CN1010318B - 液体涂料组合物和用其涂布基体的方法 - Google Patents
液体涂料组合物和用其涂布基体的方法Info
- Publication number
- CN1010318B CN1010318B CN86101964A CN86101964A CN1010318B CN 1010318 B CN1010318 B CN 1010318B CN 86101964 A CN86101964 A CN 86101964A CN 86101964 A CN86101964 A CN 86101964A CN 1010318 B CN1010318 B CN 1010318B
- Authority
- CN
- China
- Prior art keywords
- compound
- compounds
- coating composition
- amino
- grams
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
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- 239000007788 liquid Substances 0.000 title claims abstract description 5
- 238000000576 coating method Methods 0.000 title abstract description 10
- 239000011248 coating agent Substances 0.000 title abstract description 7
- 238000000034 method Methods 0.000 title abstract description 4
- 239000000758 substrate Substances 0.000 title abstract description 4
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- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 26
- 239000012948 isocyanate Substances 0.000 claims abstract description 25
- 239000004593 Epoxy Substances 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 14
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- 150000002576 ketones Chemical class 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
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- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 4
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- DOYTVCMYDUKCJY-UHFFFAOYSA-N CCCCO.OC(=O)C=C.OC(=O)C=C Chemical compound CCCCO.OC(=O)C=C.OC(=O)C=C DOYTVCMYDUKCJY-UHFFFAOYSA-N 0.000 claims 1
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- 238000010438 heat treatment Methods 0.000 description 5
- 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 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
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- 238000000746 purification Methods 0.000 description 5
- 229940126062 Compound A Drugs 0.000 description 4
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 4
