JP5027722B2 - One-part soft foam polyurethane aerosol composition - Google Patents
One-part soft foam polyurethane aerosol composition Download PDFInfo
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- JP5027722B2 JP5027722B2 JP2008105682A JP2008105682A JP5027722B2 JP 5027722 B2 JP5027722 B2 JP 5027722B2 JP 2008105682 A JP2008105682 A JP 2008105682A JP 2008105682 A JP2008105682 A JP 2008105682A JP 5027722 B2 JP5027722 B2 JP 5027722B2
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- 239000000203 mixture Substances 0.000 title claims description 71
- 239000000443 aerosol Substances 0.000 title claims description 65
- 229920002635 polyurethane Polymers 0.000 title claims description 60
- 239000004814 polyurethane Substances 0.000 title claims description 49
- 239000006260 foam Substances 0.000 title description 28
- 239000003380 propellant Substances 0.000 claims description 51
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 40
- 229920005862 polyol Polymers 0.000 claims description 34
- -1 ether polyol Chemical class 0.000 claims description 17
- 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 claims description 16
- 125000000524 functional group Chemical group 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 150000003077 polyols Chemical class 0.000 description 38
- 239000012948 isocyanate Substances 0.000 description 24
- 239000000126 substance Substances 0.000 description 19
- 150000002513 isocyanates Chemical class 0.000 description 17
- 238000010276 construction Methods 0.000 description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 15
- 239000004215 Carbon black (E152) Substances 0.000 description 13
- 239000004721 Polyphenylene oxide Substances 0.000 description 13
- 238000009835 boiling Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 239000003063 flame retardant Substances 0.000 description 13
- 229930195733 hydrocarbon Natural products 0.000 description 13
- 150000002430 hydrocarbons Chemical class 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 229920000570 polyether Polymers 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 12
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 12
- 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 11
- 239000012752 auxiliary agent Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 239000003381 stabilizer Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000009413 insulation Methods 0.000 description 8
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 8
- OQXSRALAOPBHPM-UHFFFAOYSA-N 2-hydroxypropanoic acid;silver Chemical compound [Ag].CC(O)C(O)=O OQXSRALAOPBHPM-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 7
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 6
- 239000001282 iso-butane Substances 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- 238000009423 ventilation Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920005830 Polyurethane Foam Polymers 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000004035 construction material Substances 0.000 description 5
- 239000011496 polyurethane foam Substances 0.000 description 5
- 239000002023 wood Substances 0.000 description 5
- WMNWJTDAUWBXFJ-UHFFFAOYSA-N 3,3,4-trimethylheptane-2,2-diamine Chemical compound CCCC(C)C(C)(C)C(C)(N)N WMNWJTDAUWBXFJ-UHFFFAOYSA-N 0.000 description 4
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical compound C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000004872 foam stabilizing agent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- XDGWKBYFXMRODP-UHFFFAOYSA-N 4-[2-[2-(2,6-dimethylmorpholin-4-yl)ethoxy]ethyl]-2,6-dimethylmorpholine Chemical compound C1C(C)OC(C)CN1CCOCCN1CC(C)OC(C)C1 XDGWKBYFXMRODP-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000256602 Isoptera Species 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229940067597 azelate Drugs 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000009429 electrical wiring Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
本発明は、一液軟質発泡ポリウレタンエアゾール組成物に関する。詳しくは、エアゾール容器から噴射した発泡硬化体が接着性、発泡性、柔軟性、追随性に優れ、例えば、住宅、水道管又は電気配線周りの気密補助材としての適用性が一段と拡張された一液軟質発泡ポリウレタンエアゾール組成物に関する。 The present invention relates to a one-component flexible foamed polyurethane aerosol composition. Specifically, the foamed cured product sprayed from the aerosol container is excellent in adhesiveness, foamability, flexibility, and followability. For example, the applicability as an airtight auxiliary material around a house, a water pipe or an electric wiring has been further expanded. The present invention relates to a liquid soft foamed polyurethane aerosol composition.
従来から、一液発泡ポリウレタンエアゾール組成物は、エアゾールタイプの硬質ウレタンフォームとして、建築物、水道管、電気配線周り等の断熱、気密シール、保温、保冷、接着、固定等に充填補修材や気密補助材として広く用いられている。
例えば、特開２００１−２４７６４１公報（特許第３５７９７４１号）に記載された一液発泡ポリウレタンエアゾール組成物は、ウレタン樹脂のもつ、優れた耐摩耗性、耐薬品性、密着性などに加え、弾性を有し、断熱性、遮音性などの点でも優れ、上記の用途に有効に適用されている。
しかしながら、従来の一液発泡ポリウレタンエアゾール組成物は、その発泡体の硬度が高いため、構造物の動き（木材の収縮等）に追随できず、また、一度硬化させた後、外力を加え変形させることが困難であった。例えば、建築物における実際の使用において、硬化体に無理に外力を加えると、硬化体が破壊したり、接着面から剥離したりする可能性が大きいものであった。
また、木材に接着し硬化した発泡体が、木材の収縮に追随しきれず、隙間を生じ、そこから剥離し、結果として気密性を失うなどの問題を生じ、一液発泡ポリウレタンエアゾール組成物の機能を十分に発揮できないことが指摘されていた。
すなわち、従来の一液発泡ポリウレタンエアゾール組成物は、建築物の断熱、気密、保温、保冷、固定材として、加工性と施工性に優れ、有効に適用されているものの、上記のような問題点があった。
For example, the one-component foamed polyurethane aerosol composition described in Japanese Patent Application Laid-Open No. 2001-244761 (Patent No. 3579741) has elasticity in addition to the excellent wear resistance, chemical resistance, adhesion, etc. of the urethane resin. It has excellent heat insulation and sound insulation properties and is effectively applied to the above applications.
However, the conventional one-component foamed polyurethane aerosol composition has a high hardness of the foam, so it cannot follow the movement of the structure (such as shrinkage of wood), and after being cured once, it is deformed by applying external force. It was difficult. For example, in an actual use in a building, if an external force is forcibly applied to the cured body, there is a high possibility that the cured body will be broken or peeled off from the adhesive surface.
In addition, the foam that adheres and hardens to the wood cannot follow the shrinkage of the wood, creates gaps, peels from it, and results in problems such as loss of airtightness. It was pointed out that it was not possible to fully demonstrate.
That is, the conventional one-component foamed polyurethane aerosol composition is excellent in workability and workability as a heat insulating, airtight, heat retaining, cold retaining, and fixing material for buildings, but has the above problems. was there.
本発明の課題は、気密性及び作業性を改善し、生成した発泡硬化体が使用目的に適した拡張及び向上させた物性を有し、建造物のひび割れ、隙間の深部、複雑な形状面に吹き付けて強固且つ柔軟な接着効果により、建造物の補修、気密シール補助材等として、従来の一液発泡ポリウレタンエアゾール組成物では得られなかった新たな効果を奏し、その適用性が増した一液軟質発泡ポリウレタンエアゾール組成物を提供することである。 The object of the present invention is to improve airtightness and workability, and the foamed cured product produced has expanded and improved physical properties suitable for the purpose of use, such as cracks in buildings, deep gaps, and complex shapes. One component that has improved its applicability due to a new and unobtainable effect of conventional one-component foamed polyurethane aerosol compositions, such as building repairs and hermetic seal aids, thanks to the strong and flexible adhesive effect. It is to provide a flexible foamed polyurethane aerosol composition.
