CN1129241A - 水基、无溶剂或低挥发性双成分聚氨酯涂料 - Google Patents
水基、无溶剂或低挥发性双成分聚氨酯涂料 Download PDFInfo
- Publication number
- CN1129241A CN1129241A CN95118432A CN95118432A CN1129241A CN 1129241 A CN1129241 A CN 1129241A CN 95118432 A CN95118432 A CN 95118432A CN 95118432 A CN95118432 A CN 95118432A CN 1129241 A CN1129241 A CN 1129241A
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- Prior art keywords
- polyol
- acid
- amine
- composition according
- polyols
- Prior art date
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- 239000002904 solvent Substances 0.000 title abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 70
- 239000011527 polyurethane coating Substances 0.000 title description 6
- 229920005862 polyol Polymers 0.000 claims abstract description 230
- 150000003077 polyols Chemical class 0.000 claims abstract description 224
- 239000000203 mixture Substances 0.000 claims abstract description 129
- 150000001412 amines Chemical class 0.000 claims abstract description 126
- 239000002253 acid Substances 0.000 claims abstract description 84
- 239000006185 dispersion Substances 0.000 claims abstract description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 30
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 27
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 24
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 16
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 239000008199 coating composition Substances 0.000 claims abstract description 4
- 239000012071 phase Substances 0.000 claims description 45
- 230000002378 acidificating effect Effects 0.000 claims description 44
- -1 aliphatic tertiary amine Chemical class 0.000 claims description 39
- 239000012948 isocyanate Substances 0.000 claims description 37
- 150000002513 isocyanates Chemical class 0.000 claims description 31
- 229920005906 polyester polyol Polymers 0.000 claims description 30
- 239000007795 chemical reaction product Substances 0.000 claims description 27
- 150000002009 diols Chemical class 0.000 claims description 23
- 150000008064 anhydrides Chemical class 0.000 claims description 21
- 229920000570 polyether Polymers 0.000 claims description 16
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
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- 150000002148 esters Chemical class 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 150000004072 triols Chemical class 0.000 claims description 7
- 229920001281 polyalkylene Polymers 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- 150000004984 aromatic diamines Chemical class 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 229920000768 polyamine Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 5
- 229920005903 polyol mixture Polymers 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 239000004435 Oxo alcohol Substances 0.000 claims description 3
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims 2
- 229920006243 acrylic copolymer Polymers 0.000 claims 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 1
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- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 claims 1
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- 238000000034 method Methods 0.000 description 23
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 229920002396 Polyurea Polymers 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
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- 150000007513 acids Chemical class 0.000 description 15
