JP5532224B2 - Urethane prepolymer - Google Patents
Urethane prepolymer Download PDFInfo
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- JP5532224B2 JP5532224B2 JP2010041829A JP2010041829A JP5532224B2 JP 5532224 B2 JP5532224 B2 JP 5532224B2 JP 2010041829 A JP2010041829 A JP 2010041829A JP 2010041829 A JP2010041829 A JP 2010041829A JP 5532224 B2 JP5532224 B2 JP 5532224B2
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- urethane prepolymer
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- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims description 68
- 229920005862 polyol Polymers 0.000 claims description 33
- 150000003077 polyols Chemical class 0.000 claims description 33
- 239000000853 adhesive Substances 0.000 claims description 27
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 26
- 230000001070 adhesive effect Effects 0.000 claims description 26
- 229920000570 polyether Polymers 0.000 claims description 26
- 229920005906 polyester polyol Polymers 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- -1 polytetramethylene Polymers 0.000 claims description 9
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 6
- 229920003232 aliphatic polyester Polymers 0.000 claims description 4
- QDFXRVAOBHEBGJ-UHFFFAOYSA-N 3-(cyclononen-1-yl)-4,5,6,7,8,9-hexahydro-1h-diazonine Chemical compound C1CCCCCCC=C1C1=NNCCCCCC1 QDFXRVAOBHEBGJ-UHFFFAOYSA-N 0.000 claims description 2
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 23
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 22
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 22
- 238000001723 curing Methods 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 239000000758 substrate Substances 0.000 description 16
- 230000001588 bifunctional effect Effects 0.000 description 13
- 230000035699 permeability Effects 0.000 description 13
- 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 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000001361 adipic acid Substances 0.000 description 11
- 235000011037 adipic acid Nutrition 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 229910001873 dinitrogen Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 150000002009 diols Chemical class 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 10
- 229920001451 polypropylene glycol Polymers 0.000 description 10
- 208000005156 Dehydration Diseases 0.000 description 9
- 230000018044 dehydration Effects 0.000 description 9
- 238000006297 dehydration reaction Methods 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 238000005187 foaming Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- SSUJUUNLZQVZMO-UHFFFAOYSA-N 1,2,3,4,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCC=CN2CCCNC21 SSUJUUNLZQVZMO-UHFFFAOYSA-N 0.000 description 5
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- ZKSBDEFDWSDNPW-UHFFFAOYSA-N 1-butoxy-2,4-diisocyanatobenzene Chemical compound CCCCOC1=CC=C(N=C=O)C=C1N=C=O ZKSBDEFDWSDNPW-UHFFFAOYSA-N 0.000 description 1
- SZBXTBGNJLZMHB-UHFFFAOYSA-N 1-chloro-2,4-diisocyanatobenzene Chemical compound ClC1=CC=C(N=C=O)C=C1N=C=O SZBXTBGNJLZMHB-UHFFFAOYSA-N 0.000 description 1
- NBUGUQFIYUNXCW-UHFFFAOYSA-N 2,3,3-trimethylpentane-2,4-diamine Chemical compound CC(N)C(C)(C)C(C)(C)N NBUGUQFIYUNXCW-UHFFFAOYSA-N 0.000 description 1
- DZDVHNPXFWWDRM-UHFFFAOYSA-N 2,4-diisocyanato-1-methoxybenzene Chemical compound COC1=CC=C(N=C=O)C=C1N=C=O DZDVHNPXFWWDRM-UHFFFAOYSA-N 0.000 description 1
- VXQILLTWRZPRQF-UHFFFAOYSA-N 2,4-diisocyanato-1-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(N=C=O)C=C1N=C=O VXQILLTWRZPRQF-UHFFFAOYSA-N 0.000 description 1
- ACMIJDVJWLMBCX-PXAZEXFGSA-N 4-[(3ar,6ar)-2,3,3a,4,6,6a-hexahydro-1h-pyrrolo[2,3-c]pyrrol-5-yl]-6-fluoro-n-methyl-2-(2-methylpyrimidin-5-yl)oxy-9h-pyrimido[4,5-b]indol-8-amine Chemical compound CNC1=CC(F)=CC(C2=C(N3C[C@@H]4NCC[C@@H]4C3)N=3)=C1NC2=NC=3OC1=CN=C(C)N=C1 ACMIJDVJWLMBCX-PXAZEXFGSA-N 0.000 description 1
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- VWYHWAHYVKZKHI-UHFFFAOYSA-N N=C=O.N=C=O.C1=CC(N)=CC=C1C1=CC=C(N)C=C1 Chemical compound N=C=O.N=C=O.C1=CC(N)=CC=C1C1=CC=C(N)C=C1 VWYHWAHYVKZKHI-UHFFFAOYSA-N 0.000 description 1
- AEZZSRCTSQADDX-UHFFFAOYSA-N N=C=O.N=C=O.CC1=CC(C)=CC(C)=C1 Chemical compound N=C=O.N=C=O.CC1=CC(C)=CC(C)=C1 AEZZSRCTSQADDX-UHFFFAOYSA-N 0.000 description 1
- 239000004825 One-part adhesive Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B7/00—Footwear with health or hygienic arrangements
- A43B7/14—Footwear with health or hygienic arrangements with foot-supporting parts
- A43B7/26—Footwear with health or hygienic arrangements with foot-supporting parts with toe-spacers or toe-spreaders
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B17/00—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
- A43B17/16—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined with heel or toe caps
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43C—FASTENINGS OR ATTACHMENTS OF FOOTWEAR; LACES IN GENERAL
- A43C7/00—Holding-devices for laces
- A43C7/06—Elastic bands
Landscapes
- Health & Medical Sciences (AREA)
- Epidemiology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、接着剤などに有用なウレタンプレポリマーに関するものであり、詳しくは、室温で流動性があり、湿気により発泡しながら硬化し、透湿性に優れた無溶剤系のウレタンプレポリマー、該ウレタンプレポリマーの塗工方法及び該ウレタンプレポリマーからなる接着剤に関するものである。 The present invention relates to a urethane prepolymer useful for an adhesive and the like. Specifically, the solvent-free urethane prepolymer which is fluid at room temperature, cures while foaming by moisture, and has excellent moisture permeability, The present invention relates to a urethane prepolymer coating method and an adhesive comprising the urethane prepolymer.
ウレタンプレポリマーは、接着剤、塗料、シーリング材料に用いられ、特に湿気硬化型のウレタンプレポリマーは空気中の水分で硬化するため１液で使用できる。接着強度を得るためには、樹脂の構造上常温において固形のものが多く、溶剤で希釈されたり、メルター等の装置で加熱熔融し液状にして塗工に用いられてきた。また、繊維などの多孔質基材の塗工の際には、硬化するまでにウレタンプレポリマーが基材内部に浸透するため多孔質基材の風合いや弾力性が損なわれ、接着剤に用いる場合接着力が低下するという問題があった。さらに、皮膜は透湿性に乏しく、透湿性に乏しい基材同士をラミネートする場合には、透湿性を付与するためにドット接着などの方法が用いられてきたが接着強度が不足する問題があった。 Urethane prepolymers are used in adhesives, paints, and sealing materials. In particular, moisture-curing urethane prepolymers can be used in one liquid because they are cured with moisture in the air. In order to obtain adhesive strength, the resin structure is often solid at room temperature, and has been diluted with a solvent or melted by heating with a device such as a melter to form a liquid and used for coating. Also, when applying porous substrates such as fibers, the urethane prepolymer penetrates into the substrate before it is cured, so the texture and elasticity of the porous substrate are impaired, and it is used for adhesives There was a problem that the adhesive strength was reduced. Furthermore, the film has poor moisture permeability, and when laminating substrates with poor moisture permeability, methods such as dot bonding have been used to impart moisture permeability, but there was a problem of insufficient adhesive strength. .
