators in [Table 2] are the same as in [Table 1], and the definitions of the abbreviations used as amine compounds are as follows.
- MEA ; 모노에탄올 아민(mono ethanol amine)- MEA; monoethanol amine
- HA ; 헥실 아민(hexyl amine)- HA ; hexyl amine
- AEE ; 아미노에톡시 에탄올(aminoethoxy ethanol) -AEE; aminoethoxy ethanol
[포름알데히드 방출농도 시험][Formaldehyde emission concentration test]
상기 실시예 1~10 및 비교예 1~8의 폴리우레탄 조성물에 대하여 포름알데히드 방출농도를 측정하였다. The formaldehyde emission concentration was measured for the polyurethane compositions of Examples 1 to 10 and Comparative Examples 1 to 8.
시험방법은 상기 폴리우레탄 조성물을 각각 50g씩 시료로 취하고, 클렙튼 공기 측정기(모델명 KAD918H)를 이용하여 가로 20cm, 세로 15cm, 높이 7cm의 밀폐공간 내에서 포름알데히드의 농도를 측정한 다음, 그 결과를 다음 [ 표 3 ]에 비교 수록하였다.The test method is to take 50g of each polyurethane composition as a sample, measure the concentration of formaldehyde in a closed space of 20cm wide, 15cm long, and 7cm high using a Clepton air meter (model name KAD918H), and then measure the concentration of formaldehyde. are listed for comparison in the following [Table 3].
참고로 ‘실내 공기질 관리규칙’(환경부령 제264호)에 따르면, 포름알데히드 방출농도의 기준치는 0.1mg/m3 이다.For reference, according to the 'Indoor Air Quality Management Rules' (Ministry of Environment Ordinance No. 264), the standard value of formaldehyde emission concentration is 0.1 mg/m 3 .
[평가][evaluation]
상기 [ 표 3 ]의 시험결과에서 보는 바와 같이, 본 발명의 실시예에 따른 폴리우레탄 조성물은 포름알데히드 방출농도가 평균 0.0023 mg/m3로서, 모두 기준치(0.1mg/m3)를 벗어나지 않는 것으로 나타났다. 그리고 실시예 1~10 중에서 실시예 6의 폴리우레탄 조성물이 가장 우수한 물성을 갖는 것으로 확인되었다.As seen in the test results in [Table 3], the polyurethane composition according to the example of the present invention has an average formaldehyde emission concentration of 0.0023 mg/m 3 , which is not outside the standard value (0.1 mg/m 3 ). appear. And among Examples 1 to 10, the polyurethane composition of Example 6 was confirmed to have the best physical properties.
반면, 상기 비교예 1~8에 따른 폴리우레탄 조성물은 포름알데히드 방출농도가 평균 0.730 mg/m3 정도로서, 본 발명의 실시예에 비해 포름알데히드 방출량이 약 300배 이상에 이르는 것으로 나타났다. On the other hand, the polyurethane compositions according to Comparative Examples 1 to 8 had an average formaldehyde emission concentration of about 0.730 mg/m 3 , showing that the formaldehyde emission amount was about 300 times more than that of the examples of the present invention.
따라서 본 발명에 따른 친환경 폴리우레탄 조성물은 비교예로 나타낸 종래의 폴리우레탄 조성물에 비해 포름알데히드의 방출량이 현저하게 낮은 것으로 확인되었다. Therefore, it was confirmed that the eco-friendly polyurethane composition according to the present invention emits significantly lower formaldehyde compared to the conventional polyurethane composition shown as a comparative example.
Claims (6)
49~90% by weight of polyisocyanate with a viscosity of 1200cp~3000cp, 9~50% by weight of polyol or aspartic ester resin, and a Schiff base precursor that reacts with formaldehyde to form a Schiff base. An eco-friendly polyurethane composition, characterized in that it contains 0.01 to 1% by weight.
The eco-friendly polyurethane composition of claim 1, wherein the Schiff base precursor is a hydrazide compound.
The method of claim 1 or 2, wherein the Schiff base precursor is at least one of acetic acid hydrazide, malonic acid dihydrazide, succinic acid dihydrazide, and adipic acid dihydrazide. Eco-friendly polyurethane composition.
The eco-friendly polyurethane composition according to claim 1, wherein the polyol is ethylene glycol or polyethylene glycol.
[ 화학식 I ]
(상기 화학식 I 에서, R1과 R2는 탄소수 1~10의 알킬기로서 서로 같을 수도 있고, 다를 수도 있다.)
The eco-friendly polyurethane composition according to claim 1, wherein the aspartic ester resin is represented by the following [Chemical Formula I].
[Formula I]
(In the above formula (I), R 1 and R 2 are alkyl groups having 1 to 10 carbon atoms and may be the same or different from each other.)
[ 화학식 I ]
(상기 화학식 I 에서, R1과 R2는 탄소수 1~10의 알킬기로서 서로 같을 수도 있고, 다를 수도 있다.)Characterized by comprising 60% by weight of polyisocyanate having a viscosity of 1200 cp to 3000cp, 39.9% by weight of aspartic ester resin represented by the following [Chemical Formula I], and 0.1% by weight of adipic acid dihydrazide, Eco-friendly polyurethane composition.
[Formula I]
(In the above formula (I), R 1 and R 2 are alkyl groups having 1 to 10 carbon atoms and may be the same or different from each other.)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101075566B1 (en) | 2007-12-27 | 2011-10-20 | 대한폴리텍(주) | Green sprayable polyurethane foam composition |
| KR101692970B1 (en) | 2014-12-12 | 2017-01-06 | 주식회사 태성환경연구소 | Poly urethane foam having liquid agent for removing aldehydes and preparation method thereof |
| KR102084745B1 (en) | 2018-03-09 | 2020-03-04 | 주식회사 에이치엠솔루션 | Aldehyde scavenging composition and manufacturing method of flexible polyurethane foam using the same |
| KR20210040096A (en) | 2018-08-02 | 2021-04-12 | 다우 글로벌 테크놀로지스 엘엘씨 | How to Reduce Aldehyde Emissions in Polyurethane Foam |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101075566B1 (en) | 2007-12-27 | 2011-10-20 | 대한폴리텍(주) | Green sprayable polyurethane foam composition |
| KR101692970B1 (en) | 2014-12-12 | 2017-01-06 | 주식회사 태성환경연구소 | Poly urethane foam having liquid agent for removing aldehydes and preparation method thereof |
| KR102084745B1 (en) | 2018-03-09 | 2020-03-04 | 주식회사 에이치엠솔루션 | Aldehyde scavenging composition and manufacturing method of flexible polyurethane foam using the same |
| KR20210040096A (en) | 2018-08-02 | 2021-04-12 | 다우 글로벌 테크놀로지스 엘엘씨 | How to Reduce Aldehyde Emissions in Polyurethane Foam |
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