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 239000004094 surface-active agent Substances 0.000 description 11
- 239000013638 trimer Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 9
- 229920003009 polyurethane dispersion Polymers 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 239000013530 defoamer Substances 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000004970 Chain extender Substances 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920006264 polyurethane film Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011253 protective coating Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012963 UV stabilizer Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
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- 235000011187 glycerol Nutrition 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
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- 230000003472 neutralizing effect Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
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- NONOKGVFTBWRLD-UHFFFAOYSA-N thioisocyanate group Chemical group S(N=C=O)N=C=O NONOKGVFTBWRLD-UHFFFAOYSA-N 0.000 description 3
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- OPCJOXGBLDJWRM-UHFFFAOYSA-N 1,2-diamino-2-methylpropane Chemical compound CC(C)(N)CN OPCJOXGBLDJWRM-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种基本无溶剂的水性双成分涂料组合物分散体,涂于基体后固化成膜的粘附性和粘合性等于或优于常规溶剂基双成分聚氨酯或环氧体系得到的膜。其第一成分是结合的水性多醇相和胺相。多醇相选自酸性多醇或含酸多醇的多醇混合体,其平均羟基官能度至少为1.5且酸值为15-200。胺相是含有与NCO基团反应的活性氢的胺或胺混合体,其活性氢官能度至少1.5。第二成分选自脂族聚异氰酸酯,脂环族聚异氰酸酯和芳族聚异氰酸酯及其加合物和混合物。
Description
本申请是93.3.10提交申请号为08/028966的后续申请,该申请已受理并共同待批,本文结合参照。
本发明涉及水基无溶剂双成分聚氨酯保护性涂料。本发明具体涉及水基无溶剂双成分脂族交联聚氨酯-聚脲保护性涂料体系,该体系具有的特性性能等于或优于常规的溶剂基双成分聚氨酯或聚氨酯-聚脲体系的性能。
水性的或水基聚氨酯已存在40多年了。在此期间于水性的聚氨酯领域已颁布近百件专利以改良这些体系的性能。
近年来至少有三个重要的理由要使水性聚氨酯具有商业意义。第一个理由是环境问题,考虑到溶剂和其他挥发性有机化合物(“VOC”)将散发进入大气并造成臭氧层贫化,酸雨和地球大气(ecosphere)可能的化学不平衡。第二个理由是经济上的原因,有机溶剂体系价格高昂,而水性聚氨酯却不需要溶剂成本。第三个理由,或许最重要,涉及到这样的事实,即水性聚氨酯可被改良成,就其性能而言,在许多专门应用中可相媲美或大大优于常规溶剂基聚氨酯。
水性聚氨酯通常实际上是大分子链上含有亚胺酯基(-NH-CO-O-)和脲基(-NH-CO-NH-)两者的聚氨酯-聚脲聚合物。这些基团是熟知的加聚反应生成的。聚异氰酸酯和多元醇(多醇)之间的加成反应生成亚胺酯基,可描述如下: 。
在聚异氰酸酯和胺之间生成脲基的类似加聚反应,表示如下: 。
最普遍的水性聚氨酯有个共同的制造工艺。在生产的第一阶段,中间分子量的‘预聚物’在反应器内以高温度(60-100℃)合成留下大约2%-8%的游离/终端未反应的异氰酸基(-NCO)。为使这种类型的聚氨酯具有高性能特性,例如柔韧性、硬度、耐酸、耐溶剂和其他化学特性,必须在水相中进行链扩展。链扩展相是预聚物成为高分子量聚氨酯所产生的。
这种高分子量形成物通常通过预聚物的NCO基与胺反应来实现。在这个反应过程期间必须涉及两个重要的问题:(1)控制或稳定特别快形成脲的反应,(如 ),和(2)将增加分子量所至而来的粘度增加来进行控制或减至最小。由于这个原因,目前工艺水平的水性脂族聚氨酯分散物限制到固体含量为40%或更低。并且它们的耐溶剂性(以甲乙酮“MEK”双向摩擦来测量)也通常限制在最大值为200-250次摩擦,且它们的耐化学物的特性诸如耐skydrol(喷气发动机液压油)或喷气发动机燃料的特性非常差。
为解决涉及粘度(低固体分散含量)和高性能、耐溶剂和化学物的问题,已致力于试图改良水性聚氨酯分散物,方式是在中间体作溶剂中进行反应来控制在临界链扩展阶段的粘度增加。这些工艺的代表是所谓的“丙酮”或“NMP”(N-甲基吡咯烷酮)工艺。
按照这种类型的工艺,多醇与二异氰酸酯反应生成预聚物。然后,在诸如丙酮或NMP溶剂的存在下,将预聚物与增链剂进行反应,增链剂诸如聚胺,如乙二胺或二乙三胺。然后将溶剂基扩展的氨基甲酸乙酯聚合物用水稀释形成氨基甲酸乙酯预聚物的水分散体,脂族胺链扩展的氨基甲酸乙酯聚合物和溶剂。之后必须以蒸馏去除溶剂,产生氨基甲酸乙酯的水性分散体,氨基甲酸乙酯含有的成分范围从预聚物直到最高分子量脂族胺链扩展的聚氨酯。
在这个工艺中,溶剂必须从体系蒸馏出去,仍导致伴随所得溶剂的处理问题。这不是适用的解决办法,这个工艺的商业应用相当少。
制备水性聚氨酯最大众化的工艺是所谓的“预聚物结合工艺”该工艺利用含有NCO-游离端基的亲水改性预聚物,该端基与水系更相容。这些具有亲水性预聚物与溶剂相比,在水相因而更易于与二胺进行链扩展,该水相有助于形成扩展分子量的聚氨酯聚合物,并进一步增强特性性能。
为使亲水性预聚物结合/混合工艺的最佳化,必须在尽可能短的时间周期内形成分散相,而且温度要低于临界点,该临界点即NCO快速与水开始反应形成氨基甲酸基团并随后放出二氧化碳。为使该工艺最佳化,在链扩展和或交联相期间常常需要使用5%-15%w。浓度的共溶剂如NMP来调节增加粘度。这个工艺利用了水相链扩展,结果导致预聚物既可与双官能基的胺类反应生成直链的、柔韧的聚氨酯-脲,又可与产生交联体系的多官能胺类进行交联反应。交联类型的水性聚氨酯含有离子和非离子内乳化剂的结合体。和丙酮制备的薄膜相比,本工艺得到的固化聚氨酯薄膜在与多官能胺类交联时展现改良的耐溶剂性。尽管这个类型工艺及其变体是改良体系,其固化得到的薄膜差不多总是不及双成分溶剂基脂族全交联空气干燥的聚氨酯薄膜。可以认为,这是由于水基链扩展是在不均匀相中进行,因而不如在有机溶剂体系发生的那样顺利或定量地进行,尤其是双成分全交联体系。
从溶剂基双成分制备全交联脂族聚氨酯时,具有的特性性能远远优于任何目前的水基或水性制备的聚氨酯的性能。这些溶剂基双成分全交联脂族聚氨酯可以配制而产生固化的薄膜,该薄膜浸没在skydrol(喷气发动机液压油)中可耐受30天,还可抗双向MEK摩擦超过1000次。这种溶剂基体系绝对不含有外来水,并且含有非常低的湿气成分。