かかる状況下において、特許文献１によれば、ポリテトラメチレングリコールと、４，４’−ジフェニルメタンジイソシアネートとを反応させて得られたウレタンプレポリマーからなる一液形の接着剤が提案されているが、かかるウレタンプレポリマーによっても樹脂性状のほか、接着強度は未だ十分でなく、透湿性、発泡性、耐加水分解性等の接着剤に要求されるすべての品質性状を満足させるものは得られていない。
従って、本発明の課題は、前記の欠点を解決し、メルター等を用いる必要が無く常温液状であり、多孔質基材に塗布した際にも基材内部に浸透することなく弾力性を発現し、かつ硬化皮膜は透湿性に優れた湿気硬化性のウレタンプレポリマーを提供することにある。 Therefore, the object of the present invention is to solve the above-mentioned drawbacks, is not necessary to use a melter or the like, is liquid at room temperature, and exhibits elasticity without penetrating into the substrate even when applied to a porous substrate. The cured film is intended to provide a moisture curable urethane prepolymer excellent in moisture permeability.
そこで、本発明者らは、前記の本発明の課題を解決するために、鋭意検討を重ねた結果、特定のポリエーテルポリオール成分および特定割合のポリエーテルポリオールとポリエステルポリオールならびに特定の硬化促進剤を用いることにより得られるウレタンプレポリマーが前記課題を解決できることに着目し、かかる知見に基づいて本発明に想到した。 Therefore, as a result of intensive studies in order to solve the above-described problems of the present invention, the present inventors have obtained a specific polyether polyol component, a specific proportion of polyether polyol and polyester polyol, and a specific curing accelerator. Focusing on the fact that the urethane prepolymer obtained by use can solve the above-mentioned problems, the present inventors have arrived at the present invention based on such knowledge.
かくして、本発明によれば、次の（１）〜（６）が提供される。
（１）ポリエーテルポリオール、ポリエステルポリオール及びポリイソシアネートをＮＣＯ／ＯＨ当量比１．１〜３．０で反応させた後、アミン系硬化促進剤を０．０１〜５質量％含有させてなるウレタンプレポリマーにおいて、ポリエーテルポリオール／ポリエステルポリオールの質量比が９５／５〜７５／２５であり、ポリエーテルポリオールの主成分がポリテトラメチレングリコール−ポリエチレングリコール共重合体またはポリプロピレングリコールであるウレタンプレポリマー。
（２）前記ポリエーテルポリオールの数平均分子量が５００〜３０００であり、ポリエステルポリオールの数平均分子量が３００〜３０００である前記（１）に記載のウレタンプレポリマー。
（３）前記ポリエステルポリオールが脂肪族ポリエステルポリオールである前記（１）または（２）に記載のウレタンプレポリマー。
（４）粘度が２０，０００ｄＰａ・ｓ／２５℃以下である前記（１）乃至（３）のいずれかに記載のウレタンプレポリマー。
（５）前記（１）乃至（４）のいずれかに記載のウレタンプレポリマーを、湿気により発泡させながら硬化させることを特徴とするウレタンプレポリマー塗工方法。
（６）前記（１）乃至（４）のいずれかに記載のウレタンプレポリマーからなる接着剤。
Thus, according to the present invention, the following (1) to (6) are provided.
(1) After reacting polyether polyol, polyester polyol, and polyisocyanate with an NCO / OH equivalent ratio of 1.1 to 3.0, urethane prepolymer containing 0.01 to 5% by mass of an amine curing accelerator. In the polymer, a urethane prepolymer in which the mass ratio of polyether polyol / polyester polyol is 95/5 to 75/25, and the main component of the polyether polyol is a polytetramethylene glycol-polyethylene glycol copolymer or polypropylene glycol.
(2) The urethane prepolymer according to (1), wherein the polyether polyol has a number average molecular weight of 500 to 3,000, and the polyester polyol has a number average molecular weight of 300 to 3,000.
(3) The urethane prepolymer according to (1) or (2), wherein the polyester polyol is an aliphatic polyester polyol.
(4) The urethane prepolymer according to any one of (1) to (3), wherein the viscosity is 20,000 dPa · s / 25 ° C. or less.
(5) A urethane prepolymer coating method, wherein the urethane prepolymer according to any one of (1) to (4) is cured while being foamed by moisture.
(6) An adhesive comprising the urethane prepolymer according to any one of (1) to (4).
本発明のウレタンプレポリマーは、常温で液状であることから取扱いが容易であり、かつその硬化物は透湿性を有することから、透湿性基材をラミネートする接着剤として優れた性能を発揮する。更に、繊維などの接着剤としては洗濯による耐加水分解性が求められるが、これに対しても一定の耐性を有する。 The urethane prepolymer of the present invention is easy to handle because it is liquid at room temperature, and since the cured product has moisture permeability, it exhibits excellent performance as an adhesive for laminating moisture permeable substrates. Furthermore, as an adhesive such as fiber, hydrolysis resistance by washing is required, but this also has a certain resistance.
また、アミン系硬化促進剤を添加することにより、塗工後直ちに発泡し多孔質基材への塗工時に基材に吸収されることが無く初期の強度を発揮する事が可能である。 Further, by adding an amine-based curing accelerator, it is possible to exhibit initial strength without foaming immediately after coating and being absorbed by the substrate when applied to the porous substrate.
次に好ましい実施の形態を挙げて本発明をさらに詳細に説明する。 Next, the present invention will be described in more detail with reference to preferred embodiments.
本発明に係るウレタンプレポリマーの合成成分として使用するポリエーテルポリオールは、ポリテトラメチレングリコールとポリエチレングリコールとの共重合体またはポリプロピレングリコールである。 The polyether polyol used as a synthesis component of the urethane prepolymer according to the present invention is a copolymer of polytetramethylene glycol and polyethylene glycol or polypropylene glycol.
かかるポリエーテルポリオール以外のポリエーテルポリオールを使用すると、ウレタンプレポリマーが常温で固体となったり、得られた皮膜の耐加水分解性や透湿性が低くなるという問題が生じる。 When a polyether polyol other than such a polyether polyol is used, there arises a problem that the urethane prepolymer becomes solid at room temperature, and the hydrolysis resistance and moisture permeability of the obtained film are lowered.
ラメチレングリコールとポリエチレングリコールの割合はポリテトラメチレングリコール／ポリエチレングリコールの質量比で８０／２０ 〜 ２０／８０の範囲を採用することができるが、好ましくは質量比で７０／３０〜３０／７０の範囲である。 The ratio of ramethylene glycol and polyethylene glycol can be in the range of 80/20 to 20/80 in terms of mass ratio of polytetramethylene glycol / polyethylene glycol, but preferably in the range of 70/30 to 30/70 by mass ratio. It is a range.