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- 125000002947 alkylene group Chemical group 0.000 description 4
- 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 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- GKQPCPXONLDCMU-CCEZHUSRSA-N lacidipine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C1=CC=CC=C1\C=C\C(=O)OC(C)(C)C GKQPCPXONLDCMU-CCEZHUSRSA-N 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- RHLVCLIPMVJYKS-UHFFFAOYSA-N 3-octanone Chemical compound CCCCCC(=O)CC RHLVCLIPMVJYKS-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000010533 azeotropic distillation Methods 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
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- 235000019253 formic acid Nutrition 0.000 description 3
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Piles And Underground Anchors (AREA)
- Prostheses (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Pens And Brushes (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Sampling And Sample Adjustment (AREA)
- Epoxy Resins (AREA)
- Mechanical Coupling Of Light Guides (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Abstract
本发明提供可在常温下固化的液体涂料组合物,包含至少有2个丙烯酰基或甲基丙烯酰基的化合物,和含有一个用醛或酮保护的伯氮基的氨基化合物,该氨基化合物是含2-24个碳原子的脂族或脂环族胺,或者是环氧化合物或异氰酸酯化合物或α,β-烯键不饱和羰基化合物与含有一个能与上述环氧化合物或异氰酸酯化合物或α,β-烯键不饱和羰基化合物反应的基团的伯胺生成的分子量为300-1500的加合物。也提供用这样的组合物涂布基体的方法。
Description
本发明是关于液体涂料组合物,它基于至少具有二个丙烯酰基或甲基丙烯酰基的化合物和至少具有一个用不多于10个碳原子的醛或酮保护伯氨基的氨基化合物。根据欧洲专利申请号40,288,已知上述典型的组合物在室温下受水份的作用是可以固化的。若使用含氨基的乙烯加成聚合物作为氨基化合物,由于制备方法复杂并且费时,经常导致获得带颜色的产品。就使用来说,在无色具有重要意义时,如在两层金属体系中需有本色上表层时,这是令人讨厌的。
本发明提供的涂料组合物,其成分制备迅速且相当简单,完全或几乎不会产生有颜色的产品。
本发明的涂料组合物其特征在于:氨基化合物是含有2-24个碳原子的脂族或脂环族胺,或是环氧化合物或异氰酸酯化合物或α,β-烯键不饱和羰基化合物和至少有一个伯氨基且有一个能与环氧化合物或异氰酸酯化合物或α,β-烯键不饱和羰基化合物反应的基团的氨基化合物反应的加合物,加合物的分子量为300-1500。最好是,环氧化合物或异氰酸酯化合物或α,β-烯键不饱和羰基化合物是二元的或多元的化合物。
作为至少具有2个丙烯酰基或甲基丙烯酰基的化合物的代表例,可以提到二元、三元或多元醇的(甲基)丙烯酸酯,包括聚酯多元醇和聚醚多元醇;以含羟基的多元醇的(甲基)丙烯酸酯为一方,与以至少有2个官能团的异氰酸酯为另一方的加合物;以及(甲基)丙烯
酸和至少用2个官能团的环氧化合物的加合物。上述欧洲专利申请40,288号已列出其它适用的丙烯酰基和甲基丙烯酰基化合物,这些化合物被认为包括在本发明之内。为了简便起见,所提到的这些化合物在下文属于聚(甲基)丙烯酰基化合物。