已作了大量工作来改良水基聚氨酯的耐溶剂及耐化学酸性。例如,使用者利用多氮丙烷(polyaziradines)对分散体进行后处理,对分散体使用嵌段NCO加合物以及利用烘烤固化,由于温度升高可进一步交联,所有这些皆导致来自水分散体的改良固化薄膜。另个办法是用其他类型的聚合物代替部分常用的聚氨酯。这常常形成含有主链接枝丙烯酸酯或乙烯基单体的水体系。但是,这种接枝聚合物不是100%的聚氨酯,其某些方面的性能测量仍然达不到溶剂基双成分聚氨酯薄膜的性能。
现有技术的含水氨基甲酸乙酯制备工艺的代表是Schriven等人的US4066591。用水基聚氨酯遇到的许多问题在该文献内有所叙述。此外,这篇说明书某些详述部分叙述了各种类型的异氰酸酯、多醇、含有活性氢原子的化合物、增链剂等,这些都可用来制备聚氨酯薄膜和涂料。为此,这篇说明书和定义内容在此结合参照。
水性聚氨酯领域最新最好的综述文章见Rosthauser等人“Waterborne Polyurethsanes”,J.Coated Fabrics;Vol.7月16日,1986,39-79页。
将聚酯-多醇和异氰酸酯加热制备水聚氨酯分散体见Hille等人的US4945128。在这篇公开的工艺中,优选制备水分散体的方式是,使用可混溶水的有机溶剂,诸如丙酮或甲乙酮(MET),它们在低于100℃沸腾以溶解或分散聚酯-多醇和异氰酸酯。加热分散体会造成多醇和NCO基团反应生成亚胺酯。加热工艺之前或加热这些成分期间要在较低温度将溶剂蒸馏出去。无论如何,得到的产品是交联微粒状的分散体,据说适宜各种基体的涂覆。
还有其他专利涉及双成分涂料组合物,包括用某种方法在水环境中将酸性聚酯-多醇与聚异氰酸酯相结合,以形成聚氨酯涂料。某些是先与一种异氰酸酯结合生成聚氨酯预聚物。例如,Nachtkamp等人的US4608413告诉我们含有颜料或填料的水烘干型漆(1aquers)。这些是基于含有部分或全部中和的羧基基团和嵌段异氰酸酯基团聚氨酯预聚物和含有游离羟基基团和部分或全部中和的羧基基团的聚氨酯预聚物。
Kubitza等人的US5075370公开了双成分含水涂料组合物,包括含有至少一个羟基的酸性多醇、含有一个羧基或磺酸基的聚合物和聚异氰酸酯的结合体。
Blum等人的US5331039涉及水基粘合剂组合物,包括至少两个羟基官能团的多醇的混合物,每个多醇都含有一个酸性官能团。有机聚异氰酸酯在酸性多醇的混合物中被乳化,例如NCO∶OH的当量比在0.2∶1-5∶1之间。
共同申请,93年3月10日提交已被受理待批,系列号08/028966,公开了一种水基无溶剂双成分的聚氨酯-聚脲分散体,包括高达65%的固体。第一种成分是聚酯-多醇相和水胺相的混合物。聚酯-多醇相是一种结合体,含有改进的聚酯-多醇,低粘度聚醚或聚酯-多醇,链扩展的低分子量多醇,中和胺类和洗涤剂。胺相也是一种结合体,含有中和的和链扩展的胺类,具有预先配制的比例以便得到水相中与-NCO反应基团相平衡的链扩展交联反应。聚酯-多醇和胺相于室温在水中结合,生成的水相成分含有33-48%的固体含量,并且聚酯-多醇相和胺相之间的当量比为1.75∶1-2.25∶2之间。第二种成分是100%的反应性脂族异氰酸酯,具有的粘度于25℃在1000-3500cps之间,并在聚酯-多醇/胺成分比例为大约1∶1.3-1∶1.7之间的条件下可提供NCO基团加到官能基团上。这个无溶剂分散体干燥成薄膜涂料具有的性能等于常规溶剂基聚氨酯涂料性能。由这种双成分分散体得到的聚氨酯涂料,其特性性能优于现有技术水基组合物的,等于或超过相应的溶剂基体系的。这种聚酯-多醇和胺相是许多成分制成一种混合物,每一种成分对聚氨酯涂料的高特性性能都有贡献,性能举例如硬度,耐溶剂性,耐气候性和耐磨损性等。
人们总是期望配制这样一种水基聚氨酯分散体,其涂料性能类似于或大大优于系列号为08/028966的共同申请所要求保护的涂料性能,而且不需要另外添加单独的洗涤剂成分,其中的多醇相和胺成分可被简化及更易于制备和结合,这是合乎需要的。本发明公开和要求保护的就是这种组合物及其用途。
本发明的一个目的是提供水基的,无或低VOC的双成分聚氨酯-聚脲分散体,该分散体是全交联并在水中链扩展的,它没有或基本没有挥发性有机化合物或溶剂,具有优异的涂料性能。
本发明还有一种目的是提供水基的、无溶剂的双成分聚氨酯-聚脲分散体的一种制备方法,该分散体是用于基体涂覆的,是全交联并在水中同羟基和/或胺的官能基团与脂族、脂环族或芳香族异氰酸酯反应进行链扩展,且在扩展期间是稳定的。
本发明的另个目的是提供水基的,无或低VOC的双成分聚氨酯-聚脲分散体,它不需要存在另外的洗涤剂。
本发明另个不同的目的是提供水基的双成分聚氨酯-聚脲分散体,它基于酸性多醇,存在或不存在另外的多醇的条件下,与胺的反应,胺起中和酸性多醇和具有反应性氢官能度的双重作用,还起增链剂和/或交联剂的作用。
本发明另个目的是提供链扩展的聚氨酯-聚脲聚合物分散体,它含有高固体含量却具有低粘度性质而不需要使用有机溶剂。
本发明的另个目的是提供水基的,无溶剂双成分聚氨酯-聚脲分散体,将其涂覆基体,固化成的薄膜具有的粘附性和粘合性等于或优于常规溶剂基双成分聚氨酯或环氧体系得到的薄膜性能。
利用双成分无溶剂体系可达到这些和其他目的。第一种成分是在水相中将两种成分混合而成的。第一种成分是多醇相,选自酸性多醇,酸性多醇聚合物,非酸性多醇和酸性多醇聚合物的结合物,非酸性多醇聚合物和酸性多醇聚合物的结合物以及这些结合物的混合物。第二种成分是水胺相。应当注意,多醇相可以是单一的成分或各种单体与聚合的多醇的混合体,唯一的限制是多醇相具有的平均羟基官能度至少为1.5且酸数量在大约15-200之间。胺相可是单一的胺或含有可与NCO基团反应的活性氢的胺类结合体,胺或胺类结合体的平均活性氢官能度为至少1.5或更大。要有足够量的胺或胺类结合体存在,以便基本中和多醇相的酸数。
多醇可以是各种成分或各种成分的结合体,条件是满足上述要求。例如,多醇可被选自下列的酸物组组分官能化,它们是:含有一.个酸基的聚酯二醇,多羟基聚醚和二羧酸或其酐的反应产物,亚乙基化不饱和酸、亚乙基化不饱和醇和亚乙基化不饱和酯的反应产物。
优选酸性多醇是含有酸基的聚酯二醇,其中的酸官能团既可是羧酸也可是磺酸。可配置各种结合体提供到聚酯二醇上。例如选自下面的组员:(a)二元醇、三元醇和二羧酸及其酐的反应产物;(b)二元醇、二羧酸和三元羧酸及其酐的反应产物;(c)多元醇和二羧酸及其酐的反应产物和(d)含有三个侧基官能团芳香酸的多醇类诸如二羧基苯磺酸酯化得到的那些。特别优选的是酸性聚酯二醇,其中至少部分酸官能团以α,α-二甲醇链烷醇酸存在,化学式为:其中R是含有1-8个碳原子的烷基。
酸性多醇可以是单一成分或者以酸性多醇混合体形式存在,条件是多醇相具有的酸数在大约15-200之间。
优选的多元醇是酸性多元醇类和选自下面物组其他成员的混合体:单体多醇选自于二醇,三醇,高级多官能团醇,含氧醇及其混合物;聚多元醇选自于聚酯多醇,聚醚多元醇,聚酰胺多醇,聚酯酰胺多元醇,聚己酸内酯多醇和丙烯酸内聚多元醇及其混合物;以及单体的和聚合的多元醇混合物或掺合物。
总的多元醇相具有至少1.5的羟基官能度且酸数在15-200之间。
关于多元醇或酸性多元醇成分,羟基(OH)官能团可用巯基(SH)官能团来代替,羧酸基可用磺酸基取代或替代,只要它合乎这个唯一限制要求使多醇或酸性多醇成分切实可实用于所需的目的要求。
各种胺或胺掺合物皆可使用,附加条件是它们必须含有活性氢可与NCO基团反应,且使得总的胺或胺混合体的平均活性氢官能度至少为1.5或更大,胺的量以足量存在以便基本中和多醇的酸官能团。
合适的胺或胺混合体包括选自下面的物组成份:伯的和仲的脂族、脂环族和芳族胺;叔的脂族胺;链烷醇胺,二链烷醇胺,三链烷醇胺;多胺选自脂族,脂环族和芳族的二胺,三胺和四胺;氧亚烷基胺,聚亚烷基二胺和聚氧亚烷基三胺及其混合物。当存在不含活性氢的叔胺时,整个胺相仍必须符合至少1.5的活性氢官能度的要求。
中和的多元醇和胺混合体在水相于环境温度下形成,导致多元醇/胺水相组份具有的固体含量在大约25-65%(重量)之间。
这种中和的多元醇/胺混合体在水相完全混容和/或分散,并不需另加洗涤剂或表面活性剂就得到均匀的水性混合物。然而这不是说如需要时不能添加洗涤剂和/或者表面活性剂。