本発明者等は、上記課題を解決するため鋭意検討し、本発明者等が先に発明して提供した発泡ポリウレタンエアゾール組成物（特許第３５７９７４１号）において、ウレタンプレポリマーとして、（１）官能基数２〜３、分子量１，０００〜１０，０００のポリエーテルポリオールと、（２）ピュアジフェニルメタンジイソシアネート（以下ピュアＭＤＩという）とを、ＮＣＯインデックスが３〜４．５の範囲で反応させて得られるものを選択して用いることにより、接着性、引張強度、引裂き強度、伸び等が優れた発泡硬化体が得られ、気密性に優れた各種施工が可能となった一液軟質発泡ポリウレタンエアゾール組成物を見出し、本発明を完成させた。
すなわち、本発明は、ウレタンプレポリマー（Ａ）、噴射剤（Ｂ）を含有する一液軟質発泡ポリウレタンエアゾール組成物であって、ウレタンプレポリマー（Ａ）が、官能基数２〜３、分子量１，０００〜１０，０００のポリエーテルポリオール（ａ−１）とピュアＭＤＩ（ａ−２）とをＮＣＯインデックス３〜４．５の範囲で反応させて得られるウレタンプレポリマーであることを特徴とする一液軟質発泡ポリウレタンエアゾール組成物である。
該組成物中に上記のウレタンプレポリマー（Ａ）と噴射剤（Ｂ）とを、該ポリマー（Ａ）４０〜９９重量部と該噴射剤（Ｂ）１〜６０重量部の割合で含有する一液軟質発泡ポリウレタンエアゾール組成物である。
また、噴射剤（Ｂ）が、沸点範囲が１０〜１００℃の炭化水素系溶剤及び噴射剤を含有する高沸点炭化水素系溶剤含有噴射剤（Ｂ−１）又は噴射剤（Ｂ−２）である一液軟質発泡ポリウレタンエアゾール組成物である。
In order to solve the above-mentioned problems, the present inventors have intensively studied, and in the polyurethane foam aerosol composition (Japanese Patent No. 35579741) previously invented and provided by the present inventors, as a urethane prepolymer, (1) functional Obtained by reacting a polyether polyol having 2 to 3 groups and a molecular weight of 1,000 to 10,000 with (2) pure adiphenylmethane diisocyanate (hereinafter referred to as pure MDI) in the range of NCO index of 3 to 4.5. By selecting and using one, a foamed cured product with excellent adhesiveness, tensile strength, tear strength, elongation, etc. was obtained, and a one-component flexible foamed polyurethane aerosol composition capable of various constructions with excellent airtightness. The present invention was completed.
That is, the present invention is a one-pack soft foamed polyurethane aerosol composition containing a urethane prepolymer (A) and a propellant (B), wherein the urethane prepolymer (A) has 2 to 3 functional groups, a molecular weight of 1, A urethane prepolymer obtained by reacting 000 to 10,000 polyether polyol (a-1) and pure MDI (a-2) in the range of NCO index 3 to 4.5. It is a liquid soft foamed polyurethane aerosol composition.
The urethane prepolymer (A) and the propellant (B) are contained in the composition in a proportion of 40 to 99 parts by weight of the polymer (A) and 1 to 60 parts by weight of the propellant (B). It is a liquid soft foamed polyurethane aerosol composition.
The propellant (B) is a high-boiling hydrocarbon solvent-containing propellant (B-1) or propellant (B-2) containing a hydrocarbon solvent having a boiling range of 10 to 100 ° C. and a propellant. A certain one-component soft foamed polyurethane aerosol composition.
本発明の一液軟質発泡ポリウレタンエアゾール組成物は、エアゾール容器から噴射して得られるポリウレタン発泡体が、接着性、発泡体の伸び、引張強度、引裂き強度等の性能に優れている。すなわち、被噴射体に噴射されて形成される発泡硬化体は、接着性に優れ、柔軟性を有し、壁面において垂れがなく、保持性にも優れている。
そのため、気密性を賦与しようとする建造物等に噴射した発泡硬化体は、木材のへたりが起きたときなどにクラックを生じることがなく、へたりに追随し気密性を永く保持できる。また、壁面に板を張付けるような施工における補助剤としても有効に適用できる等、従来の一液発泡ポリウレタンエアゾール組成物では達成出来なかった効果が得られ、また施工困難であって新たな施工にも適用できる可能性を有するものである。
In the one-component soft foamed polyurethane aerosol composition of the present invention, the polyurethane foam obtained by spraying from an aerosol container is excellent in performance such as adhesiveness, foam elongation, tensile strength, and tear strength. That is, the foamed cured body formed by being sprayed onto the body to be ejected is excellent in adhesiveness, has flexibility, does not sag on the wall surface, and is excellent in retention.
Therefore, the foamed and hardened body sprayed onto a building or the like to impart airtightness does not cause cracks when wood sag occurs, and can follow the sag and maintain airtightness for a long time. In addition, it can be effectively applied as an auxiliary agent in construction such as sticking a plate to the wall surface, and effects that cannot be achieved with the conventional one-component foamed polyurethane aerosol composition are obtained. There is a possibility that it can also be applied.
以下、本発明を詳しく説明する。
本発明の一液軟質発泡ポリウレタンエアゾール組成物は、次の成分が耐圧容器に充填され、使用時にこの耐圧容器に、取り付けたノズルを通して容器内の該組成物を噴霧又は棒状に吐出させて、様々の施工形状や施工個所、例えば、ひび割れ、隙間、壁面、その他の複雑な形状に発泡硬化体を形成させ、目的の施工に適用するものである。
耐圧容器に充填される組成物は、ポリオール（ａ−１）とイソシアネート化合物（ａ−２）を反応させて得られるウレタンプレポリマー（Ａ）と噴射剤（Ｂ）を含有するものであり、その他の必要に応じて添加する助剤として、整泡剤、難燃剤、反応触媒等を含有する。
組成物は、耐圧容器に、ポリオール（ａ−１）及び整泡剤、難燃剤、触媒などの助剤を混合して含有するレジン原液を充填し、ついでウレタンプレポリマー（Ａ）を生成するためのイソシアネート化合物（ａ−２）、噴射剤（Ｂ）を順次充填する。
又は、ウレタンプレポリマー（Ａ）を、整泡剤、難燃剤、反応触媒などの助剤を含有するポリオール（ａ−１）とイソシアネート化合物（ａ−２）とを所定の反応温度で反応させて調製し、このウレタンプレポリマー（Ａ）、噴射剤（Ｂ）を耐圧容器に順次充填する方法であってもよい。
The present invention will be described in detail below.
The one-component soft foamed polyurethane aerosol composition of the present invention is filled with the following components in a pressure-resistant container, and when used, the composition in the container is sprayed or ejected in a rod shape through a nozzle attached to the pressure-resistant container. The foamed cured body is formed into a complicated shape such as cracks, gaps, wall surfaces, and other complicated shapes and applied to the intended construction.