作为适用的二元、三元或多元羟基化合物的(甲基丙烯酯的实例可以提到乙二醇、丙二醇、二乙二醇、1,4-丁二醇、新戊二醇、1,6-己二醇环己二醇、双-(4-羟基环己基)甲烷、丙三醇、三(羟甲基)乙烷、三(羟甲基)丙烷、三(2-羟乙基)异氰脲酸酯和季戊四醇。这些酯可选择性地含有羟基。这些多元醇及其它适用的羟基化合物,例如聚酯二元醇和多元醇以及聚醚二元醇和多元醇,已为H·Wagner和H.F.Sarx在《油漆合成树脂》1971年第5版中作了介绍(Carl Hanser Verlag,Munchen)。以至少有二个官能团的异氰酸酯化合物或环氧化合物生成加合物条件下的含羟基的(甲基)丙烯酸酯是多元醇的(甲基)丙烯酸酯,这些也已在上文介绍过。最好是,应当使用含2-6个羟基和2-10个碳原子的羟基化合物的丙烯酸酯,例如二(羟甲基)环己烷、乙二醇、己二醇、丙三醇、三(羟甲基)丙烷季戊四醇和二季戊四醇的丙烯酸酯。更具体地说要使用二丙烯酸三(羟甲基)丙烷酯或季戊四醇三丙烯酸酯。
作为上述加合物中可以用的至少为2个官能团异氰酸酯类化合物的一些实例,可以提到:脂肪族、脂环族或芳香族二、三、四异氰酸酯,它们可以是也可以不是烯键不饱和化合物,例如1,2-亚丙基二异氰酸酯、亚丙基二异氰酸酯、亚丁基二异氰酸酯、2,3-亚丁基二异氰酸酯、亚己基二异氰酸酯、亚辛基二异氰酸酯、2,2,4
-三甲基亚己基二异氰酸酯、2,4,4-三甲基亚己基二异氰酸酯亚十二(烷)基二异氰酸酯、ω,ω′-二亚丙醚二异氰酸酯、1,3-环戊烷二异氰酸酯、1,2-环己烷二异氰酸酯、1,4-环己烷-异氰酸酯、异佛尔酮二异氰酸酯、4-甲基-1,3-二异氰酸根合环己烷、反-亚乙烯基二异氰酸酯、二环乙基甲烷-4,4′-二异氰酸酯、3,3′二甲基-二环己基-二环己基甲烷-4,4′二异氰酸酯、甲苯二异氰酸酯、1,3-双(异氰酸根合甲基)苯、苯二甲基二异氰酸酯、1,5-二甲基-2,4-双(异氰酸根合甲基)苯、1,3,5-三乙基-2,4-双(异氰酸根合甲基)苯、酸根合联苯、3,3′-二苯基-4,4′-二异氰酸根合联苯、3,3′-二甲氧(基)-4,4′-二异氰酸根合联苯、4,4′-二异氰酸根合二苯基甲烷、3,3′-二甲基-4,4′-二异氰酸根合二苯基甲烷、二异氰酸根合萘、二个分子的二异氰酸酯(例如亚己基二异氰酸酯或异佛尔酮二异氰酸酯)和丁二醇(例如乙二醇)的加合物、三个分子的亚己基二异氰酸酯和一个分子水的加合物(拜尔公司销售,商标为Desmodur N)、1分子三(羟甲基)丙烷和3分子的甲苯二异氰酸酯加合物(拜尔公司销售,商标为Desmodur L)、1分子三(羟甲基)丙烷和3分子的异佛尔酮二异氰酸酯的加合物,以下化合物,例如1,3,5-三异氰酸根合苯和2,4,6-三异氰酸哥合甲苯,以及1分子季戊四醇和4分子甲苯二异氰酸酯。最好是,应当使用含8-36个碳原子的脂族或脂环族的二或三异氰酸酯。
作为可用于上面提到的加合物的至少有双官能团的固体或液体环氧类化合物的一些实例,可以提到的是:(环)脂族或芳香族羟基化
合物的二或多环氧甘油醚,象乙二醇、丙三醇、环己二醇、单核的二元或多元酚、双酚(如双酚A、双酚F),以及多核酚;酚醛线型清漆的多环氧甘油醚;环氧化及随后任选的氢化的苯乙烯或二乙烯基苯;含(例如)6-24个碳原子脂肪酸的缩水甘油酯;(甲基)丙烯酸缩水甘油酯;有异氰脲酸酯基的环氧化合物;环氧化的聚链二烯,例如环氧化的聚丁二烯;乙内酰脲环氧树脂;通过脂族烃和/脂环族烯烃环氧化得到的环氧树脂,例如双戊烯二氧化物、二环戊二烯二氧化物和乙烯基环己基二氧化物,以及含有缩水甘油基的树脂,例如每个分子含1个或几个缩水甘油基的聚酯或聚亚胺酯,或上述环氧树脂的混合物。环氧树脂为本领域专业人员所了解,这里不需作进一步介绍。最好应当使用脂环族环氧化合物含有环氧基的烯键不饱和化合物,象(甲基)丙烯酸缩水甘油酯、N-缩水甘油基(甲基)丙烯酰胺和/或烯丙基缩水甘油醚,和任意选择的一种或多种其它可以共聚的烯键不饱和单体。这些(共)聚合物可以通过自由基聚合反应,使用紫外光和/或过氧化物或含偶氮的引发剂,例如过氧化氢、氢过氧化枯烯、过氧化二叔丁基、过氧化苯甲酰、过苯甲酸叔丁酯、过三甲基己酸叔丁酯、偶氮二异丁腈和偶氮二戊腈来制备。在(甲基)丙烯酸对环氧化合物加成反应中,可选择性地采用催化剂和/或阻聚剂。作用适用的催化剂的一些实例,可以提到的是:三乙胺、吡啶、季铵盐、三芳基膦化氢和铬(Ⅲ)盐。适用的阻聚剂包括:苯醌、氢醌、对甲氧基苯酚和亚甲基盐。最好是,聚(甲基)丙烯酰基化合物是至少双官能团异氰酸酯化合物和含2-6个羟基及2-10个碳原子的羟基化合物的羟基丙烯酸酯的加合物,或者是至少二个官能团的环氧化合物和α,β-烯键不饱和羧酸的加合物。聚(甲基)丙烯酰基化
合物的分子量一般约为290-15000,最好是800-10000。