第二种成分基本是100%的固态脂族,环脂族或芳族异氰酸酯或者各种脂族,环脂族和/或芳族异氰酸酯的混和物。异氰酸酯当量与多醇和胺的活性氢当量之和的比例至少为0.5∶1,但优选更大的值。
优选使用酸性多醇或含有酸性多醇成分的多醇混合体作为多醇相,其中多醇相具有至少为2的平均羟基官能度和大约15-200之间的酸数。多元醇/胺混合体的平均活性氢官能度优选至少为2,并且NCO当量与活性氢当量之和的比例至少是1.1∶1。换言之,优选使所用的异氰酸酯的量应能足够对在多醇/胺成分中的官能团提供超过指数的-NCO基团,以便保证足够的-NCO基使得在聚氨酯-聚脲结构内进行最大的链扩展和交联。
第一和第二种成分可简单搅拌就能结合得到固体含量高达65%的聚氨酯-聚脲分散体,随后完全交联有几个小时的适用期。多元醇和胺相的混合体可配伍,使得异氰酸酯前体优选趋于在水相与多醇及胺反应而不是与水反应。优选方案中,多元醇和胺成分可选择地反应,使之在水相中与-NCO基团的反应能得到最佳化的选择生反应,生成紧密交联的聚合物网络结构。混合后混合物的适用期高达几小时。这种没有或低有机溶剂成分的工艺可生成聚氨酯-聚脲产物,其于环境温度下完全固化后得到的交联薄膜所具有的特性性能等于或优于溶剂基双成分聚氨酯的。
这些水基无溶剂双成分脂族聚氨酯-聚脲薄膜形成的涂料可耐30天的Skydrol浸没,耐受1500次双向MEK摩擦并有优良的粘附性,和它们溶剂基对应物相比,这是由于它们的键合结构所致。而且,加入异氰酸酯后,这种水体系可达到固体含量高达大约75%重量而不存在增加粘度伴随的问题。按照本发明的一般分散体,具有的固体含量在35-75%之间,且粘度适合于一般涂料的涂覆方法。固体含量可以降低,用日常自来水(如果需要或用去离子水)稀释低至大约35%仍具效果。
由于低容量或没有挥发性的有机溶剂(VOCs),实际上没有环境污染,再结合其特性性能,则使它成为真正的优异产品。
下面详述本发明及本发明实践中最好的方式。显然,阅读本文所公开的的内容以后可采取其它等效措施或方法来达到这种双成分无溶剂聚氨酯/聚脲分散体的要求。
即使不完全理解科学术语,本发明方法的基础是异氰酸酯基团与活性氢基团优选反应而不是与水反应。下一个反应是与多元醇和胺的反应,结果产生线性和交联聚合反应。
这个体系基本由双成分混合物混和在一起构成,第一种成分包括多醇相的水混合体和胺或胺类混合体,多醇相具有至少为1.5的平均羧基官能度和15-200之间的酸数,胺具有的活性氢官能度至少1.5,第二种成分包括脂族,环脂族或芳族异氰酸酯。
应当注意,多元醇和反应胺组分的普通性能是,它们两者必须含有“活性”氢原子。术语“活性氢原子”指的是氢,由于它们在分子中的位置而能按照Zerewtinoff试验起活性作用。因此,活性氢包括连接到氧、氮或硫的氢原子,因而有用的化合物包含有以适当方式结合的:-OH,-SH,-NH和-NH2基团。
OH和SH官能团性能近似,因之可包括在本文的术语诸如“二醇”或“羟基”之内。换言之,硫醇和巯基包括在上述术语之内。通过每个“活性氢原子”经氧或硫而连接的烃或取代烃可是脂族,脂环族,芳族或其中不含有羰基,磷酰基或磺酰基的键合的混和型。多元醇:
多元醇/胺混合体的多元醇相部分必须具有至少1.5的羟基官能度和大约15-200之间的酸数。如果需要,多醇相可由100%重量的酸性的多醇成分构成,但优选的是酸性多醇和非酸性多醇成分的混合体。多元醇相可包括这样的成分或这些成分的混和物,使多醇相具有平均至少1.5而优选为2的羟基官能度和大约15-200之间的酸数。
涉及酸性多元醇成分或成分类时,所用术语“酸性多元醇”,“含酸多元醇”或“酸性多醇成分”或者任何的类似相的含义包括酸性多元醇成分,其能保证总的多醇相具有大约15-200之间的酸数。含酸多元醇可以是酸性二醇单体或者是其中结合有酸性官能团的聚合主链,下面将进一步说明。
多元醇的酸官能度的存在对本发明的作用是必不可少的。当酸被含有活性氢官能度的胺相中和时,使羧酸盐(或磺酸盐)离子化,使得各成分成为水溶解性或分散性,还对异氰酸酯提供活性氢与之反应生成含有聚脲基团的高聚物。由于这个原因,多醇相的酸数必须在大约15-200范围内。
酸性多醇可以各种方式被制成。在一个实施方案中,含酸多醇包括多羟聚醚和二元羧酸或其酐的反应产物。
任何合适的多羟聚醚或聚亚烷基醚多醇都可使用,包括具有以下化学式的那些:
H-[-O-(CHR)n-]m-OH其中取代基R是氢或低级烷基,包括混和的取代基,n通常是2-6而m则从2至100甚至更大。被包括的有聚氧四亚甲基二醇,聚氧亚乙基二醇,聚丙二醇以及乙二醇与环氧乙烷和环烷丙烷混和物的反应产物。
也可使用通过各种多醇经烷氧基化得到的聚醚多醇,例如二醇类如乙二醇,1,6-己二醇,双酚A以及类似物,或高级多醇如三羟甲基丙烷,季戊四醇和类似物。如所表述过的可利用的较高官能度的多醇制备方法是如通过诸如山梨糖醇或蔗糖的化合物进行烷氧基化而得到。常规使用的烷氧基化的方法是使用多元醇与烯化氧反应,例如环氧乙烷或环氧丙烷在酸性或碱性催化剂条件下进行。
除了聚氧化烯基二醇之外,任何合适的多羟聚硫醚也可使用,例如,硫二醇的缩合产物,或者多羟基醇的反应产物诸如本文在制备羟基聚酯时所公开的用硫二醇或其他任何合适二醇制备。
这些多羟基聚醚可与多元羧酸或其酐起反应。合适的多元羧酸是低分子量的多元羧酸或其酐,含有大约2-18之间的碳原子,例如草酸,丁二酸,富马酸,苯二甲酸,间苯二甲酸,对苯二甲酸,四氢苯二甲酸,六氢苯二甲酸,己二酸,壬二酸,癸二酸,马来酸,戊二酸,六氯壬二酸,四氯苯二甲酸,偏苯三酸,丙三羧酸以及它们存在的酐。
另个实施方案中,含酸多元醇包括乙烯基不饱和酸,乙烯基不饱和醇和乙烯基化不饱和酯的反应产物。乙烯基化不饱和酸的羟基化烷基酯举例,如单丙烯酸或甲基丙烯酸的二醇所衍生的含羟基基团产物,诸如羟烷基丙烯酸酯或甲基丙烯酸酯。实例包括乙二醇和1,2-丙二醇的丙烯酸和甲基丙烯酸酯,诸如丙烯酸和甲基丙烯酸羟乙酯,甲基丙烯酸羟丙酯,以及单丙烯酸聚乙二醇酯和单丙烯酸聚己酸内酯二醇酯或多醇单丙烯酸酯。丙烯酸羟丁酯,甲基丙烯酸羟辛酯等是乙烯基化不饱和酸羟烷基酯的另些实例。也可使用这些不饱和酸的含羟基酯,不饱和酸举例如马来酸,富马酸,衣康酸等。羟烷基酯的分子量一般在大约100-1500范围之间,优选大约100-1000。
与羟烷基酯内聚的乙烯基化不饱和酯可以是任何与羟烷酯共聚的乙烯基化不饱和酯,这种聚合是通过乙烯基化不饱和键发生的。这些包括不饱和有机酸的酯,不饱和酸酰胺及酯,不饱和酸腈等。这些单体的实例包括甲基丙烯酸甲酯,丙烯酰胺,丙烯腈,马来二甲酯及其混合物和类似物。
合适的乙烯基化不饱和酸包括丙烯酸,甲基丙烯酸,丁烯酸,异丁烯酸,山梨酸,肉桂酸,马来酸,富马酸及其存在的酐,如马来酸酐。
羟基化烷基和烷基的甲基丙烯酸酯实例可以是它们与甲基丙烯酸的结合,生成酸性多元醇。
优选含酸多醇,它们是含羧酸或磺酸基团的聚酯多醇。
制备聚酯多醇可用有机多元羧酸或其酐与有机多醇进行聚酯化反应。多羧酸和多元醇通常是脂族或芳族二元酸和二酯,但三官能团酸和三元甚至更高元的多醇也可使用。
制备聚酯时通常采用的二醇包括亚烷基二醇如乙二醇和丁二醇,新戊二醇和其他二醇类,如氢化双酚A,环己二醇,环己二甲醇,己内酯二醇(如己内酯与乙二醇的反应产物),羟烷基化双酚类,聚醚二醇(如聚氧四甲基二醇)等。然而其他各种类型的二醇,已所述那样,更高官能度的多醇类也可使用。这些高级多醇包括,例如三甲醇丙烷,三甲醇乙烷,季戊四醇等,以及更高分子量的多醇,诸如通过低分子量多醇进行烷氧基化得到的那些(如环氧乙烷和三甲醇丙烷以大约10∶1-30∶1摩尔比时的反应产物)。
用以生成聚酯多醇的多羧酸及其酐和以上确定的与多羟基聚醚反应时所用那些相同。
有各种多元醇和酸的结合物可反应生成酸性多元醇。一种实施方案中,包括二羟多醇,三羟多醇和二羧酸及其酐的反应产物,例如己二醇,三甲醇丙烷和己二酸的反应产物。
第二个方案中包括二羟多醇,二羧酸和三羧酸及其酐的反应产物,例如己二醇,已二酸和偏苯三酸的反应产物。
还有另个方案包括多羟醇和二羧酸及其酐的反应产物,例如甘油和己二酸的反应产物。
仍有不同方案包括含酸聚酯/含磺酸侧基的多醇,例如己二醇,己二酸和2,4-二羧基苯磺酸的反应产物,其中通过羧酸基团发生酯化。
本发明对任何实用酸性多醇都不限制,因为可使用酸性多醇的结合体。