The composition filled in the pressure vessel contains a urethane prepolymer (A) and a propellant (B) obtained by reacting the polyol (a-1) and the isocyanate compound (a-2). As an auxiliary agent added as necessary, a foam stabilizer, a flame retardant, a reaction catalyst, and the like are contained.
The composition fills a pressure-resistant container with a resin stock solution containing a mixture of polyol (a-1) and auxiliary agents such as a foam stabilizer, a flame retardant, and a catalyst, and then generates a urethane prepolymer (A). The isocyanate compound (a-2) and the propellant (B) are sequentially filled.
Alternatively, the urethane prepolymer (A) is reacted at a predetermined reaction temperature with a polyol (a-1) containing an auxiliary agent such as a foam stabilizer, a flame retardant, and a reaction catalyst, and an isocyanate compound (a-2). A method of preparing and sequentially filling the pressure-resistant container with the urethane prepolymer (A) and the propellant (B) may be used.
（Ａ）成分のウレタンプレポリマーは、ポリオール（ａ−１）としては、水酸基数２〜３、分子量１，０００〜２０，０００のポリエーテルポリオールを用いる。具体的には、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレンエーテルグリコール、ポリエチレンアジペートグリコール、ポリブチレンアジペートグリコール、ポリブチレンアゼラエートグリコール、ポリカプロラクトングリコール等が挙げられる。好ましくは、ポリプロピレングリコールである。例えば、三井化学ポリウレタン（株）社製のアクトコールＭＮ−１０００（ＯＨ価１６０±５ｍｇＫＯＨ／ｇ、平均分子量１，０００）、アクトコールＤｉｏｌ−２０００、（ＯＨ価５６±５ｍｇＫＯＨ／ｇ、平均分子量２，０００）等が、好ましく用いられる。 As the urethane prepolymer (A), a polyether polyol having a hydroxyl number of 2 to 3 and a molecular weight of 1,000 to 20,000 is used as the polyol (a-1). Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polyethylene adipate glycol, polybutylene adipate glycol, polybutylene azelate glycol, polycaprolactone glycol, and the like. Polypropylene glycol is preferable. For example, Actol MN-1000 (OH number 160 ± 5 mgKOH / g, average molecular weight 1,000), Actol Diol-2000, (OH number 56 ± 5 mgKOH / g, average molecular weight 2) manufactured by Mitsui Chemicals Polyurethane Co., Ltd. , 000) etc. are preferably used.
また、イソシアネート化合物（ａ−２）は、ピュアＭＤＩであり、４，４’−及び／又は２，４’−ジフェニルメタンジイソシアネートを用いる。従来の一液硬化発泡ポリウレタンエアゾール組成物で用いられるポリメリックＭＤＩでは、本発明の効果が得られず、イソシアネート化合物としてピュアＭＤＩを用いることにより本発明の効果を得ることができる。
ピュアＭＤＩとしては、例えば、三井化学ポリウレタン（株）社製のコスモネートＬＬ、コスモネートＬＫ、その他、市販のピュアＭＤＩが使用できる。
The isocyanate compound (a-2) is pure MDI, and 4,4′- and / or 2,4′-diphenylmethane diisocyanate is used. The polymeric MDI used in the conventional one-component cured foamed polyurethane aerosol composition does not provide the effects of the present invention, and the effects of the present invention can be obtained by using pure MDI as the isocyanate compound.
As the pure MDI, for example, Cosmonate LL, Cosmonate LK manufactured by Mitsui Chemicals Polyurethane Co., Ltd., and other commercially available pure MDI can be used.
ウレタンプレポリマー（Ａ）は、上記のポリオール（ａ−１）とイソシアネート化合物（ａ−２）とを、ＮＣＯインデックスが３〜４．５、好ましくは３〜４の範囲で反応させる。
ＮＣＯインデックスが、３未満では、噴射して形成される硬化体は、フォームの形成が不十分で、柔かく、収縮することがあり、一方、４．５を超えると硬度が高く、所望の物性を有する発泡体を得にくくなるので好ましくない。
硬化反応触媒としては、２，２’−ジモルホリノジエチルエーテル（ＤＭＤＥＥ）、ジ（２，６−ジメチルモルホリノエチル）エーテルなどがあり、好ましくは２，２’−ジモルホリノジエチルエーテル（ＤＭＤＥＥ）が用いられる。触媒の使用量は、ポリオール１００重量部に対して、０．０５〜３．０重量部であり、好ましくは０．３〜１．５重量部である。
反応温度、時間などの反応条件は、特に限定はない。
通常、ポリオールとイソシアネートを耐圧容器内に充填し、ウレタンプレポリマーを生成させる場合は、これらは常温で充填する。
また、予めウレタンプレポリマーを調製して、これを耐圧容器に充填する場合は、実用されている反応条件、例えば、７０℃、１時間程度の反応条件でポリオールとイソシアネートを反応させる。
In the urethane prepolymer (A), the polyol (a-1) and the isocyanate compound (a-2) are reacted in an NCO index of 3 to 4.5, preferably 3 to 4.
When the NCO index is less than 3, the cured product formed by spraying may have insufficient foam formation and may be soft and shrink. On the other hand, when it exceeds 4.5, the hardness is high and the desired physical properties are obtained. Since it becomes difficult to obtain the foam which has, it is not preferable.
Examples of the curing reaction catalyst include 2,2′-dimorpholinodiethyl ether (DMDEE), di (2,6-dimethylmorpholinoethyl) ether, and preferably 2,2′-dimorpholinodiethyl ether (DMDEE) is used. It is done. The usage-amount of a catalyst is 0.05-3.0 weight part with respect to 100 weight part of polyols, Preferably it is 0.3-1.5 weight part.
Reaction conditions such as reaction temperature and time are not particularly limited.
Usually, when a pressure-resistant container is filled with polyol and isocyanate to produce a urethane prepolymer, these are filled at room temperature.
Moreover, when preparing a urethane prepolymer beforehand and filling this with a pressure vessel, a polyol and isocyanate are made to react on reaction conditions currently used, for example, reaction conditions of 70 degreeC and about 1 hour.
噴射剤（Ｂ）は、沸点範囲が１０〜１００℃の炭化水素系溶剤（ｂ−１）に噴射剤（ｂ−２）を含有する高沸点炭化水素溶剤含有噴射剤（Ｂ−１）、又は噴射剤（Ｂ−２）〔高沸点炭化水素溶剤を含まない噴射剤（ｂ−２）を指す〕が用いられる。
高沸点炭化水素溶剤含有噴射剤（Ｂ−１）において、沸点範囲が１０〜１００℃の炭化水素系溶剤（ｂ−１）は、イソペンタン、ノルマルペンタン、ノルマルヘキサン、イソヘキサン、シクロヘキサン又はノルマルヘプタン、あるいはこれらの２種以上の混合物である。
また、高沸点炭化水素系溶剤含有噴射剤（Ｂ−１）に含まれる噴射剤（ｂ−２）、及び噴射剤（Ｂ−２）は、ジメチルエーテル、メタン、エタン、プロパン、ノルマルブタン、イソブタン、炭酸ガス又は窒素あるいはこれらの２種以上を組み合わせた混合物である。
The propellant (B) is a high-boiling hydrocarbon solvent-containing propellant (B-1) containing a propellant (b-2) in a hydrocarbon solvent (b-1) having a boiling range of 10 to 100 ° C, or A propellant (B-2) [refers to a propellant (b-2) not containing a high-boiling hydrocarbon solvent] is used.