ポリエーテルポリオールの分子量は、数平均分子量で５００〜３０００であることが好ましく、８００〜２５００であることがより好ましい。数平均分子量が５００未満では硬化皮膜の透湿性が悪くなり、一方、数平均分子量が３０００を超えると多孔質基材との接着性が低下する。 The molecular weight of the polyether polyol is preferably 500 to 3000, more preferably 800 to 2500 in terms of number average molecular weight. When the number average molecular weight is less than 500, the moisture permeability of the cured film is deteriorated. On the other hand, when the number average molecular weight exceeds 3000, the adhesion with the porous substrate is lowered.
ポリエーテルポリオールは単独でまたは２種以上組み合わせて用いることもできる。 Polyether polyols can be used alone or in combination of two or more.
本発明に係るウレタンプレポリマーの合成成分として使用するポリエステルポリオールは特に限定されないが、２官能が好ましく、更には脂肪族ポリエステルポリオールが好ましい。脂肪族ポリエステルポリオールの酸成分としては、コハク酸、アジピン酸、セバシン酸、アゼライン酸などの二塩基酸が挙げられ、アルコール成分としてはエチレングリコール、１、２−プロパンジオール、ｎ−プロパンジオール、１，３−ブタンジオール、１，４−ブタンジオール、１，６−ヘキサンジオールなどが挙げられる。 The polyester polyol used as a synthesis component of the urethane prepolymer according to the present invention is not particularly limited, but is preferably bifunctional, and more preferably an aliphatic polyester polyol. Examples of the acid component of the aliphatic polyester polyol include dibasic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid. Examples of the alcohol component include ethylene glycol, 1,2-propanediol, n-propanediol, , 3-butanediol, 1,4-butanediol, 1,6-hexanediol and the like.
ポリエステルポリオールの分子量は、数平均分子量で３００〜３０００であることが好ましい。数平均分子量が３００未満では多孔質基材との接着性が低下する。また、数平均分子量が３０００を超えると常温でのプレポリマーの流動性が悪くなる。
ポリエステルポリオールは単独でまたは２種以上組み合わせて用いることも出来る。
The molecular weight of the polyester polyol is preferably 300 to 3000 in terms of number average molecular weight. If the number average molecular weight is less than 300, the adhesion to the porous substrate is lowered. On the other hand, if the number average molecular weight exceeds 3000, the fluidity of the prepolymer at normal temperature is deteriorated.
Polyester polyols can be used alone or in combination of two or more.
ポリエーテルポリオールとポリエステルポリオールの割合は、ポリエーテルポリオール／ポリエステルポリオールの質量比で９５／５〜７５／２５であり、好ましくは９０／１０〜８０／２０である。ポリエーテルポリオール／ポリエステルポリオールの質量比が９５／５を超えると多孔質基材との接着強度が低下し好ましくない。また、ポリエーテルポリオール／ポリエステルポリオールの質量比が７５／２５未満では透湿性や耐加水分解性が低下し好ましくない。 The ratio of the polyether polyol to the polyester polyol is 95/5 to 75/25, preferably 90/10 to 80/20, in terms of the mass ratio of polyether polyol / polyester polyol. When the mass ratio of polyether polyol / polyester polyol exceeds 95/5, the adhesive strength with the porous substrate is undesirably lowered. Moreover, when the mass ratio of polyether polyol / polyester polyol is less than 75/25, moisture permeability and hydrolysis resistance are lowered, which is not preferable.
本発明に係るウレタンプレポリマーの合成成分として使用するポリイソシアネートは特に限定されないが、２官能のポリイソシアネートが好ましい。ポリイソシアネートの具体例としては、トリレンジイソシアネート、４−メトキシ−１，３−フェニレンジイソシアネート、４−イソプロピル−１，３−フェニレンジイソシアネート、４−クロル−１，３−フェニレンジイソシアネート、４−ブトキシ−１，３−フェニレンジイソシアネート、２，４−ジイソシアネート−ジフェニルエーテル、メシチレンジイソシアネート、４，４′−メチレンビス（フェニルイソシアネート）、ジュリレンジイソシアネート、１，５−ナフタレンジイソシアネート、ベンジジンジイソシアネート、ｏ−ニトロベンジジンジイソシアネート、４，４−ジイソシアネートジベンジル、１，４−テトラメチレンジイソシアネート、１，６−ヘキサメチレンジイソシアネート、１，１０−デカメチレンジイソシアネート、１，４−シクロヘキシレンジイソシアネート、キシレンジイソシアネート、４，４−メチレンビス（シクロヘキシルイソシアネート）、１，５−テトラヒドロナフタレンジイソシアネート、イソホロンジイソシアネートなどである。 The polyisocyanate used as a synthesis component of the urethane prepolymer according to the present invention is not particularly limited, but a bifunctional polyisocyanate is preferable. Specific examples of the polyisocyanate include tolylene diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl-1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1 , 3-phenylene diisocyanate, 2,4-diisocyanate-diphenyl ether, mesitylene diisocyanate, 4,4'-methylenebis (phenyl isocyanate), jurylene diisocyanate, 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4, 4-diisocyanate dibenzyl, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate Over DOO, 1,4-cyclohexylene diisocyanate, xylylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, and the like.
また、本発明の効果を損なわない範囲で、低分子のポリオールを使用してもよい。 Moreover, you may use a low molecular polyol in the range which does not impair the effect of this invention.
ポリオールとポリイソシアネートの比率は、ＮＣＯ／ＯＨ当量比で１．１〜３．０である。ＮＣＯ／ＯＨ当量比が１．１未満では、接着後の硬化皮膜強度が劣る事により接着強度が低下し好ましくなく、一方、ＮＣＯ／ＯＨ当量比が３．０を超えると接着後の硬化皮膜強度が硬くなり構成体としての風合いを損ない好ましくない。 The ratio of polyol and polyisocyanate is 1.1 to 3.0 in terms of an NCO / OH equivalent ratio. If the NCO / OH equivalent ratio is less than 1.1, the cured film strength after bonding is inferior due to the inferior cured film strength. On the other hand, if the NCO / OH equivalent ratio exceeds 3.0, the cured film strength after bonding is not preferable. Becomes hard, and the texture as a structure is impaired.
本発明に係るウレタンプレポリマーに対する配合成分として使用する硬化促進剤は、アミン系硬化促進剤が好ましい。かかるアミン系硬化促進剤以外の硬化促進剤は硬化皮膜の発泡性に乏しく好ましくない。 The curing accelerator used as a blending component for the urethane prepolymer according to the present invention is preferably an amine-based curing accelerator. Curing accelerators other than such amine-based curing accelerators are not preferred due to poor foaming properties of the cured film.
アミン系硬化促進剤の具体例として、トリエチルアミン、トリエチレンジアミン、テトラメチル−１，３−ブタンジアミン、エチルモルホリン、ジアザビシクロウンデセン、ジアザビシクロノネン等が挙げられる。 Specific examples of the amine curing accelerator include triethylamine, triethylenediamine, tetramethyl-1,3-butanediamine, ethylmorpholine, diazabicycloundecene, diazabicyclononene, and the like.