一般优选使用一种或多种酸性多醇与其他非酸性多醇混合的结合物,以得到具有最佳特性性能的多醇混合物。
术语多醇包括低分子量的二醇,三醇和更高级的醇,低分子量的含酰胺多醇和更高级的聚合多醇,如聚酯多醇,聚醚多醇和含羟基丙烯酸内聚物。
用于本发明的低分子量二醇,三醇和更高级的醇是本领域公知的那些。它们的羟基数量在200或更高,通常在200-1500范围内。这种物质包括脂族多醇,特别是含2-18碳原子的亚烷基多醇。举例包括乙二醇,1,2-丙二醇,1,3-丙二醇,1,4-丁二醇,1,6-己二醇;环脂多醇如1,2-环己二醇和环己二甲醇。三醇和更高的醇实例包括三甲醇丙烷、丙三醇和季戊四醇。也使用含醚键的多醇诸如二亚乙基二醇和三乙醇及烷氧基化的甘油。
还可使用低分子量酰胺多醇,其羟基值在100或更大。当聚合物结合有低分子量含酰胺多醇时,它们增强了水分散性。在要求柔韧性和弹性时可使用高分子量的聚合多醇。合适的聚合多醇包括聚亚烷基醚多醇,包括硫醚,包括多羟聚酯酰胺的聚酯多醇,含羟基聚己内酯和含羟基丙烯酸内聚物。
所用的酸性多醇和其他多醇成份是在低速简单混和在一起就形成了多醇相。在零VOC体系混合时,对于各种组分不需要利用封闭反应器以及在干燥氮气下掩盖以隔离大气湿气,而这些在制备上述水性脂族聚氨酯分散体的现有工艺中是需要的。尽管在大气湿气存在时混和掺合多醇,仍不成问题,因为本工艺的优点是在零VOC的水基体系下进行的。制备时,混合的多醇相基本是100%的多醇,而很小量的溶剂和水不必排除。如上述可知,多醇应有至少为1.5且优选至少为2的平均羟基官能度和15-200之间的酸数。胺:
在区分各种胺时所用的各种术语,如中和及链扩展,其目的是鉴别而不是分类。某些胺起中和剂和增链剂两者的作用,试图仅按照其一作用将其归类不是精确的。然而胺或胺类结合体在本发明的作用方面是必不可少。需要胺的存在目的是中和多醇中的酸,将其转化成盐,使得它具有水混容性,溶解性或分散性。还有,由于活性氢,例如来自胺氢或胺上的羟基基团,胺可通过与异氰酸酯反应生成聚氨酯和聚脲来进行链扩展和交联体系。
而且,酸性多醇成分和胺或胺掺合体的结合物在双成分体系中对所有成分都起有效分散剂的作用,如异氰酸酯和其他多醇,而无需外加表面活性剂或洗涤剂来增加该体系水溶解性,乳化性或分散性。
起中和酸作用和与异氰酸酯反应制备本发明的氨基甲酸乙酯时所采用的胺可选自下列物组:氨、伯的和仲的脂族,脂环族和芳族胺;叔脂胺和芳香胺;链醇胺,二链醇胺,三链醇胺;聚胺如脂族,脂环族和芳族二胺,三胺和四胺,烷氧基胺,聚氧亚烷基二胺,聚氧亚烷基三胺及其混和物。氨和胺不具有或具有不足的活性氢,例如叔烷基胺,可利用它的中和能力,保证全部胺混合体具有的平均活性氢官能度至少为1.5,优选至少2。
下面是可利用胺的实例,并不意味着穷举。
伯胺的代表是C1-C12胺,诸如甲胺,乙胺,丙胺,异丙胺,1,3-二甲基丁胺,3,3-二甲基丁胺,1-甲基丁胺,2-甲基丁胺,2-乙基丁胺,异戊胺,己胺,1,5-二甲基己胺,1,2-二甲基丙胺,壬胺,十二胺,环己胺,对氨基酚和苯胺。
叔胺的代表是二乙胺,二丙胺,二异丙胺,二丁胺,二异丁基胺,N-甲基乙胺,N-甲基丁胺,N-乙基丁胺,N-甲基环已胺,N-甲基苯胺。
叔胺实例为三乙胺,三甲胺,三丙胺,三异丙胺,三丁胺和甲基二乙胺。具有活性氢的那些包括三乙醇胺,三异丙醇胺,N-乙基二乙醇胺,N,N-二甲基乙醇胺,N,N-二乙基乙醇胺,N,N-二乙基甲胺,3-二乙氨基丙醇,1,3-双(二甲氨基)-2-丙醇,5-二乙氨基-2-戊醇,1-二乙氨基-2-丙醇,2-(二乙氨基)-1,2-丙二醇,2-(二异丙氨基)乙醇,3-二异丙氨基-1,2-丙二醇,1-二甲氨基-2-丙醇,3-二甲氨基-1-丙醇,3-二甲氨基丙胺以及三(3-氨丙基)胺。叔胺也可归类于链醇胺,二胺等。
代表性链醇胺是乙醇胺,2-氨基-1-丁醇,4-氨基-1-丁醇,2-氨基乙二醇,2-氨基-1-己醇,2-氨基-3-甲基-1-丁醇,2-氨基-2-甲基-1-丙醇,2-氨基-2-甲基-1,3-丙二醇,5-氨基-1-戊醇,3-氨基-1-丙醇,2-(甲氨基)乙醇,2-(丙氨基)乙醇,和三(羟甲基)氨基甲烷。
二链醇胺的代表是二乙醇胺,二丙醇胺,二异丙醇胺,二正丁醇胺,二异丁醇胺,1-[N,N-双(2-羟乙基)氨基]-2-丙醇和N-甲基二乙醇胺。
合适的三链醇胺是三甲醇胺,三乙醇胺,三异丙醇胺。
脂族,肪环族和芳族二胺,三胺和四胺的实例如下:
合适的二胺包括:乙二胺,六亚甲基二胺,1,4-二氨基丁烷,1,3-二氨基丙烷,1,2-二氨基丙烷,1,3-二氨基戊烷,1,5-二氨基戊烷,2-甲基五亚甲基二胺,1,7-二氨基庚烷,1,8-二氨基辛烷,1,9-二氨基壬烷,1,10-二氨基癸烷,1,12-二氨基十二烷,1,3-二氨基-2-羟基丙烷,1,2-二氨基-2-甲基丙烷,3-(二丁基胺)丙胺,N-异丙基亚乙基二胺,N,N-二甲基-N′-亚乙基二胺,N,N′-二甲基-1,6-己二胺,2,5-二甲基-2,5-己二胺,N-甲基亚乙基二胺,N-甲基-1,3-丙二胺,N,N′-双(2-氨乙基)-1,3-丙二胺,N,N′-双(3-氨丙基)-1,3-丙二胺N,N′-双(2-羟乙基)亚乙基二胺,N-异丙基-2-甲基-1,2丙二胺,N,N-2,2-四甲基-1,3-丙二胺,异佛尔酮二胺,丙烷-2,2-环己胺,邻苯二胺,对氨基二苯胺,对甲苯二胺,N,N′-二甲基-邻亚苯基二胺,和N,N′-双-对甲苯-间-亚苯基二胺。
三胺的代表是二亚乙基三胺和3,3-二氨基-N-甲基二丙胺。
四胺的代表是三亚乙基四胺。
氧化亚烷基胺和聚氧亚烷基的二和三胺代表如下:3-乙氧基丙胺,聚氧亚乙基胺,聚氧亚丙基胺,聚氧亚乙基二胺,聚氧亚丙基二胺,聚氧亚乙基三胺和聚氧亚丙基三胺。特别合适的是聚氧亚烷基二胺和聚氧亚烷基三胺,它们可在Huntsman化学公司以商标名Jeffamine下排布为:如Jeffamine M600,D230,D400,ED600,ED2001,ED4000,ED6000,DU700和T300等售出。
各种胺成分在水(自来水是合适的)中混合在一起形成含有的胺含量在大约20-100%重量之间的混合体。胺和多醇的添加:
多醇和胺可于室温在开放器皿中直接混合在一起,因为它们不涉及溶剂。
有许多方式或方法形成这种多醇/胺成分。优选的是多醇相在混和罐中用含有任何所需要添加剂的水进行混合,添加剂包括如消泡剂,表面张力降低剂,pH调节剂(如氨水)等。使用时,任何合适的消泡剂或一些试剂的混合体皆可使用,试剂举例如硅烷或非离子炔属二醇,它并非必须具备但却是有作用的。这些水性混合体可在室温配制。于是,混合的胺相使得总的多醇/胺成分具有的固体含量在大约33-80%重量之间。如果需要,胺相的胺成分可随后添加。这种聚酯-多醇/胺成分的一个实用优点是,多醇混合体和胺混合体可以配剂,并可分开运输。然后,这些相可用水在任何合适地点混合,并不需要运输水,而水在最终混合物中含量超过50%。异氰酸酯:
本发明所用有机聚异氰酸酯可为脂族,脂环族或芳族聚异氰酸酯或其混合物。脂族或脂环族聚异氰酸酯是优选的,因为发现它们具有选择性的反应性。还优选二异氰酸酯,尽管可用更高的聚异氰酸酯取代或者用二异氰酸酯和/或一异氰酸酯的结合。如果使用较高官能度的聚异氰酸酯时,某些单一官能基的异氰酸酯可以存在,以便降低平均官能度;但使用单一官能度的异氰酸酯并不优选。合适的更高聚异氰酸酯的实例是1,2,4-苯三异氰酸酯和聚亚乙基聚苯基的异氰酸酯。合适的一异氰酸酯的实例是异氰酸环己酯,异氰酸苯酯和异氰酸甲苯酯。可接受的芳族二异氰酸酯实例是4,4′-二苯甲烷二异氰酸酯,1,3-亚苯基二异氰酸酯,1,4-亚苯基二异氰酸酯和亚甲苯基二异氰酸酯。合适的脂族二异氰酸酯举例如直链脂族二异氰酸酯,诸如1,4-四亚甲基二异氰酸酯和1,6-六亚甲基二异氰酸酯。也可使用脂环族二异氰酸酯。实例包括1,4-环己基二异氰酸酯,异佛尔酮二异氰酸酯、α,α-二甲苯亚基二异氰酸酯和4,4-亚甲基-双(环己基二异氰酸酯)。也可使用取代的有机聚异氰酸酯,其中取代基是硝基,氯代基,烷氧基和其他基团,只要它们不与羟基或活性氢起反应,并且保证取代基不定位到使得异氰酸酯基团不发生反应的位置上。