In the high-boiling hydrocarbon solvent-containing propellant (B-1), the hydrocarbon solvent (b-1) having a boiling point range of 10 to 100 ° C. is isopentane, normal pentane, normal hexane, isohexane, cyclohexane or normal heptane, or It is a mixture of two or more of these.
The propellant (b-2) and propellant (B-2) contained in the high-boiling hydrocarbon-based solvent-containing propellant (B-1) are dimethyl ether, methane, ethane, propane, normal butane, isobutane, Carbon dioxide, nitrogen, or a mixture of two or more of these.
上記の高沸点炭化水素溶剤含有噴射剤（Ｂ−１）は、通常、エアゾール組成物の各成分を耐圧容器に充填するに際して、レジン原液、イソシアネート化合物、次いで、高沸点炭化水素溶剤と噴射剤とを充填する。又、予めウレタンプレポリマーを調製して、耐圧容器に充填するときは、ウレタンプレポリマーに引き続き、高沸点炭化水素溶剤と噴射剤とを充填する。 The above-mentioned high-boiling hydrocarbon solvent-containing propellant (B-1) is usually a resin stock solution, an isocyanate compound, and then a high-boiling hydrocarbon solvent and a propellant when filling each component of the aerosol composition into a pressure-resistant container. Fill. Further, when a urethane prepolymer is prepared in advance and filled in a pressure resistant container, the urethane prepolymer is subsequently filled with a high boiling point hydrocarbon solvent and a propellant.
本発明の一液軟質発泡ポリウレタンエアゾール組成物は、（Ａ）成分のウレタンプレポリマーと（Ｂ）成分の噴射剤とが含有されるものであり、エアゾール組成物中に（Ａ）成分のウレタンプレポリマーが４０〜９９重量部、好ましくは５０〜９０重量部と、（Ｂ）成分の噴射剤が、６０〜１重量部、好ましくは５０〜１０重量部の合計１００重量部の配合割合で含有される。なお、ここに示すウレタンプレポリマーとは、ポリオールとイソシアネートから得られるウレタンプレポリマーに難燃剤、整泡剤及び触媒を含むものを言う。
また、噴射剤（Ｂ）が高沸点炭化水素溶剤含有噴射剤（Ｂ−１）であるとき、高沸点炭化水素溶剤（ｂ−１）と噴射剤（ｂ−２）との比率は、重量比で（ｂ−２）／（ｂ−１）＝９９／１〜７０／３０が好適であり、好ましくは９７／３〜８０／２０である。
The one-component soft foamed polyurethane aerosol composition of the present invention contains a urethane prepolymer of component (A) and a propellant of component (B), and the urethane composition of component (A) is contained in the aerosol composition. 40 to 99 parts by weight of the polymer, preferably 50 to 90 parts by weight, and the propellant of the component (B) is contained in a blending ratio of 100 parts by weight in total of 60 to 1 part by weight, preferably 50 to 10 parts by weight. The In addition, the urethane prepolymer shown here means what contains a flame retardant, a foam stabilizer, and a catalyst in the urethane prepolymer obtained from a polyol and isocyanate.
When the propellant (B) is a high-boiling point hydrocarbon solvent-containing propellant (B-1), the ratio of the high-boiling point hydrocarbon solvent (b-1) to the propellant (b-2) is a weight ratio. (B-2) / (b-1) = 99/1 to 70/30 is preferred, preferably 97/3 to 80/20.
本発明のエアゾール組成物中には、上記ウレタンプレポリマー（Ａ）及び噴射剤（Ｂ）に加え、難燃剤、整泡剤、触媒等の助剤の外、その他の改質剤、顔料等の着色剤などを本発明の効果を阻害しない範囲で配合することもできる。これらの改質剤や着色剤等の配合成分は、ウレタンプレポリマーの製造時、あるいはエアゾール組成物の充填時などに配合することができる。
上記助剤の添加量は、本発明の効果が得られる範囲で添加すれば特に限定される量ではないが、通常、難燃剤はポリオール１００重量部に対して、５０〜１５０重量部、整泡剤はポリオール１００重量部に対して、１〜６重量部であり、また、触媒は上記のとおりである。
In the aerosol composition of the present invention, in addition to the urethane prepolymer (A) and the propellant (B), in addition to auxiliary agents such as flame retardants, foam stabilizers and catalysts, other modifiers, pigments, etc. Coloring agents and the like can be blended within a range that does not impair the effects of the present invention. These components such as a modifier and a colorant can be blended when the urethane prepolymer is produced or when the aerosol composition is filled.
The amount of the auxiliary agent added is not particularly limited as long as the effect of the present invention is obtained. Usually, the flame retardant is 50 to 150 parts by weight with respect to 100 parts by weight of the polyol. The agent is 1 to 6 parts by weight with respect to 100 parts by weight of the polyol, and the catalyst is as described above.
本発明の一液軟質発泡ポリウレタンエアゾール組成物をエアゾール容器などの耐圧容器に充填する方法としては、合成したウレタンプレポリマーをエアゾール容器に充填する方法とエアゾール容器内でウレタンプレポリマーを作成する方法とが挙げられる。
前者の方法では、所定量のポリオールを、難燃剤、整泡剤及び触媒等の助剤、又は本発明の効果を阻害しない範囲で必要により添加することもあるその他の添加剤を含有する混合物を、イソシアネートと適切な反応温度で反応させてウレタンプレポリマーを調製する。得られたウレタンプレポリマーと噴射剤とを耐圧容器に充填する。
また、後者の方法では、所定量の難燃剤、整泡剤及び触媒等の助剤、また本発明の効果を阻害しない範囲で必要により添加することもあるその他の添加剤、及びポリオールを耐圧容器に充填し、続いてイソシアネート、さらに噴射剤を充填し、耐圧容器内でポリオールとイソシアネートとを反応させてウレタンプレポリマーを生成させることにより、簡易型の一液軟式発泡ポリウレタンエアゾール製品が得られる。
これらエアゾール製品の耐圧容器内の圧力は、２５℃で０．２０〜０．６２ＭＰａ程度である。
As a method of filling a pressure-resistant container such as an aerosol container with the one-component soft polyurethane foam aerosol composition of the present invention, a method of filling a synthesized urethane prepolymer into an aerosol container and a method of creating a urethane prepolymer in an aerosol container; Is mentioned.
In the former method, a mixture containing a predetermined amount of polyol, auxiliary agents such as flame retardants, foam stabilizers and catalysts, or other additives that may be added as necessary within the range not impairing the effects of the present invention. The urethane prepolymer is prepared by reacting with an isocyanate at an appropriate reaction temperature. The obtained pressure-resistant container is filled with the urethane prepolymer and the propellant.