アミン系硬化促進剤の添加量はウレタンプレポリマーに対して０．０１〜５質量％であり、好ましくは０．１〜２質量％である。添加量が０．０１質量％未満では硬化皮膜の発泡性に乏しいので好ましくなく、一方、５．０質量％を超えるとポットライフが短くなり作業性が低下し好ましくない。 The addition amount of the amine curing accelerator is 0.01 to 5% by mass, preferably 0.1 to 2% by mass with respect to the urethane prepolymer. If the addition amount is less than 0.01% by mass, the cured film is poor in foaming property. On the other hand, if it exceeds 5.0% by mass, the pot life is shortened and the workability is lowered.
本発明に係るウレタンプレポリマーの粘度は２０，０００ｄＰａ・ｓ／２５℃以下であることが好ましい。好ましくは１０，０００ｄＰａ・ｓ／２５℃以下であり、特に好ましくは３，０００ｄＰａ・ｓ／２５℃以下である。また、常態が液状であれば、下限値は特に限定されるものではないが、５０ｄＰａ・ｓ／２５℃以上であることが特に好ましい。
粘度が２０，０００ｄＰａ・ｓ／２５℃以上では作業性に問題があり好ましくない。
The viscosity of the urethane prepolymer according to the present invention is preferably 20,000 dPa · s / 25 ° C. or less. Preferably it is 10,000 dPa * s / 25 degrees C or less, Most preferably, it is 3,000 dPa * s / 25 degrees C or less. If the normal state is liquid, the lower limit is not particularly limited, but is particularly preferably 50 dPa · s / 25 ° C. or higher.
When the viscosity is 20,000 dPa · s / 25 ° C. or higher, there is a problem in workability, which is not preferable.
本発明のウレタンプレポリマーを基材に塗工すると、空気中の湿気により二酸化炭素を発生しながら硬化する。発泡しながら硬化するため、多孔質基材に塗工した際にウレタンプレポリマーが内部に浸透することがないため、基材の風合いや弾力性を損なうことがなく、また接着剤として使用する際は基材表面に必要量のウレタンプレポリマーが存在するため、塗布量不足による接着力低下がない。 When the urethane prepolymer of the present invention is applied to a substrate, it is cured while generating carbon dioxide due to moisture in the air. Because it cures while foaming, the urethane prepolymer does not penetrate inside when coated on a porous substrate, so the texture and elasticity of the substrate are not impaired, and when used as an adhesive Since the necessary amount of urethane prepolymer is present on the surface of the substrate, there is no decrease in adhesive strength due to insufficient coating amount.
本発明のウレタンプレポリマーは、接着剤のほか、塗料、シーリング材料などに有用に用いられる。 The urethane prepolymer of the present invention is useful for paints, sealing materials, etc. in addition to adhesives.
本発明に係るウレタンプレポリマーからなる接着剤は、かかるウレタンプレポリマーの用途の一つとして主要な領域を締めるものであり、本発明に係るウレタンプレポリマーの特異性が生かされたものである。 The adhesive made of the urethane prepolymer according to the present invention is one of the uses of the urethane prepolymer, which is used to tighten the main area, and makes use of the specificity of the urethane prepolymer according to the present invention.
すなわち、当該ウレタンプレポリマーは、ポリエーテルポリオール、ポリエステルポリオール及びポリイソシアネートをＮＣＯ／ＯＨ当量比１．１〜３．０で反応させた後、アミン系硬化促進剤を０．０１〜５質量％含有させてなるものであり、ポリエーテルポリオール／ポリエステルポリオールの質量比が９５／５〜７５／２５であり、前記ポリエーテルポリオールの主成分がポリテトラメチレングリコールとポリエチレングリコールとの共重合体またはポリプロピレングリコールに特定されたものであり、かかるウレタンプレポリマーは、所定の粘度を有し、環境温度（常温）において常態が液状である。従って、接着剤として使用するためにさらに溶剤を必要とすることなしに、無溶剤系接着剤を提供することができる。 That is, the urethane prepolymer contains 0.01 to 5% by mass of an amine curing accelerator after reacting polyether polyol, polyester polyol and polyisocyanate at an NCO / OH equivalent ratio of 1.1 to 3.0. The polyether polyol / polyester polyol mass ratio is 95/5 to 75/25, and the main component of the polyether polyol is a copolymer of polytetramethylene glycol and polyethylene glycol or polypropylene glycol The urethane prepolymer has a predetermined viscosity and is normally in a liquid state at ambient temperature (normal temperature). Therefore, a solventless adhesive can be provided without the need for additional solvents for use as an adhesive.
また、接着剤として要求される接着強度等の品質性状は、後述の実施例においても示すようにすべて満たしたものである。 Further, quality properties such as adhesive strength required as an adhesive are all satisfied as shown in Examples described later.
なお、接着剤として使用するために、各種の添加剤、例えば、充填剤、可塑剤、安定剤等を所望により添加してもよい。 In addition, in order to use as an adhesive agent, you may add various additives, for example, a filler, a plasticizer, a stabilizer, etc. if desired.
次に、本発明を実施例、参考例および比較例によりさらに詳細に説明する。もっとも、本発明は実施例等によって限定されるものではない。 Next, the present invention will be described in more detail with reference to Examples, Reference Examples and Comparative Examples. However, the present invention is not limited to the examples.
尚、実施例、比較例等において部で表す数値は質量基準である。 In addition, the numerical value represented by a part in an Example, a comparative example, etc. is a mass reference | standard.
また、本発明に係るウレタンプレポリマー、該ウレタンプレポリマーの製造に使用するポリエーテルポリオール及びポリエステルポリオールの数平均分子量はＧＰＣにより測定した。 The number average molecular weights of the urethane prepolymer according to the present invention and the polyether polyol and polyester polyol used for the production of the urethane prepolymer were measured by GPC.
[参考例１]
攪拌機、温度計、ガス導入口などを付与した２リットルのガラス製反応容器にポリプロピレングリコール（数平均分子量２，０００、ＯＨ価５６）６１０部と１，４ブタンジオールとアジピン酸からなる二官能ポリエステルジオール（数平均分子量５００、ＯＨ価２３５）１５２部を仕込み、加熱減圧して脱水処理後、窒素ガスを導入し内温を９０〜１００℃とする。予め加温熔融した４，４′−メチレンビス（フェニルイソシアネート）を２３４部仕込み１００℃で２時間攪拌反応させた。反応終了後４０℃以下に冷却しアミン系硬化促進剤（１，８−ジアザビシクロ（５，４，０）−ウンデセン）３．０部添加し攪拌混合した後に取り出した。
[ Reference Example 1]
Bifunctional polyester consisting of 610 parts of polypropylene glycol (number average molecular weight 2,000, OH value 56), 1,4 butanediol and adipic acid in a 2 liter glass reaction vessel provided with a stirrer, thermometer, gas inlet, etc. A diol (number average molecular weight 500, OH number 235) 152 parts is charged, heated and depressurized, and after dehydration treatment, nitrogen gas is introduced to bring the internal temperature to 90 to 100 ° C. 234 parts of 4,4'-methylenebis (phenylisocyanate), which had been heated and melted in advance, was charged and reacted at 100 ° C for 2 hours with stirring. After completion of the reaction, the reaction mixture was cooled to 40 ° C. or lower, added with 3.0 parts of an amine curing accelerator (1,8-diazabicyclo (5,4,0) -undecene), stirred and mixed, and then taken out.