可以使用对应上述的硫代异氰酸酯以及含有异氰酸酯和硫代异氰酸酯基团两者的混和的化合物。在本发明的说明书及权利要求收中使用的术语“聚异氰酸酯”和“二异氰酸酯”,是想复盖含有硫代异氰酸酯基团或异氰酸酯基团的化合物或加合物以及含有两者基团的化合物和加合物。其中的加合物是异氰尿酸酯,二脲二酮(uretdiones),碳化二亚胺的缩二脲,以及由过量的多官能基异氰酸酯与多醇进行的预聚物。
特别优选的异氰酸酯加合物是基于六亚甲基二异氰酸酯(HDI)的那些。
形成这种双成分体系是通过对多醇/胺成分的每个活性氢当量至少要混合0.5当量的异氰酸酯。对于多醇/胺成分的每个活性氢当量优选异氢酸酯当量在1.1-3之间,而最佳在1.3-2之间。这种异氰酸酯的用量要充足,以便得到超过多醇/胺中-NCO基团对官能基的指数。这样就能提供足够的-NCO基团使链扩散和交联在聚氨酯-聚脲结构中进行得最大。
这种混合体形成一种水性无有机溶剂的聚氨酯分散体,其固体含量在大约30-85%之间。它提供了一种优异的零VOC保护性涂料混合物,可涂覆应用到差不多任何基体上如混凝土,木材及金属上。它特别适合用于的基体是承受腐蚀性化学物泄漏的基体,或者需要耐磨损的拥挤路面。也可设计用于需要高度美术性特别持久性的保护性涂料之处。它是一种适合于严酷海洋性、海滩和化学环境中的涂料,在这些地方,要求进行腐蚀保护和抵抗由于暴露于日光下而产生的退色,剥落或粉化的双重作用。再者,它是突出的抗末道浆涂料。它可在大约50°F以上温度时涂覆到干净和干燥的基体上并能用肥皂和水易于完全清除。
这种双成分体系通过化学反应固化,因而不取决于大气条件。另外,该混合物是水可还原的。当稀薄或者还原时用普通自来水即可。对稀薄化或还原的程度并无限制。然而对最佳的结果还原混合体的固体含量应不低于大约35%。
水性多醇/胺混合体可与着色剂混合,例如颜料,染料及染色剂等。另外,也可混合其他水基添加剂如流平剂,触变剂,防止mar或防滑剂或任何其他试剂,只要它们对水分散体不起反作用并有能够涂覆和固化到基体上就行。
实施例1
使用酸性聚酯-多醇,它是适当部分的与苯六酸酐起反应的己二醇新戊基二醇。它具有的平均分子量大约1500并含有羧酸和羟基两者。这种多醇有大约1250的当量,酸值大约50,羟基值大约66且羟基/酸官能度比值大约1.8∶1.3。这种多醇是浅色蜡状液体,其粘度在25℃时为大约2800cps而60℃时为大约2700cps。为说明起见,这种酸性聚酯多醇用符号“Polyol A”来代表。
50克Polyol A用50mls水稀释形成50/50重量的多醇/混合体。向这种混合体加入大约6克的三乙醇胺,胺当量为149。酸/胺的当量比是1∶1,以提供足量胺来中和多醇的酸官能团。
向多醇/水混合体加入40克100%固态六亚甲基二异氰酸酯的异氰酸酯三聚体,三聚体的当量为大约181,从而提供充足NCO的当量,以便得到NCO/活性氢比值为大约1.2∶1。所得混合物是水系聚氨酯分散体,具有的适用期超过2小时。涂覆基体时,它的压干时间为大约5-7小时并有接近HB铅笔硬度。它的环境固化特性显示出耐溶剂性在耐300-500次MEK摩擦之间,且浸没在水中有合适的耐水性。加热到180°F时涂料有些发黄。
实施例2
使用4克的二乙醇胺(当量105)作为胺得到酸/胺当量比大约1∶1,重复实施例1。使用48克实施例1的异氰酸酯三聚物,得到NCO/活性氢比值为大约1.5∶1,其他条件同实施例1。所得混合物是水性聚氨酯分散体,其适用期超过3小时。涂覆基体时,它的压干时间为大约6-8小时并有F铅笔硬度。它的环境固化特性显示出耐溶剂在300-500次MEK摩擦,且浸没在水中有合适的耐水性。加热到180°F时涂料保持清晰。
实施例3
使用2克的2-甲基-1,5-二氨基戊烷(MDP)(当量58)作为胺得到酸/胺当量比大约1∶1,重复实施例1。使用26克实施例1的异氰酸酯三聚物,得到NCO/活性氢比值为大约1.5∶1,其他条件同实施例1。所得混合物是水性聚异氨酯分散体,其适用期少于1小时。涂覆基体时,它的压干时间为大约4小时并有H铅笔硬度。它的环境固化特性显示出耐溶剂在500次MEK摩擦,且浸没在水中有合适的耐水性。加热到180°F时涂料保持清晰。
实施例4
使用0.2克的2-甲基-1,5-二氨基戊烷(MDP)(当量58)和3.0克28%氢氧化铵(当量17)的混合体作为胺,得到酸/胺当量比大约0.7∶1,重复实施例1。使用30克实施例1的异氰酸酯三聚物,得到NCO/活性氢比值为大约1.5∶1,其他条件同实施例1。所得混合物是水性聚氨酯分散体,其适用期大约2小时。涂覆基体时,它的压干时间为大约6小时并有HB铅笔硬度。它的环境固化特性显示出耐溶剂性在300-500次MEK摩擦,且浸没在水中有合适的耐水性。加热到180°F时涂料保持清晰。
实施例5
使用2.8克的2-氨基-2-二甲基丙烷(AMP)(当量45)和0.2克的2-甲基-1,5-二氨基戊烷(MDP)(当量58)的混合体作为胺,得到酸/胺当量比大约0.6∶1,重复实施例1。使用35克实施例1的异氰酸酯三聚物,得到NCO/活性氢比值为大约1.5∶1,其他条件同实施例1。所得混合物是水性聚氨酯分散体,其适用期大约2-3小时。涂覆基体时,它的压干时间为大约6小时并有B铅笔硬度。它的环境固化特性显示出耐溶剂性在300-500次MEK摩擦,且浸没在水中有合适的耐水性。加热到180°F时涂料保持清晰。
实施例6
制备水性多醇混合体,方式是将下列物进行结合:29份重量的Polyol A,25份非酸性聚酯-多醇(King K-Flex 188)其当量238,1份重量的胺混合体(Amine A),该胺混合体是由50%二乙醇胺、10%的MDP和40%的AMP构成,1.3份28%的氢氧化铵,5份重量的三羟甲基丙烷(TMP),0.5份重量的聚氧亚丙基三胺其分子量大约3000(Jeffamine 3000),36.2份重量的水,1.0份重量的UV稳定剂混合物(CIBA,TINUVIN 292和1130)和1.O份重量的表面活性剂/消泡剂(Byk 346表面活性剂,Deefo消泡剂)混合物。这种混合体的酸当量是0.023,胺当量0.026,所以有稍过量的胺来中和酸官能团且活性氢当量大约0.25。
制备白色颜料化溶液,方式是漆研磨下列物的混合物,大约55份重量的上述多醇/胺,28份重量的TiO2,16份重量的水和1.0份重量的表面活性剂混合物。
然后将100份这种颜料化多醇/胺混合体结合50份重量的实施例1异氰酸酯三聚物,得到NCO/活性氢比值大约2∶1。
这种分散体适用期大约3.5小时。该分散体置于基体后,它的压干时间为大约4-5小时,固化干燥后有3H铅笔硬度。它的环境固化特性显示出耐溶剂性超过2000次MEK摩擦,且浸没在水中长达七天有优异的耐水性。加热到180°F时涂料不发黄并在加速UV稳定性试验时有优异的保光性。
实施例7
向100份实施例6颜料化化多醇/胺混合体中结合45份六亚甲基二异氰酸酯的缩二脲三聚物(Miles N3200)得到的可喷雾涂料,其NCO/活性氢比值大约2∶1。这种分散体适用期大约2.5小时,压干时间为大约4-5小时。它的固化薄膜特性差不多与实施例6所报道的相同。
实施例8
制备水性多醇混合体,方式是将下列物进行结合:29份重量的Polyol A,25份非酸性聚酯-多醇(King K-Flex 165)其当量238,1.5份重量的胺混合体(Amine B),该胺混合体是由30%三乙醇胺、40%的MDP和30%的AMP构成,1.3份28%的氢氧化铵,5份重量的三羟甲基丙烷(TMP),36.18份重量的水,1.0份重量的UV稳定剂混合物(CTBA TINUVIN 292和1130),1.0份重量的流动性控制添加剂混合物(3M FC-120表面活性剂,Air Products DF574消泡剂)和0.02份锡催化剂[T12(DBTLD)]。这种混合体的酸当量是0.023,胺当量0.030,所以有过量的胺来中和酸官能团且活性氢当量大约0.25。
制备白色颜料化溶液,方式是混合下列物质:大约55份重量的上述多醇/胺,28份重量的TiO2,16份重量的水和1.0份重量的表面活性剂混合物。
然后将100份这种颜料化多醇/胺混合体结合50份重量的实施例1异氰酸酯三聚物,得到NCO/活性氢比值大约2∶1。
这种分散体适用期大约2.5小时。该分散体置于基体后,它的压干时间为大约5-7小时之间并有3-4H铅笔硬度。它的环境固化特性显示出耐溶剂性超过3000次MEK摩擦,且浸没在水中七天有优异的耐水性。加热到180°F时涂料不发黄并在加速UV稳定性试验时有优异的保光性。