Further, in the latter method, a predetermined amount of an auxiliary agent such as a flame retardant, a foam stabilizer and a catalyst, other additives which may be added as necessary within the range not impairing the effects of the present invention, and a polyol are added. Then, an isocyanate and further a propellant are charged, and a polyol and isocyanate are reacted in a pressure vessel to produce a urethane prepolymer, whereby a simple one-component soft foamed polyurethane aerosol product is obtained.
The pressure in the pressure vessel of these aerosol products is about 0.20 to 0.62 MPa at 25 ° C.
本発明の一液軟質発泡ポリウレタンエアゾール組成物により、次のような施工が可能になった。
１．住宅建設における水周り個所の気密性代替施工
通常、住宅等建築物の基礎と土台の間には空間を設け、床下の換気効率を上げ木材の腐敗菌類やイエシロアリを寄せ付けないような施工が施される。しかし、水周りや玄関周りでは通気を止め、気密性を確保する施工が行われる。
本発明の一液軟質発泡ポリウレタンエアゾール組成物を使用することにより次のような施工を行うことができる。
住宅建築物等の床下に良好な通気を確保するために基礎と土台の間に床下換気工法材が用いられている。該工法材の一つとして、再生材料であるフイラー強化ポリプロピレン樹脂複合材で作られた防鼠タイプであり、かつ通気孔が設けられた材料［例えば、サスマックス（ロングタイプ）：商品名、三井化学産資株式会社］がある。通常、このような工法材を基礎と土台の間に配置し、床下の換気を行う施工をする場合がある。
With the one-component soft polyurethane foam aerosol composition of the present invention, the following construction has become possible.
1. Alternative construction for airtightness in the area around water in housing construction Normally, a space is provided between the foundation and base of a building such as a house, and the construction is performed so as to increase the ventilation efficiency under the floor and keep wood spoilage fungi and termites away. The However, construction is performed to stop air flow around the water and the entrance to ensure airtightness.
The following construction can be performed by using the one-component soft foamed polyurethane aerosol composition of the present invention.
Under-floor ventilation materials are used between the foundation and the foundation to ensure good ventilation under the floor of residential buildings. One of the construction materials is a fender type made of recycled material, such as a filler-reinforced polypropylene resin composite, and a material provided with vents [for example, Susmax (long type): trade name, Mitsui Chemical Industrial Co., Ltd.]. Usually, there is a case where such a construction method material is arranged between the foundation and the foundation and ventilation is performed under the floor.
一方、住宅の浴室や玄関などの水周りでは気密性を確保するため通気を止める施工が必要である。係る場合、本発明の一液軟質発泡ポリウレタンエアゾール組成物を用い、上記の床下工法材を有効に転用して、簡易に通気を止める施工をすることができる。
すなわち、床下工法材を設置する基礎と土台の個所に床下工法材を土台の大きさに合わせて本発明の組成物を所要の厚さに噴射して発泡硬化層を形成させ、その上に床下工法材を配置し、圧着する。発泡硬化層は、床下工法材の通気孔を埋めて硬化し、気密性を確保できる。したがって、本発明の一液軟質発泡ポリウレタンエアゾール組成物を用いることにより、特定の目的に使用されていた材料をそのまま正反対の目的に使用して、水周りの気密性確保の施工を経済的に簡易に行うことができる。
On the other hand, in order to ensure airtightness around the water, such as in a bathroom or entrance of a house, it is necessary to perform construction to stop ventilation. In such a case, using the one-component soft foamed polyurethane aerosol composition of the present invention, the above-mentioned underfloor construction method material can be effectively diverted to easily stop the ventilation.
That is, the underfloor construction material is adjusted to the size of the foundation and the base where the underfloor construction material is installed, and the composition of the present invention is sprayed to the required thickness to form a foamed hardened layer. Arrange the construction materials and crimp them. The foamed hardened layer can be hardened by filling the air holes of the underfloor construction material to ensure airtightness. Therefore, by using the one-component soft foamed polyurethane aerosol composition of the present invention, the material used for a specific purpose can be used for the opposite purpose as it is, and the construction for ensuring airtightness around the water is economically simplified. Can be done.
２．床・壁材に化粧板等の取付施工における接着補助剤として
床・壁材の表面に化粧版等を取り付ける施工がある。係る施工に、本発明の一液軟質発泡ポリウレタンエアゾール組成物の垂れ難い性能を効果的に活用し接着補助材として適用できる。壁面に化粧版を取り付ける施工は、壁面に接着剤を塗布し化粧板を圧着する。この工法は壁面に接着剤を広範囲で塗布するような手間のかかる方法である。
これに対して、本発明の一液軟質発泡ポリウレタンエアゾール組成物は、垂れの物性が良好である（垂れ難い）ので、化粧板を取り付ける壁面又は化粧板の所定の位置に組成物を吹き付け、直ちに化粧板を接着固定し、硬化後吹き付け位置をネジ止めすることにより、化粧板をより簡易な作業で壁面に固定することが可能になる。
2. As an adhesive aid in the installation of decorative panels, etc. on floors and wall materials, there is a method of attaching decorative plates etc. on the surface of floors and wall materials. For such construction, the one-component soft foamed polyurethane aerosol composition of the present invention can be applied as an adhesion aid by effectively utilizing the performance of the one-component soft foam polyurethane aerosol composition. When installing the decorative plate on the wall surface, an adhesive is applied to the wall surface and the decorative plate is pressure-bonded. This method is a time-consuming method in which an adhesive is applied to a wall surface over a wide range.
On the other hand, since the one-component soft foamed polyurethane aerosol composition of the present invention has good sag properties (it is difficult to sag), the composition is sprayed on a wall surface or a predetermined position of the decorative plate to which the decorative plate is attached. It is possible to fix the decorative plate to the wall surface by a simpler operation by bonding and fixing the decorative plate and screwing the spraying position after curing.
３．窓枠サッシ周りへの適用
窓の下地にサッシを填め込むに際して、両者を固定接着するため、従来から一液硬式発泡ポリウレタンエアゾール組成物が好ましく適用されている。しかし、従来の一液硬式発泡ポリウレタンエアゾール組成物では、空隙を埋めるために使用する材料としては硬化発泡体が硬すぎるため、発泡体の発泡圧力によりドア枠又はサッシ枠を変形させたり、経時による構造物の変形に追従できなかったり、断熱・気密効果が失われやすい。これに対して、本発明の一液軟質発泡ポリウレタンエアゾール組成物では、この惧れがなく、ドア枠とサッシ枠の隙間を柔軟に埋め、構造物の変形に追従できるので、断熱・気密効果を向上できる。
3. Application to window frame sashes The one-component hard foam polyurethane aerosol composition has been conventionally applied to fix and bond the sashes to the base of the window. However, in the conventional one-component hard foamed polyurethane aerosol composition, since the cured foam is too hard as a material used to fill the void, the door frame or sash frame is deformed by the foaming pressure of the foam, It is difficult to follow the deformation of the structure, and heat insulation and airtight effects are easily lost. On the other hand, in the one-component soft foam polyurethane aerosol composition of the present invention, there is no such concern, and the gap between the door frame and the sash frame can be flexibly filled to follow the deformation of the structure. It can be improved.