得られたウレタンプレポリマーの粘度は、９５０ｄＰａ−ｓ／２５℃であった。この物のＮＣＯ／ＯＨ当量比は、１．５４である。 The viscosity of the obtained urethane prepolymer was 950 dPa-s / 25 ° C. The NCO / OH equivalent ratio of this product is 1.54.
[実施例１]
攪拌機、温度計、ガス導入口などを付与した２リットルのガラス製反応容器に二官能ポリエーテルポリオール（ポリテトラメチレングリコールとポリエチレングリコールの共重合ポリエーテルポリオール、数平均分子量１，８００、OH価６２）５８８部と１，４ブタンジオールとアジピン酸からなる二官能ポリエステルジオール（数平均分子量５００、ＯＨ価２３５）１５９部を仕込み、加熱減圧して脱水処理後、窒素ガスを導入し内温を９０〜１００℃とする。２，４−トリレンジイソシアネートを１７６部仕込み１００℃で２時間攪拌反応させた。反応終了後４０℃以下に冷却しアミン系硬化促進剤（１，８−ジアザビシクロ（５，４，０）−ウンデセン）３．０部添加し攪拌混合した後に取り出した。
[Example 1 ]
Bifunctional polyether polyol (polytetramethylene glycol-polyethylene glycol copolymer polyether polyol, number average molecular weight 1,800, OH number 62) was added to a 2 liter glass reaction vessel equipped with a stirrer, thermometer, gas inlet, etc. ) 588 parts, bifunctional polyester diol consisting of 1,4 butanediol and adipic acid (number average molecular weight 500, OH number 235) 159 parts are charged, heated and depressurized, and after dehydration treatment, nitrogen gas is introduced to bring the internal temperature to 90 ˜100 ° C. 176 parts of 2,4-tolylene diisocyanate was added and stirred at 100 ° C. for 2 hours. After completion of the reaction, the reaction mixture was cooled to 40 ° C. or lower, added with 3.0 parts of an amine curing accelerator (1,8-diazabicyclo (5,4,0) -undecene), stirred and mixed, and then taken out.
得られたウレタンプレポリマーの粘度は、１、０５０ｄＰａ−ｓ／２５℃であった。この物のＮＣＯ／ＯＨ当量比は、１．５７である。 The viscosity of the obtained urethane prepolymer was 1,050 dPa-s / 25 ° C. The NCO / OH equivalent ratio of this product is 1.57.
[参考例２]
攪拌機、温度計、ガス導入口などを付与した２リットルのガラス製反応容器にポリプロピレングリコール（数平均分子量２，０００、ＯＨ価５６）７９７部と、１，４ブタンジオールとアジピン酸からなる二官能ポリエステルジオール（数平均分子量２，０００、ＯＨ価５６）４２部を仕込み、加熱減圧して脱水処理後、窒素ガスを導入し内温を９０〜１００℃とする。予め加温熔融した４，４′−メチレンビス（フェニルイソシアネート）を１５７部仕込み１００℃で２時間攪拌反応させた。反応終了後４０℃以下に冷却しアミン系硬化促進剤（１，５−ジアザビシクロ（４，３，０）−ノネン−５）２．８部添加し攪拌混合した後に取り出した。
[ Reference Example 2]
Bifunctional composed of 797 parts of polypropylene glycol (number average molecular weight 2,000, OH number 56), 1,4 butanediol and adipic acid in a 2 liter glass reaction vessel equipped with a stirrer, thermometer, gas inlet, etc. 42 parts of polyester diol (number average molecular weight 2,000, OH number 56) are charged, heated and depressurized, and after dehydration treatment, nitrogen gas is introduced to bring the internal temperature to 90 to 100 ° C. 157 parts of 4,4'-methylenebis (phenylisocyanate) previously heated and melted was added and stirred at 100 ° C for 2 hours. After completion of the reaction, the reaction mixture was cooled to 40 ° C. or lower, added with 2.8 parts of an amine curing accelerator (1,5-diazabicyclo (4,3,0) -nonene-5), stirred and mixed, and then taken out.
得られたウレタンプレポリマーの粘度は、２，０２０ｄＰａ−ｓ／２５℃であった。この物のＮＣＯ／ＯＨ当量比は、１．５０である。
[参考例３]
攪拌機、温度計、ガス導入口などを付与した２リットルのガラス製反応容器にポリプロピレングリコール（数平均分子量２，０００、ＯＨ価５６）６７１部と１，４ブタンジオールとアジピン酸からなる二官能ポリエステルジオール（数平均分子量２，０００、ＯＨ価５６）１６８部を仕込み、加熱減圧して脱水処理後、乾燥窒素ガスを導入し常圧に戻しながら内温を９０〜１００℃とする。予め加温熔融した４，４′−メチレンビス（フェニルイソシアネート）を１５７部仕込み１００℃で２時間攪拌反応させた。反応終了後４０℃以下に冷却しアミン系硬化促進剤（１，５−ジアザビシクロ（４，３，０）−ノネン−５）２．８部添加し攪拌混合した後に取り出した。
The viscosity of the obtained urethane prepolymer was 2,020 dPa-s / 25 ° C. The NCO / OH equivalent ratio of this product is 1.50.
[ Reference Example 3]
Bifunctional polyester consisting of 671 parts polypropylene glycol (number average molecular weight 2,000, OH number 56), 1,4 butanediol and adipic acid in a 2 liter glass reaction vessel equipped with a stirrer, thermometer, gas inlet, etc. 168 parts of diol (number average molecular weight 2,000, OH value 56) are charged, heated and depressurized, and after dehydration treatment, the inside temperature is set to 90 to 100 ° C. while introducing dry nitrogen gas and returning to normal pressure. 157 parts of 4,4'-methylenebis (phenylisocyanate) previously heated and melted was added and stirred at 100 ° C for 2 hours. After completion of the reaction, the reaction mixture was cooled to 40 ° C. or lower, added with 2.8 parts of an amine curing accelerator (1,5-diazabicyclo (4,3,0) -nonene-5), stirred and mixed, and then taken out.
得られたウレタンプレポリマーの粘度は、２，３４０ｄＰａ−ｓ／２５℃であった。この物のＮＣＯ／ＯＨ当量比は、１．５０である。
[参考例４]
攪拌機、温度計、ガス導入口などを付与した２リットルのガラス製反応容器にポリプロピレングリコール（数平均分子量２，０００、ＯＨ価５６）６２９部と１，４ブタンジオールとアジピン酸からなる二官能ポリエステルジオール（数平均分子量２，０００、ＯＨ価５６)２１０部を仕込み、加熱減圧して脱水処理後、乾燥窒素ガスを導入し常圧に戻しながら内温を９０〜１０５℃とする。予め加温熔融した４，４′−メチレンビス（フェニルイソシアネート）を１５７部仕込み１００℃で３時間攪拌反応させた。反応終了後４０℃以下に冷却しアミン系硬化促進剤（１，５−ジアザビシクロ（４，３，０）−ノネン−５）２．８部添加し攪拌混合した後に取り出した。
The viscosity of the obtained urethane prepolymer was 2,340 dPa-s / 25 ° C. The NCO / OH equivalent ratio of this product is 1.50.