实施例9
制备水性多醇混合体,方式是将下列物进行结合:26.4份重量的Po1yol A,13份重量的非酸性芳族聚酯-二醇(Stephan 4000)其当量140,1.5份重量的胺混合体(Amine C),该胺混合体是由35%三乙醇胺、10%二乙醇胺,25%的1,3-戊二胺和30%的AMP构成,0.8份28%的氢氧化铵,11份重量的三甲醇丙烷(TMP),4.4份重量的聚氧亚丙基三胺其分子量大约3000(Jeffamine 3000),41.73份重量的水,1.15份重量的表面活性剂/消泡剂混合物(Byk 364表面活性剂,DF574消泡剂)和0.02份重量的锡催化剂[T12(DBTLD)]。这种混合体的酸当量是0.021,胺当量0.026,所以酸/胺比值0.4∶1,有过量的胺来中和酸官能团且活性氢当量大约0.37。
制备黑色颜料化溶液,方式是漆研磨下列物的混合物:大约100份重量的上述多醇/胺,25份重量的酸性功能丙烯酸树脂(COOk Chemical 4301),20份重量的水和10份重量的黑色颜料分散体(Huls 896 W/B)。
然后将100份这种颜料化多醇/胺混合体结合50份重量的实施例1异氰酸酯三聚物,得到NCO/活性氢比值大约2∶1。
这种分散体适用期大约1.25-2小时。该分散体置于基体后,它的压干时间为大约4-5小时之间并有3-4H铅笔硬度。它的环境固化特性显示出耐溶剂超过2000次MEK摩擦,且浸没在水中七天有优异的耐水性。加热到180°F时涂料有优异的保光性。
实施例10
两升反应容器装配机械搅拌器、氮气、加热和冷却系统以及水分离器,装载1000克Ruco聚酯二醇,包括新戊二醇、己二醇和已二酸,其平均分子量大约1000且羟基数65。搅拌加热该多醇至150°F,之后加入100克二甲醇丙二酸和0.5克的对甲苯磺酸催化剂。温度增至260°F经30分钟,再保持该温度10小时同时保持缓慢的氮气清洗,用冷阱收集大约10-12克水。反应混合物冷却到180°F并对产物进行酸数操作。一般加入10克丁二酸酐的季铵氯化物,然后加热混合物直至酸数达45-50范围且羟基数大约60。
类同于实施例6所示制备多醇胺混合体,用30克上述二甲醇丙二酸,含有聚酯二醇代替Polyol A。将其结合20克脂族聚酯多醇(K-Flex 188),1.5克的胺混合体,该胺混合体是由34%三乙醇胺、33%的DMP和33%的AMP构成,1.4克28%的氢氧化铵,8克三羟甲基丙烷(TMP),37克水,1克UV稳定剂(Tinuvin 292)和1克表面活性剂/消泡剂混合物。这种混合体的酸当量是0.025,胺当量0.045,活性氢当量大约0.35。
制备清晰涂料,方法是将100份上述多醇/胺混合体结合80份实施例1所用六亚甲基二异氰酸酯的异氰酸酯三聚物,得到NCO/活性氢当量比值大约1.25∶1。所得乳化体用80份水还原得到低粘度分散体,其固体含量大约54%,适用期超过2小时。该分散涂料体置于金属基体后,它的压干时间为大约4-6小时之间环境温度5-7天实现完全固化。所得薄膜有H-2H铅笔硬度,具有耐500次以上MEK摩擦,且在QUV和加热到180°F老化试验时涂料保持无色。
以上表明本发明完善和优选实施方案时,本领域技术人员显然可对其作出一定的改进和替代而不偏离本发明范围,该范围被申请的权利要求及其等同替代所限定。
Claims (26)
1.一种基本无溶剂水性双成分涂料组合物分散体,包括:
a)一种水相,包括:
1)一种多醇相,选自含酸多醇和含酸含多醇的多醇混合体,这种多醇相的平均羟基官能度至少1.5,所述多醇相具有的酸数在大约15-200之间;
2)一种含有与NCO基团反应的活性氢的胺或胺混合体,其活性氢官能度至少1.5,胺或胺混合体以最小量存在但足以基本中和含酸多醇;和
b)一种选自下列的成员:脂族聚异氰酸酯,脂环族聚异氰酸酯和芳族聚异氰酸酯及其混合物,其中异氰酸酯对多醇和胺的活性氢之和的当量比至少为0.5∶1。
2.根据权利要求1的双成分组合物,其中所述含酸多醇选自下列成员:
a)多羟聚醚和多官能团羧酸或其酐的反应产物;
b)乙烯化不饱和酸,乙烯化不饱和醇和乙烯化不饱和酯的反应产物;和
c)多羟基多醇和多官能羧酸或其酐的反应产物。
3.根据权利要求2的双成分组合物,其中所述多醇相的羟基官能度至少2,所述胺或胺混合体具有的平均活性氢官能度至少2,且其中NCO对多醇和胺的活性氢之和的当量比至少为1.1∶1。
4.根据权利要求3的双成分组合物,其中所述含酸多醇是聚酯多醇并包括多羟基多醇和多官能羧酸或其酐的反应产物。
5.根据权利要求4的双成分组合物,其中所述含酸多醇是聚酯多醇并包括二羟基多醇,三羟基多醇和二羧酸或其酐的反应产物。
6.根据权利要求4的双成分组合物,其中所述含酸多醇是聚酯多醇并包括二羟基多醇,二羧酸和三羧酸或其酐的反应产物。
7.根据权利要求4的双成分组合物,其中所述含酸多醇是聚酯多醇并包括多羟基醇和二羧酸或其酐的反应产物。
8.根据权利要求4的双成分组合物,其中所述含酸多醇是聚酯多醇并含有三元芳族酸部分。
9.根据权利要求4的双成分组合物,其中所述含酸多醇是聚酯多醇并含有作为一种成分的含羧酸基的二醇。
10.根据权利要求9的组合物,其中所述含羧酸基二醇是α,α-二羟甲基链烷醇酸,化学式:其中R是含有1-8个碳原子的烷基。
11.根据权利要求3的组合物,其中所述含酸多醇是聚醚多醇并包括多羟基聚醚和多官能羧酸或其酐的反应产物。
12.根据权利要求3的双成分组合物,其中所述含酸多醇是聚丙烯酸酯多醇,包括乙烯化不饱和酸,乙烯化不饱和醇和乙烯化不饱和酯的反应产物。
13.根据权利要求2的组合物,其中所述多醇是含酸含多醇的多醇混合体。
14.根据权利要求13的组合物,其中所述多醇混合体除所述含酸多醇之外包括至少一种选自下列成员的非酸性多醇:
a)一种单体多醇,选自二醇,三醇,高级多官能醇,氧醇及其混合物,
b)一种聚合多醇,选自聚酯多醇,聚醚多醇,聚酰胺多醇,聚酯酰胺多醇,聚己内酯多醇和丙烯酸共聚物多醇及其混合物,
c)单体的和聚合的多醇混合物。
15.根据权利要求14的组合物,包括至少一种单体多醇选自二醇,三醇,高级多官能醇,氧醇及其混合物。
16.根据权利要求15的组合物,其中所述单体多醇是三醇,选自三羟甲基丙烷,三羟甲基乙烷和甘油。
17.根据权利要求16的组合物,其中所述三醇是三羟甲基丙烷。
18.根据权利要求14的组合物,其中包括的至少一种聚合多醇选自聚酯多醇,聚醚多醇,聚酰胺多醇,聚酯酰胺多醇,聚己内酯多醇和丙烯酸内聚多醇及其混合物。
19.根据权利要求18的组合物,其中所述聚合多醇是聚酯多醇。
20.根据权利要求18的组合物,其中所述聚合多醇是聚醚多醇。
21.根据权利要求18的组合物,其中所述聚合多醇是聚酰胺多醇。
22.根据权利要求18的组合物,其中所述聚合多醇是聚酯酰胺多醇。
23.根据权利要求18的组合物,其中所述聚合多醇是聚己内酯多醇。
24.根据权利要求18的组合物,其中所述聚合多醇是丙烯酸内聚多醇。
25.根据权利要求3的组合物,其中所述胺或胺混合体选自下列成员:氨,初级和二级脂族,脂环族和芳族胺;脂族叔胺;链醇胺,二链醇胺,三链醇胺;多胺选自脂族,脂环族和芳族二胺,三胺和四胺;氧亚烷基胺,聚亚烷基二胺和聚亚烷基三胺。
26.根据权利要求14的组合物,其中所述胺或胺混合体选自下列成员:氨,初级和二级脂族,脂环族和芳族胺;脂族叔胺;链醇胺,二链醇胺,三链醇胺;多胺选自脂族,脂环族和芳族二胺,三胺和四胺;氧亚烷基胺,聚亚烷基二胺和聚氧亚烷基三胺。
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Application Number | Priority Date | Filing Date | Title |
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US303,356 | 1989-01-27 | ||
US303356 | 1989-01-27 | ||
US08/303,356 US5508340A (en) | 1993-03-10 | 1994-09-09 | Water-based, solvent-free or low voc, two-component polyurethane coatings |