その他、従来の一液発泡ポリウレタンエアゾール組成物が、住宅等建造物の断熱・気密性を高める目的のために使用されていた多くの様々な施工における問題点が、本発明の一液軟質発泡エアゾール組成物を用いることにより改善できる。 In addition, there are many problems in various constructions in which the conventional one-component foamed polyurethane aerosol composition has been used for the purpose of enhancing the heat insulation and airtightness of buildings such as houses. This can be improved by using the composition.
以下、本発明を実施例及び比較例により具体的に説明する。
実施例１
水酸基数３、分子量１，０００のポリエーテルポリオール〔商品名：アクトコールＭＮ−１０００（水酸基価：１６０ｍｇＫＯＨ／ｇ）、三井化学ポリウレタン（株）社製〕１００重量部と、水酸基数２、分子量２，０００のポリエーテルポリオール〔商品名：Ｄｉｏｌ２０００（水酸基価：５６ｍｇＫＯＨ／ｇ）、三井化学ポリウレタン（株）社製〕４重量部とを混合したポリエーテルポリオール、難燃剤としてトリス（β−クロロエチル）フォスフェ−ト（ＴＣＰＰ）６５重量部、整泡剤としてシロキサンオキシアルキレンコポリマー３重量部及び触媒としてテトラメチルへキサンジアミン２重量部との混合物を耐圧容器に充填した。続いてピュアージフェニルメタンジイソシアナート〔商品名：コスモネートＬＬ（ＮＣＯ％：２９．５％）、三井化学ポリウレタン（株）社製〕１３０．８重量部、噴射剤Ａ（イソペンタン１０．０重量％、ジメチルエーテル６．７重量％、プロパン１８．３重量％及びイソブタン６５．０重量からなる噴射剤組成物）８６重量部の順に充填した。ポリエーテルポリオールとイソシアナートの反応により得られたウレタンプレポリマーが噴射剤とともに充填された耐圧容器に、噴射ノズルを付けて密封しエアゾール製品を調製した。
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
Example 1
Polyether polyol having a hydroxyl number of 3 and a molecular weight of 1,000 [trade name: Actol MN-1000 (hydroxyl value: 160 mgKOH / g), manufactured by Mitsui Chemicals Polyurethane Co., Ltd.], a hydroxyl number of 2, and a molecular weight of 2 Polyether polyol (trade name: Diol 2000 (hydroxyl value: 56 mg KOH / g), Mitsui Chemicals Polyurethane Co., Ltd.) mixed with 4 parts by weight, tris (β-chloroethyl) phosphate as a flame retardant -A mixture of 65 parts by weight (TCPP), 3 parts by weight of a siloxane oxyalkylene copolymer as a foam stabilizer and 2 parts by weight of tetramethylhexanediamine as a catalyst was charged in a pressure vessel. Subsequently, pure diphenylmethane diisocyanate [trade name: Cosmonate LL (NCO%: 29.5%), manufactured by Mitsui Chemicals Polyurethane Co., Ltd.] 130.8 parts by weight, propellant A (isopentane 10.0% by weight, A propellant composition comprising 6.7% by weight of dimethyl ether, 18.3% by weight of propane and 65.0% by weight of isobutane) was charged in the order of 86 parts by weight. An aerosol product was prepared by attaching an injection nozzle to a pressure-resistant container filled with a urethane prepolymer obtained by reaction of polyether polyol and isocyanate together with a propellant, and sealing it.
調製したエアゾール容器から、一液軟質発泡ポリウレタンエアゾール組成物をノズルから噴射して発泡硬化体を生成させ、その発泡硬化体の諸物性を測定した。
諸物性の測定は、次の方法で行った。
タックフリータイム（分）：発泡体を指で触って表面のべとつきがなくなった時間を測定。
フォーム密度（ｋｇ／ｍ３）：ＪＩＳ Ａ９５１１
圧縮強度（Ｎ／ｍｍ２）：ＪＩＳ Ａ９５１１
２５％ＣＬＤ硬度（Ｎ／１００ｃｍ２）：ＪＩＳ Ｋ６４００−２：２００４ Ｄ法に準拠し、ポリウレタン発泡体、３０×２００×２００ｍｍの試験片を速度１０ｍｍ／ｍｉｎで全面押圧し、圧縮する方法で行った。
伸び（％）：ＪＩＳ Ａ９５１１
曲げ強度（Ｎ／ｍｍ２）：ＪＩＳ Ａ９５１１
引張強度（Ｎ／ｍｍ２）：ＪＩＳ Ａ９５１１
熱伝導率（Ｗ／ｍＫ） ：ＪＩＳ Ａ９５１１
弾性体のフォームの状態：◎−良好、×−不良
結果を表−１に示す。
From the prepared aerosol container, a one-component soft foamed polyurethane aerosol composition was sprayed from a nozzle to produce a foamed cured product, and various physical properties of the foamed cured product were measured.
Various physical properties were measured by the following methods.
Tack free time (minutes): Measures the time when the foam is touched with a finger and the surface is not sticky.
Foam density (kg / m 3 ): JIS A9511
Compressive strength (N / mm 2 ): JIS A9511
25% CLD hardness (N / 100 cm 2 ): in accordance with JIS K6400-2: 2004 D method, polyurethane foam, 30 × 200 × 200 mm test piece is pressed all over at a speed of 10 mm / min and compressed. It was.
Elongation (%): JIS A9511
Bending strength (N / mm 2 ): JIS A9511
Tensile strength (N / mm 2 ): JIS A9511
Thermal conductivity (W / mK): JIS A9511
The state of the foam of the elastic body: ◎ -good, x-defective results are shown in Table-1.
実施例２〜７
表−１に示すポリオール、イソシアネート、助剤及び噴射剤を用い、実施例１の方法に準じてエアゾール製品を調製した。調製したエアゾール容器から、一液軟質発泡ポリウレタンエアゾール組成物をノズルから噴射して発泡硬化体を生成させ、発泡硬化体の諸物性を測定した。結果を表−１に纏めて示す。
Examples 2-7
An aerosol product was prepared according to the method of Example 1 using the polyol, isocyanate, auxiliary agent and propellant shown in Table-1. From the prepared aerosol container, a one-component soft foamed polyurethane aerosol composition was sprayed from a nozzle to produce a foamed cured product, and various physical properties of the foamed cured product were measured. The results are summarized in Table 1.