[ Reference Example 4]
Bifunctional polyester consisting of 629 parts of polypropylene glycol (number average molecular weight 2,000, OH value 56), 1,4 butanediol and adipic acid in a 2 liter glass reaction vessel provided with a stirrer, thermometer, gas inlet, etc. After adding 210 parts of diol (number average molecular weight 2,000, OH value 56), heating and depressurizing and dehydrating, the inside temperature is set to 90 to 105 ° C. while introducing dry nitrogen gas and returning to normal pressure. 157 parts of 4,4'-methylenebis (phenylisocyanate) previously heated and melted was charged and stirred at 100 ° C for 3 hours. After completion of the reaction, the reaction mixture was cooled to 40 ° C. or lower, added with 2.8 parts of an amine curing accelerator (1,5-diazabicyclo (4,3,0) -nonene-5), stirred and mixed, and then taken out.
得られたウレタンプレポリマーの粘度は、２，６５０ｄＰａ−ｓ／２５℃であった。この物のＮＣＯ／ＯＨ当量比は、１．４９である。 The viscosity of the obtained urethane prepolymer was 2,650 dPa-s / 25 ° C. The NCO / OH equivalent ratio of this product is 1.49.
[比較例１]
攪拌機、温度計、ガス導入口などを付与した２リットルのガラス製反応容器にポリエチレングリコール（数平均分子量２，０００、ＯＨ価５６）６２０部と１，４ブタンジオールとアジピン酸からなる二官能ポリエステルジオール（数平均分子量５００、ＯＨ価２３５）１４８部を仕込み、加熱減圧して脱水処理後、窒素ガスを導入し内温を９０〜１００℃とする。予め加温熔融した４，４′−メチレンビス（フェニルイソシアネート）を２３２部仕込み１００℃で２時間攪拌反応させた。反応終了後４０℃以下に冷却しアミン系硬化促進剤（１，８−ジアザビシクロ（５，４，０）−ウンデセン)３．０部添加し攪拌混合した後に取り出した。
[Comparative Example 1]
Bifunctional polyester composed of 620 parts of polyethylene glycol (number average molecular weight 2,000, OH value 56), 1,4 butanediol and adipic acid in a 2 liter glass reaction vessel provided with a stirrer, thermometer, gas inlet, etc. 148 parts of diol (number average molecular weight 500, OH number 235) are charged, heated and depressurized, and after dehydration treatment, nitrogen gas is introduced to adjust the internal temperature to 90 to 100 ° C. 232 parts of 4,4'-methylenebis (phenylisocyanate) previously heated and melted was charged and stirred at 100 ° C. for 2 hours. After completion of the reaction, the mixture was cooled to 40 ° C. or lower, added with 3.0 parts of an amine curing accelerator (1,8-diazabicyclo (5,4,0) -undecene), stirred and mixed, and then taken out.
得られたウレタンプレポリマーは、２５℃で固体であり、１５０ｄＰａ−ｓ／１００℃
であった。
この物のＮＣＯ／ＯＨ当量比は、１．５３である。
[比較例２]
攪拌機、温度計、ガス導入口などを付与した２リットルのガラス製反応容器にポリプロピレングリコール（数平均分子量２，０００、ＯＨ価５６）６１０部と１，４ブタンジオールとアジピン酸からなる二官能ポリエステルジオール（数平均分子量５００、ＯＨ価２３５）１５２部を仕込み、加熱減圧して脱水処理後、窒素ガスを導入し内温を９０〜１００℃とする。予め加温熔融した４，４′−メチレンビス（フェニルイソシアネート）を２３４部仕込み１００℃で２時間攪拌反応させた。反応終了後４０℃以下に冷却した後に取り出した。
The obtained urethane prepolymer is solid at 25 ° C. and is 150 dPa-s / 100 ° C.
Met.
The NCO / OH equivalent ratio of this product is 1.53.
[Comparative Example 2]
Bifunctional polyester consisting of 610 parts of polypropylene glycol (number average molecular weight 2,000, OH value 56), 1,4 butanediol and adipic acid in a 2 liter glass reaction vessel provided with a stirrer, thermometer, gas inlet, etc. A diol (number average molecular weight 500, OH number 235) 152 parts is charged, heated and depressurized, and after dehydration treatment, nitrogen gas is introduced to bring the internal temperature to 90 to 100 ° C. 234 parts of 4,4'-methylenebis (phenylisocyanate), which had been heated and melted in advance, was charged and reacted at 100 ° C for 2 hours with stirring. After completion of the reaction, the reaction mixture was cooled to 40 ° C. or lower and taken out.
得られたウレタンプレポリマーは、２５℃で９００ｄＰａ−ｓであった。この物のＮＣＯ／ＯＨ当量比は、１．５４である。 The obtained urethane prepolymer was 900 dPa-s at 25 ° C. The NCO / OH equivalent ratio of this product is 1.54.
[比較例３]
攪拌機、温度計、ガス導入口などを付与した２リットルのガラス製反応容器に二官能ポリエーテルポリオール（ポリテトラメチレングリコールとポリエチレングリコールの共重合ポリエーテルポリオール、数平均分子量１，８００、ＯＨ価６２）６７８部を仕込み、加熱減圧して脱水処理後、窒素ガスを導入し内温を９０〜１００℃とする。２，４−トリレンジイソシアネートを１０２部仕込み内温９０〜１００℃で３時間攪拌反応させた。反応終了後４０℃以下に冷却しアミン系硬化促進剤（１，８−ジアザビシクロ（５，４，０）−ウンデセン）３．０部添加し攪拌混合した後に取り出した。
[Comparative Example 3]
A bifunctional polyether polyol (copolyether polyol of polytetramethylene glycol and polyethylene glycol, number average molecular weight 1,800, OH number 62) was added to a 2 liter glass reaction vessel provided with a stirrer, thermometer, gas inlet, and the like. ) 678 parts are charged, heated and depressurized, and after dehydration treatment, nitrogen gas is introduced to bring the internal temperature to 90 to 100 ° C. 102 parts of 2,4-tolylene diisocyanate was charged and the reaction was stirred at an internal temperature of 90 to 100 ° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to 40 ° C. or lower, added with 3.0 parts of an amine curing accelerator (1,8-diazabicyclo (5,4,0) -undecene), stirred and mixed, and then taken out.
得られたウレタンプレポリマーは、２５℃で３４０ｄＰａ−ｓであった。この物のＮＣＯ／ＯＨ当量比は、１．５６である。 The obtained urethane prepolymer was 340 dPa-s at 25 ° C. The NCO / OH equivalent ratio of this product is 1.56.