Publications (2)
Publication Number | Publication Date |
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CN1129241A true CN1129241A (zh) | 1996-08-21 |
CN1048276C CN1048276C (zh) | 2000-01-12 |
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CN95118432A Expired - Fee Related CN1048276C (zh) | 1994-09-09 | 1995-09-09 | 水基、无溶剂或低挥发性双成分聚氨酯涂料 |
Country Status (19)
Country | Link |
---|---|
US (2) | US5508340A (zh) |
EP (1) | EP0700945B1 (zh) |
JP (1) | JP3221650B2 (zh) |
KR (1) | KR100191952B1 (zh) |
CN (1) | CN1048276C (zh) |
AT (1) | ATE228148T1 (zh) |
AU (1) | AU685309B2 (zh) |
BR (1) | BR9503992A (zh) |
CA (1) | CA2157696C (zh) |
CZ (1) | CZ232795A3 (zh) |
DE (1) | DE69528872T2 (zh) |
DK (1) | DK0700945T3 (zh) |
ES (1) | ES2182859T3 (zh) |
FI (1) | FI110785B (zh) |
HU (1) | HUT72726A (zh) |
NO (1) | NO310470B1 (zh) |
NZ (1) | NZ272951A (zh) |
PL (1) | PL310369A1 (zh) |
ZA (1) | ZA957608B (zh) |
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- 1995-09-07 NZ NZ272951A patent/NZ272951A/en unknown
- 1995-09-07 CA CA002157696A patent/CA2157696C/en not_active Expired - Fee Related
- 1995-09-08 ES ES95114151T patent/ES2182859T3/es not_active Expired - Lifetime
- 1995-09-08 DK DK95114151T patent/DK0700945T3/da active
- 1995-09-08 FI FI954214A patent/FI110785B/fi not_active IP Right Cessation
- 1995-09-08 HU HU9502664A patent/HUT72726A/hu unknown
- 1995-09-08 EP EP95114151A patent/EP0700945B1/en not_active Expired - Lifetime
- 1995-09-08 NO NO19953552A patent/NO310470B1/no unknown
- 1995-09-08 AT AT95114151T patent/ATE228148T1/de not_active IP Right Cessation
- 1995-09-08 CZ CZ952327A patent/CZ232795A3/cs unknown
- 1995-09-08 DE DE69528872T patent/DE69528872T2/de not_active Expired - Fee Related
- 1995-09-08 JP JP26606795A patent/JP3221650B2/ja not_active Expired - Fee Related
- 1995-09-09 CN CN95118432A patent/CN1048276C/zh not_active Expired - Fee Related
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102911556A (zh) * | 2012-08-28 | 2013-02-06 | 东莞市万钧化工新材料科技有限公司 | 一种环保尼龙材料用油墨及其制备方法 |
CN103589315A (zh) * | 2013-11-13 | 2014-02-19 | 宁德师范学院 | 一种离子液体液化木材制备聚氨酯涂料的方法 |
CN103589315B (zh) * | 2013-11-13 | 2015-11-18 | 宁德师范学院 | 一种离子液体液化木材制备聚氨酯涂料的方法 |
CN108003774A (zh) * | 2017-12-21 | 2018-05-08 | 新纳奇材料科技江苏有限公司 | 一种纳米材料改性的无溶剂聚氨酯木器漆及其制备方法 |
CN111334176A (zh) * | 2020-03-09 | 2020-06-26 | 沪宝新材料科技(上海)股份有限公司 | 一种塑胶跑道的无溶剂双组分面漆 |
Also Published As
Publication number | Publication date |
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PL310369A1 (en) | 1996-03-18 |
US5508340A (en) | 1996-04-16 |
KR100191952B1 (ko) | 1999-06-15 |
FI110785B (fi) | 2003-03-31 |
HU9502664D0 (en) | 1995-11-28 |
HUT72726A (en) | 1996-05-28 |
CN1048276C (zh) | 2000-01-12 |
EP0700945A1 (en) | 1996-03-13 |
DE69528872D1 (de) | 2003-01-02 |
JPH08193181A (ja) | 1996-07-30 |
NO953552L (no) | 1996-03-11 |
NO953552D0 (no) | 1995-09-08 |
AU3058495A (en) | 1996-03-21 |
AU685309B2 (en) | 1998-01-15 |
EP0700945B1 (en) | 2002-11-20 |
CA2157696C (en) | 1999-05-18 |
ZA957608B (en) | 1997-03-11 |
DK0700945T3 (da) | 2002-12-16 |
US5693703A (en) | 1997-12-02 |
JP3221650B2 (ja) | 2001-10-22 |
BR9503992A (pt) | 1996-04-02 |
NZ272951A (en) | 1996-09-25 |
CZ232795A3 (en) | 1996-06-12 |
CA2157696A1 (en) | 1996-03-10 |
DE69528872T2 (de) | 2003-03-27 |
KR960010811A (ko) | 1996-04-20 |
FI954214A0 (fi) | 1995-09-08 |
NO310470B1 (no) | 2001-07-09 |
ES2182859T3 (es) | 2003-03-16 |
FI954214A (fi) | 1996-03-10 |
ATE228148T1 (de) | 2002-12-15 |
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