比較例１
イソシアネートとしてポリメリックジフェニルメタンジイソシアナートを用いる組成物である。水酸基数３、分子量１，０００のポリエーテルポリオール〔商品名：アクトコールＭＮ−１０００（水酸基価：１６０ｍｇＫＯＨ／ｇ）、三井化学ポリウレタン（株）社製〕１００重量部と、水酸基数２、分子量２，０００のポリエーテルポリオール〔商品名：Ｄｉｏｌ２０００（水酸基価：５６ｍｇＫＯＨ／ｇ）、三井化学ポリウレタン（株）社製〕４重量部、難燃剤としてトリス（β−クロロエチル）フォスフェ−ト（ＴＣＰＰ）６５重量部、整泡剤としてシロキサンオキシアルキレンコポリマー３重量部及び触媒としてテトラメチルへキサンジアミン２重量部を耐圧容器に充填した。続いてポリメリックジフェニルメタンジイソシアナート〔商品名：コスモネートＭ−５０（ＮＣＯ％：３１．５％）、三井化学ポリウレタン（株）社製〕２３７．２重量部、噴射剤Ａ（イソペンタン１０重量％、ジメチルエーテル７重量％、プロパン１８重量％及びイソブタン６５重量％からなる噴射剤組成物）９４．７重量部の順に充填した。耐圧容器内にポリエーテルポリオールとイソシアナートの反応により得られたウレタンプレポリマーを噴射剤とともに充填された耐圧容器に、噴射ノズルを付けて密封しエアゾール製品を調製した。
調製したエアゾール容器から、一液発泡ポリウレタンエアゾール組成物をノズルから噴射して発泡硬化体を生成させ、その発泡硬化体の諸物性を測定した。結果を表−１に示す。
Comparative Example 1
It is a composition using polymeric diphenylmethane diisocyanate as an isocyanate. Polyether polyol having a hydroxyl number of 3 and a molecular weight of 1,000 [trade name: Actol MN-1000 (hydroxyl value: 160 mgKOH / g), manufactured by Mitsui Chemicals Polyurethane Co., Ltd.], a hydroxyl number of 2, and a molecular weight of 2 Polyether polyol [trade name: Diol 2000 (hydroxyl value: 56 mgKOH / g), manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.] 4 parts by weight, tris (β-chloroethyl) phosphate (TCPP) 65 weight as a flame retardant Parts, 3 parts by weight of a siloxane oxyalkylene copolymer as a foam stabilizer, and 2 parts by weight of tetramethylhexanediamine as a catalyst were filled in a pressure vessel. Subsequently, 237.2 parts by weight of polymeric diphenylmethane diisocyanate [trade name: Cosmonate M-50 (NCO%: 31.5%), manufactured by Mitsui Chemicals Polyurethane Co., Ltd.], propellant A (isopentane 10% by weight, A propellant composition comprising 7% by weight of dimethyl ether, 18% by weight of propane and 65% by weight of isobutane was charged in the order of 94.7 parts by weight. An aerosol product was prepared by attaching a spray nozzle to a pressure-resistant container filled with a urethane prepolymer obtained by reaction of polyether polyol and isocyanate in a pressure-resistant container together with a propellant.
From the prepared aerosol container, a one-component foamed polyurethane aerosol composition was sprayed from a nozzle to produce a foamed cured product, and various physical properties of the foamed cured product were measured. The results are shown in Table-1.
比較例２
イソシアネートとしてポリメリックジフェニルメタンジイソシアナートを用いる組成物である。比較例１と同様のポリエーテルポリオール１０４重量部、表−１に示す難燃剤、整泡剤及び触媒を、表−１に示す量を用い、イソシアネートとしてコスモネートＭ−２００（ＮＣＯ％：３１．４％）、三井化学ポリウレタン（株）社製〕２１７．３重量部、噴射剤Ｂ（ジメチルエーテル２５重量％、プロパン２８重量％及びイソブタン４７重量％からなる噴射剤組成物）８６重量部の順に充填した。ポリエーテルポリオールとイソシアナートとの反応によりウレタンプレポリマーを合成し、噴射ノズルを付けて密封してエアゾール製品を調製した。
得られた一液発泡ポリウレタンエアゾール組成物をノズルから噴射して発泡硬化体を生成させ、発泡硬化体の諸物性を測定した。結果を表−１に示す。
Comparative Example 2
It is a composition using polymeric diphenylmethane diisocyanate as an isocyanate. Cosmonate M-200 (NCO%: 31.N) as an isocyanate using 104 parts by weight of the same polyether polyol as in Comparative Example 1, flame retardants, foam stabilizers and catalysts shown in Table 1 in amounts shown in Table 1. 4%), made by Mitsui Chemicals Polyurethanes Co., Ltd.] 217.3 parts by weight, propellant B (a propellant composition consisting of 25% by weight of dimethyl ether, 28% by weight of propane and 47% by weight of isobutane) in this order. did. A urethane prepolymer was synthesized by reaction of polyether polyol and isocyanate and sealed with a spray nozzle to prepare an aerosol product.
The obtained one-component foamed polyurethane aerosol composition was sprayed from a nozzle to produce a foamed cured product, and various physical properties of the foamed cured product were measured. The results are shown in Table-1.
比較例３
イソシアネートとしてポリメリックジフェニルメタンジイソシアナートを用いる組成物である。比較例１に準じる方法により、表−１に示す種類と量のポリオール、イソシアネート及び助剤、さらに噴射剤を順次、耐圧容器に充填した。
得られた一液発泡ポリウレタンエアゾール組成物をノズルから噴射して発泡硬化体を生成させ、発泡硬化体の諸物性を測定した。結果を表−１に纏めて示す。
Comparative Example 3
It is a composition using polymeric diphenylmethane diisocyanate as an isocyanate. By the method according to Comparative Example 1, the pressure vessel was sequentially filled with the types and amounts of polyols, isocyanates and auxiliaries and propellants shown in Table-1.
The obtained one-component foamed polyurethane aerosol composition was sprayed from a nozzle to produce a foamed cured product, and various physical properties of the foamed cured product were measured. The results are summarized in Table 1.
表−１において
１）アクトコールＭＮ−１０００：商品名、分子量１０００のポリオール、水酸基価：１６０ｍｇＫＯＨ／ｇ、
２）アクトコールＤｉｏｌ−２０００：商品名、分子量２０００のポリオール、水酸基価：５６ｍｇＫＯＨ／ｇ、三井化学ポリウレタン（株）社製。
３）コスモネートＭ−５０：商品名、ポリメリックＭＤＩ、ＮＣＯ（％）３１．５％、三井化学ポリウレタン（株）社製。
４）コスモネートＭ−２００：商品名、ポリメリックＭＤＩ、ＮＣＯ（％）３１．４％、三井化学ポリウレタン（株）社製。
５）コスモネートＬＬ：商品名、ピュアＭＤＩ、ＮＣＯ（％）２９．５％、三井化学ポリウレタン（株）社製。
６）コスモネートＬＫ：商品名、ピュアＭＤＩ、ＮＣＯ（％）２８．３％三井化学ポリウレタン（株）社製。
７）難燃剤：トリス（β−クロロエチル）フォスフェ−ト
８）整泡剤：シロキサンオキシアルキレンコポリマー
９）触媒：テトラメチルヘキサンジアミン
１０）噴射剤Ａ：イソペンタン１０重量％、ジメチルエーテル７重量％、プロパン１８重量％及びイソブタン６５重量％からなる噴射剤組成物。
１１）噴射剤Ｂ：ジメチルエーテル２５重量％、プロパン２８重量％及びイソブタン４７重量％からなる噴射剤組成物。
１２）ウレタンプレポリマーの重量部と噴射剤の重量部は、ポリオール、イソシアネート、難燃剤、整泡剤、触媒量を合計してウレタンプレポリマーの重量部とし、この重量部と噴射剤の重量部との合計が１００重量部となる量を示す。
In Table 1, 1) Actol MN-1000: trade name, polyol having a molecular weight of 1000, hydroxyl value: 160 mgKOH / g,
2) Actol Diol-2000: trade name, polyol having a molecular weight of 2000, hydroxyl value: 56 mgKOH / g, manufactured by Mitsui Chemicals Polyurethanes.