[比較例４]
攪拌機、温度計、ガス導入口などを付与した２リットルのガラス製反応容器にポリプロピレングリコール（数平均分子量２，０００、ＯＨ価５６）４２０部と１，４ブタンジオールとアジピン酸からなる二官能ポリエステルジオール（数平均分子量５００、ＯＨ価２３５)２７９部を仕込み、加熱減圧して脱水処理後、窒素ガスを導入し内温を９０〜１００℃とする。予め加温熔融した４，４′−メチレンビス（フェニルイソシアネート）を２９８部仕込み９０〜１００℃で２時間攪拌反応させた。反応終了後４０℃以下に冷却しアミン系硬化促進剤（１，５−ジアザビシクロ（４，３，０）−ノネン−５）３．０部添加し攪拌混合した後に取り出した。
[Comparative Example 4]
Bifunctional polyester consisting of 420 parts of polypropylene glycol (number average molecular weight 2,000, OH value 56), 1,4 butanediol and adipic acid in a 2 liter glass reaction vessel provided with a stirrer, thermometer, gas inlet, etc. 279 parts of diol (number average molecular weight 500, OH number 235) are charged, heated and depressurized, and after dehydration treatment, nitrogen gas is introduced to adjust the internal temperature to 90 to 100 ° C. 298 parts of 4,4'-methylenebis (phenylisocyanate), which was previously heated and melted, was charged and stirred at 90-100 ° C for 2 hours. After completion of the reaction, the reaction mixture was cooled to 40 ° C. or lower, 3.0 parts of an amine curing accelerator (1,5-diazabicyclo (4,3,0) -nonene-5) was added, stirred and mixed, and then taken out.
得られたウレタンプレポリマーは、２５℃で９４０ｄＰａ−ｓであった。この物のＮＣＯ／ＯＨ当量比は、１．５５である。
[比較例５]
攪拌機、温度計、ガス導入口などを付与した２リットルのガラス製反応容器にポリテトラメチレングリコール（数平均分子量２，０００、ＯＨ価５５）６１６部と１，４ブタンジオールとアジピン酸からなる二官能ポリエステルジオール（数平均分５００、ＯＨ価２３５)１４９部を仕込み、加熱減圧して脱水処理後、乾燥窒素ガスを導入し常圧に戻しながら内温を９０〜１００℃とする。予め加温熔融した４，４′−メチレンビス（フェニルイソシアネート）を２３５部仕込み１００℃で２．５時間攪拌反応させた。反応終了後４０℃以下に冷却し、アミン系硬化促進剤（１，８−ジアザビシクロ（５，４，０）−ウンデセン）を３．０部添加し攪拌混合した後に取り出した。
The obtained urethane prepolymer was 940 dPa-s at 25 ° C. The NCO / OH equivalent ratio of this product is 1.55.
[Comparative Example 5]
A 2 liter glass reaction vessel provided with a stirrer, a thermometer, a gas inlet, etc., is composed of 616 parts of polytetramethylene glycol (number average molecular weight 2,000, OH value 55), 1,4 butanediol and adipic acid. 149 parts of functional polyester diol (number average 500, OH number 235) are charged, heated and depressurized, and after dehydration treatment, dry nitrogen gas is introduced and the internal temperature is set to 90 to 100 ° C. while returning to normal pressure. 235 parts of 4,4′-methylenebis (phenylisocyanate), which had been heated and melted in advance, was added and stirred at 100 ° C. for 2.5 hours. After completion of the reaction, the reaction mixture was cooled to 40 ° C. or lower, and 3.0 parts of an amine curing accelerator (1,8-diazabicyclo (5,4,0) -undecene) was added and stirred and mixed.
得られたウレタンプレポリマーは、２５℃で固体であり、６３０ｄＰａ−ｓ／１００℃
であった。この物のＮＣＯ／ＯＨ当量比は、１．５５である。
[比較例６]
攪拌機、温度計、ガス導入口などを付与した２リットルのガラス製反応容器にポリプロピレングリコール（数平均分子量２，０００、ＯＨ価５６）６１０部と１，４ブタンジオールとアジピン酸からなる二官能ポリエステルジオール（数平均分子量５００、ＯＨ価２３５)１５２部を仕込み、加熱減圧して脱水処理後、窒素ガスを導入し内温を９０〜１００℃とする。予め加温熔融した４，４′−メチレンビス（フェニルイソシアネート）を２３４部仕込み１００℃で２時間攪拌反応させた。反応終了後４０℃以下に冷却し亜鉛系硬化促進剤（オクチックス亜鉛)３．０部添加し攪拌混合した後に取り出した。
The obtained urethane prepolymer is solid at 25 ° C. and is 630 dPa-s / 100 ° C.
Met. The NCO / OH equivalent ratio of this product is 1.55.
[Comparative Example 6]
Bifunctional polyester consisting of 610 parts of polypropylene glycol (number average molecular weight 2,000, OH value 56), 1,4 butanediol and adipic acid in a 2 liter glass reaction vessel provided with a stirrer, thermometer, gas inlet, etc. After charging 152 parts of diol (number average molecular weight 500, OH number 235), heating and depressurizing and dehydrating, nitrogen gas is introduced and the internal temperature is set to 90 to 100 ° C. 234 parts of 4,4'-methylenebis (phenylisocyanate), which had been heated and melted in advance, was charged and reacted at 100 ° C for 2 hours with stirring. After completion of the reaction, the mixture was cooled to 40 ° C. or lower, added with 3.0 parts of a zinc-based curing accelerator (octix zinc), stirred and mixed, and then taken out.
得られたウレタンプレポリマーの粘度は、９９０ｄＰａ−ｓ／２５℃であった。この物のＮＣＯ／ＯＨ当量比は、１．５４である。 The viscosity of the obtained urethane prepolymer was 990 dPa-s / 25 ° C. The NCO / OH equivalent ratio of this product is 1.54.
実施例１、参考例１，３〜５及び比較例１〜６で得られたウレタンプレポリマーを評価する為に以下の測定を実施した。
〔樹脂性状〕２５℃及び１００℃における粘度を測定した。（ＪＩＳ Ｋ７１１７に準拠）
〔発泡性〕ＰＥＴ上に厚み１００ミクロンになるようにウレタンプレポリマーを塗布し、
温度４０℃、湿度６０%の恒温槽に２４時間放置後のフィルム断面の外観を評価した。
○：均一な発泡層を確認 ×：発泡層は確認できない
〔透湿性試験〕ウレタンプレポリマーを離型紙上に塗布し、温度４０℃、湿度６０％の恒温槽に１６８時間放置後剥離して厚さ１００ミクロンのフィルムを得た。これらのフィルムについてＪＩＳ Ｌ１０９９ Ａ−１法に準じて透湿性を測定した。
〔耐加水分解性〕ウレタンプレポリマーを離型紙上に塗布し、温度４０℃、湿度６０％の恒温槽に１６８時間放置後剥離して厚さ１００ミクロンのフィルムを得た。これらのフィルムについて温度７０℃、湿度９５％条件下で４週間放置後の耐加水分解性試験を行い、試験前のフイルム物性（１００％伸張後のモジュラス）と比較した。
○：保持率８０％以上 △：保持率８０％未満５０％以上
×：保持率５０％未満
〔接着強度（ピール強度［Ｎ／２５ｍｍ］）〕：構成：ＰＥＴ／織布（綿布）
ウレタンプレポリマーをＰＥＴフィル上に１００ミクロン塗工し、直ちに綿布を貼り合せ１ｋｇローラで圧着し、温度４０℃、湿度60％条件下にて７日間養成した後、２５ｍｍ巾の短冊状の測定試料を作成し、３００ｍｍ／ｍｉｎの速度で引張り接着強度を測定した。
In order to evaluate the urethane prepolymers obtained in Example 1, Reference Examples 1, 3 to 5, and Comparative Examples 1 to 6, the following measurements were performed.
[Resin properties] Viscosity at 25 ° C and 100 ° C was measured. (Conforms to JIS K7117)
[Foaming] Apply urethane prepolymer on PET to a thickness of 100 microns,
The appearance of the film cross-section after being allowed to stand for 24 hours in a constant temperature bath at a temperature of 40 ° C. and a humidity of 60% was evaluated.
○: Confirmation of a uniform foam layer ×: No foam layer can be confirmed [Moisture permeability test] A urethane prepolymer is coated on a release paper, left in a constant temperature bath at a temperature of 40 ° C. and a humidity of 60% for 168 hours, and then peeled off. A 100 micron film was obtained. These films were measured for moisture permeability according to JIS L1099 A-1.
[Hydrolysis resistance] A urethane prepolymer was coated on a release paper, left in a constant temperature bath at a temperature of 40 ° C. and a humidity of 60% for 168 hours, and then peeled to obtain a film having a thickness of 100 microns. These films were subjected to a hydrolysis resistance test after being left for 4 weeks under conditions of a temperature of 70 ° C. and a humidity of 95%, and compared with film physical properties before the test (modulus after 100% elongation).
○: Retention rate 80% or more Δ: Retention rate less than 80% 50% or more X: Retention rate less than 50% [Adhesive strength (peel strength [N / 25 mm])]: Composition: PET / woven fabric (cotton fabric)
A urethane prepolymer is coated on a PET film with a thickness of 100 microns, a cotton cloth is immediately bonded, and a 1 kg roller is pressed, and after 7 days of culturing at a temperature of 40 ° C. and a humidity of 60%, a strip-shaped measurement sample having a width of 25 mm is obtained. The tensile adhesive strength was measured at a speed of 300 mm / min.
前記の実施例及び比較例の各ウレタンプレポリマーの成分配合割合及び性能評価結果を表−１にまとめた。 Table 1 summarizes the component blending ratios and performance evaluation results of the urethane prepolymers of the above Examples and Comparative Examples.
前記の通り、実施例及び比較例の結果から、明らかなように、本発明に係るウレタンプレポリマーは接着強度、樹脂性状、透湿性、発泡性および耐加水分解性等の要求品質性状すべてを満たすことができる。 As described above, as is clear from the results of Examples and Comparative Examples, the urethane prepolymer according to the present invention satisfies all required quality properties such as adhesive strength, resin properties, moisture permeability, foamability, and hydrolysis resistance. be able to.
本発明のウレタンプレポリマーは、接着剤、塗料、シーリング材料などの多方面の分野において用いることができ、有用な材料として産業上の利用可能性は極めて高い。 The urethane prepolymer of the present invention can be used in various fields such as adhesives, paints, and sealing materials, and has a very high industrial applicability as a useful material.
Claims (8)
The urethane prepolymer according to claim 4 , which has a viscosity of 3000 dPa · s / 25 ° C or lower and 50 Pa · s / 25 ° C or higher.
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| TW099145694A TWI508988B (en) | 2010-02-26 | 2010-12-24 | Amine ester prepolymer |
| CN201010618525.3A CN102167794B (en) | 2010-02-26 | 2010-12-31 | Polyurethane prepolymer |
| KR1020110001893A KR101514107B1 (en) | 2010-02-26 | 2011-01-07 | Urethane Prepolymer |
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| US20140005329A1 (en) * | 2011-05-24 | 2014-01-02 | The Yokohama Rubber Co., Ltd. | Urethane Resin Adhesive Composition |
| CN103508074B (en) * | 2012-06-26 | 2016-03-16 | 层层包装事业股份有限公司 | Packaging for foodstuff material |
| CN105288631B (en) * | 2015-11-17 | 2018-10-30 | 杭州普施康生物科技有限公司 | A kind of new anticancer drug nanometer formulation and preparation method thereof |
| CN106519448A (en) * | 2016-11-21 | 2017-03-22 | 郑州源冉生物技术有限公司 | Environment-friendly foamed plastic and preparation method thereof |
| CN106496797A (en) * | 2016-11-21 | 2017-03-15 | 郑州源冉生物技术有限公司 | A kind of foam plasticss and preparation method thereof |
| JP6323580B1 (en) * | 2017-02-14 | 2018-05-16 | 東洋インキＳｃホールディングス株式会社 | Adhesive and adhesive sheet |
| CN109456462A (en) * | 2018-10-29 | 2019-03-12 | 中海油能源发展股份有限公司 | For the composition of polyurethane foam, polyurethane foam and preparation method and purposes |
| CN111320930A (en) * | 2020-04-09 | 2020-06-23 | 武汉仕全兴聚氨酯科技有限公司 | Solvent-free polyurethane moisture curing coating and preparation method thereof |
| CN111690360B (en) * | 2020-06-22 | 2023-03-03 | 万华化学（北京）有限公司 | Reactive moisture-curing polyurethane hot melt adhesive and preparation method thereof |
| CN114806359A (en) * | 2021-01-29 | 2022-07-29 | 海洋化工研究院有限公司 | Durable universal colorful road surface antiskid coating and preparation method thereof |
| CN118344723B (en) * | 2024-05-14 | 2024-10-18 | 昆山红苹果塑胶新材料有限公司 | TPU film with moisture permeability and processing technology thereof |
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| JPH08199142A (en) * | 1995-01-20 | 1996-08-06 | Sekisui Chem Co Ltd | One pack-type solventless reaction type urethane-based adhesive and floor structure |
| JP3447555B2 (en) * | 1998-03-17 | 2003-09-16 | コニシ株式会社 | One-part moisture-curable urethane liquid adhesive composition |
| WO2001053423A1 (en) * | 2000-01-19 | 2001-07-26 | Sunstar Giken Kabushiki Kaisha | Moisture-curable one-pack-type urethane adhesive composition |
| CN1322085C (en) * | 2005-09-21 | 2007-06-20 | 北京高盟化工有限公司 | Single-copmonent no-solvent polyurethane adhesive for low temperature painting and its prepn process |
| EP2025730B1 (en) * | 2006-12-01 | 2014-04-16 | DIC Corporation | Moisture-curable polyurethane hot melt adhesive and multilayer sheet using the same |
| CN101319129A (en) * | 2007-06-08 | 2008-12-10 | 上海精细文化用品有限公司 | Single-component solvent-free damp solidifying polyurethane adhesion agent and method of producing the same |
| CN101629061B (en) * | 2008-07-14 | 2013-06-05 | 上海新光化工有限公司 | Monocomponent moisture cure urethanes adhesive |
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| CN102167794B (en) | 2015-05-06 |
| TWI508988B (en) | 2015-11-21 |
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| CN102167794A (en) | 2011-08-31 |
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