3) Cosmonate M-50: trade name, polymeric MDI, NCO (%) 31.5%, manufactured by Mitsui Chemicals Polyurethanes.
4) Cosmonate M-200: trade name, polymeric MDI, NCO (%) 31.4%, manufactured by Mitsui Chemicals Polyurethanes.
5) Cosmonate LL: trade name, Pure MDI, NCO (%) 29.5%, manufactured by Mitsui Chemicals Polyurethanes.
6) Cosmonate LK: Trade name, Pure MDI, NCO (%) 28.3%, manufactured by Mitsui Chemicals Polyurethanes.
7) Flame retardant: Tris (β-chloroethyl) phosphate 8) Foam stabilizer: Siloxane oxyalkylene copolymer 9) Catalyst: Tetramethylhexanediamine 10) Propellant A: Isopentane 10% by weight, dimethyl ether 7% by weight, propane 18 A propellant composition comprising wt% and isobutane 65 wt%.
11) Propellant B: A propellant composition comprising 25% by weight of dimethyl ether, 28% by weight of propane and 47% by weight of isobutane.
12) The weight part of the urethane prepolymer and the weight part of the propellant are the weight part of the urethane prepolymer by adding the polyol, isocyanate, flame retardant, foam stabilizer and catalyst amount, and this weight part and the weight part of the propellant. And the total amount is 100 parts by weight.
比較例４及び５
実施例１のポリオール、イソシアネートをＮＣＯインデックスが２．５または５．０となる量を用い、その外、助剤及び噴射剤を実施例１と同量を用いて実施例１に同様の方法で一液軟質発泡ポリウレタンエアゾール組成物を含有するエアゾール製品を調製した。ノズルから噴射して発泡硬化体を生成させたが、ＮＣＯインデックスが２．５では硬化発泡体が柔かすぎて収縮し、また、ＮＣＯインデックスが５では発泡硬化体が硬すぎて、本願発明の効果が得られなかった。
Comparative Examples 4 and 5
In the same manner as in Example 1, using the polyol and isocyanate of Example 1 in an amount such that the NCO index is 2.5 or 5.0, and using the same amount of auxiliary agent and propellant as in Example 1. An aerosol product containing a one-part soft foamed polyurethane aerosol composition was prepared. A foamed cured product was produced by spraying from a nozzle. When the NCO index was 2.5, the cured foam was too soft and contracted, and when the NCO index was 5, the foamed cured product was too hard. The effect was not obtained.
実施例８
（合成したウレタンプレポリマーをエアゾール容器に充填する例）
水酸基数３、分子量１０００のポリエーテルポリオール〔商品名：アクトコールＭＮ−１０００（水酸基価：１６０ｍｇＫＯＨ／ｇ）、三井化学ポリウレタン（株）社製〕１００重量部と水酸基数２、分子量２０００のポリエーテルポリオール〔商品名：アクトコールＤｉｏｌ２０００（水酸基価：５６ｍｇＫＯＨ／ｇ）、三井化学ポリウレタン（株）社製〕４重量部に、ピュアージフェニルメタンジイソシアナート〔商品名：コスモネートＬＬ（ＮＣＯ％：２９．５％）、三井化学ポリウレタン（株）社製〕１３０．８重量部、難燃剤としてトリス（β−クロロエチル）フォスフェ−ト（ＴＣＰＰ）６５重量部、及び整泡剤としてシロキサンオキシアルキレンコポリマー３重量部を混合し、７０℃で１時間反応させた。粘度が約２０，０００ｃｐｓ（２５℃）である淡黄色のウレタンプレポリマーを調製した。このウレタンプレポリマーに触媒としてテトラメチルへキサンジアミン２重量部を加え合計３０５重量部のレジン原液を調製した。
この原液１６４重量部を耐圧容器に充填し、続いて噴射剤Ａ４６重量部の順に充填し密封したエアゾール製品を調製した。
調製したエアゾール製品の一液軟式発泡ポリウレタンエアゾール組成物をノズルから噴射して発泡硬化体を生成させ、発泡硬化体の諸物性を測定した。その結果、タックフリータイム、フォーム密度、２５％ＣＬＤ、伸び、引張強度及び熱伝導率と実施例１の発泡硬化体と略同じ、良好な物性を有し、弾性体のフォームの状態は良好であった。
Example 8
(Example of filling the urethane container with the synthesized urethane prepolymer)
Polyether polyol having 3 hydroxyl groups and 1000 molecular weight [Trade name: Actol MN-1000 (hydroxyl value: 160 mgKOH / g), manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.], 100 parts by weight, polyether having 2 hydroxyl groups and 2000 molecular weight Polydiphenylmethane diisocyanate [trade name: Cosmonate LL (NCO%: 29.5%) is added to 4 parts by weight of polyol [trade name: Actol Diol 2000 (hydroxyl value: 56 mg KOH / g), manufactured by Mitsui Chemicals Polyurethanes, Inc.]. %), Made by Mitsui Chemicals Polyurethanes Co., Ltd.] 130.8 parts by weight, 65 parts by weight of tris (β-chloroethyl) phosphate (TCPP) as a flame retardant, and 3 parts by weight of a siloxane oxyalkylene copolymer as a foam stabilizer. The mixture was mixed and reacted at 70 ° C. for 1 hour. A pale yellow urethane prepolymer having a viscosity of about 20,000 cps (25 ° C.) was prepared. As a catalyst, 2 parts by weight of tetramethylhexanediamine was added to this urethane prepolymer to prepare a total of 305 parts by weight of a resin stock solution.
An aerosol product was prepared by filling 164 parts by weight of this undiluted solution into a pressure-resistant container, and subsequently filling and sealing in the order of 46 parts by weight of propellant A.
The prepared one-component soft foamed polyurethane aerosol composition was sprayed from a nozzle to produce a foamed cured product, and various physical properties of the foamed cured product were measured. As a result, tack-free time, foam density, 25% CLD, elongation, tensile strength and thermal conductivity were almost the same as the foamed cured product of Example 1, and the physical properties of the elastic foam were good. there were.
本発明の一液軟質発泡ポリウレタンエアゾール組成物は、従来の一液発泡ポリウレタンエアゾール組成物に比べ、接着性、気密性、柔軟性、伸び等に優れ、住宅建造物の断熱、気密性等に効果を示し、産業上極めて有効である。 The one-component soft foamed polyurethane aerosol composition of the present invention is superior in adhesiveness, airtightness, flexibility, elongation, etc. compared to conventional one-component foamed polyurethane aerosol compositions, and is effective for heat insulation, airtightness, etc. of residential buildings. It is extremely effective in industry.
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