根据本发明,可以醛亚胺化或酮亚胺化形式用作组合物中第二成分的有代表性氨基化合物的实例,可以提到的是脂族或脂环族胺类,它至少有1个,最好是2-4个伯胺基和2-24个碳原子以及分子量不大于580。最好是,这些胺应该有0-4个仲胺基。适用的氨基化合物的实例包括乙二胺、丙二胺、乙醇胺、丙醇胺、丁二胺、戊二胺、己二胺、癸二胺、4,7-二噁十二烷-1,10-二胺、十二烷二胺、4,9-噁十二烷-1,12-二胺、7-甲基-4,10-二噁十三烷-1,13-二胺、1,2-氨基环己烷、1,4-二氨基环己烷、4,4′-二氨基二环己基甲烷、异佛尔酮二胺、双-(3-甲基-4-氨基环己基)甲烷、2,2-双-(4-氨基环己基)丙烷、次氮基三乙胺、聚醚、聚胺(例如人们熟知的Jefferson化学公司,商标为Jeffamine的那些产品)、双-(3-氨基丙基)甲胺、3-氨基-1-(甲氨基)丙烷、3-氨基-1-(环己基氨基)丙烷、N-(2-羟乙基)乙二胺和分子式为H2N-(R2NH)nR1-NH2的聚胺,式中R1基团和n个R2基团可以相同或各异,代表含有2-6个、最好是2-4个碳原子的亚烷基,n为数字1-6,最好是1-3。这里所
指的亚烷基也可以理解为环亚烷基或者含一个醚-氧原子的亚烷基。有代表性的聚亚烷基聚胺的实例包括:二亚乙基三胺、二亚丙基三胺及二亚丁基三胺。其它适用的氨基化合物是聚胺或羟胺与单环氧基化合物、单异氰酸酯或单官能团的α,β-烯键不饱和羰基化合物的加合物。最好是,氨基化合物应该具有脂环族性质并含有5-15个碳原子,例如异佛尔酮二胺、4,4′-二环己基甲烷二胺和3,3′-二甲基-4,4′-二环己基二胺。
根据本发明,可优先选择的其它适用的氨基化合物是分子量为300-1500的二元或多元环氧或者异氰酸酯类化合物,或α,β-烯键不饱和羰基化合物与至少含1个伯胺基和1个能与二元或多元化合物反应的基团的氨基化合物的加合物。这里所指的多官能团化合物可以与上述作为聚(甲基)丙烯酰基化合物的起始原料的化合物相同。当然,并不要求用作聚(甲基)丙烯酰基化合物和氨化合物的起始原料是同样的多官能团化合物。至于那些多官能团化合物,可参考上述内容。与氨基化合物一起用于生成加合物的α,β-烯键不饱和化合物最好是上述的聚(甲基)丙烯酰基化合物;另一方面,还可使用有1个或多个α,β-烯键不饱和二羧酸单元的化合物,例如马来酸或富马酸或其酯。这里所指的多官能团化合物,当然应该这样选择:它与氨基化合物生成的加合物具有本发明所需要的分子量300-1500。
用于与多官能环氧化合物或异氰酸酯类化合物或α,β-烯键不饱和羰基化合物生成加合物的氨基化合物,最好可以是上述含有2-24个碳原子的氨基化合物,或任意选择的单元胺,最好是有一个基团的伯单胺,例如该基团为羟基或巯基,它能与环氧化合物或异氰酸酯类化合物或α,β-烯键不饱和羰基化合物反应。最好是,氨基化合物应该是分子式为H2N-(R- 2NH)n-R1-NH2的聚胺(式中R1和n个R2基团可以相同或各异,代表有2-6个、最好有2-4个碳原子的亚烷基,n是数字1-6,最好是1-3)与二元或多元环氧化合物或异氰酸酯类化合物或α,β-烯
键不饱和羰基化合物的加合物。
根据本发明,在涂料组合物中所用的上述氨基化合物中的氨基,用不大于10个碳原子,最好是3-8个碳原子的醛或酮加以保护。适用的氨基保护剂的实例包括丙酮、甲基·乙基酮、甲基·异丁基酮、二乙基酮、甲基·异丙基酮、异丁醛、2-戊酮、环己酮、乙基·戊基酮、二异丁基酮、3-辛酮和癸酮。最好是,应当采用脂肪族或脂环族酮,尤其是含3-8个碳原子的。
制备上述加合物的一个有效方法是,例如上述环氧或异氰酸酯化合物或前述α,β-烯键不饱和羰基化合物与氨基、羟基、巯基官能团的酮亚胺或醛亚胺的加成反应。在加成反应后,可以选择性地对氨基加以保护。氨基保护已为大家所知,这里不需要进一步叙述。
根据本发明,在涂料组合物中,聚(甲基)的烯酰基化合物和氨基被保护的化合物,一般的用量是:烯不饱和双键的当量数与胺-氢当量数之比的范围为0.3-3.0,最好是1/2-2。
该组合物一般含有(例如)在油漆工业制品中普通应用的有机溶剂,如脂族或芳香族烃、酯、醚、醇、酮和醚乙酸酯类化合物。
涂料组合物还可含有常用的添加剂,例如颜料;填料;均化剂,例如丙烯酸酯低聚体;防沫剂,例如硅酮油;流变控制剂,例如膨润土、氢化蓖麻油衍生物和二异氰酸酯或三异氰酸酯与单胺或二胺的加合物;催化剂,例如硫酸、磷酸、磺酸酯、膦酸酯、磷酸酯和羧酸;抗氧化剂,例如取代的苯酚;还原剂,例如三烷基亚磷酸盐、三烷基磷化氢。Cu(I)盐、氢化硼、氢化铝、腈、亚硫酸盐和金属配合物,例如聚羧酸和二烷基酮肟;紫外线稳定剂,例如二苯酮、三唑、三氮烯、苯甲酸盐和受阻双哌啶胺;以及流挂控制剂,例如豆卵磷脂和焦化硅石。该组合物可选择性地含有一种或多种化合物,例如丙烯酸酯(共)聚合物、乙酰-丙酸纤维素、乙酰-丁酸纤维素、硝基纤维素、聚乙烯、环氧树脂或含乙酰乙酸酯基的化合
物。涂料组合物可以任何适当的方法涂布基体,例如用滚涂、喷涂、刷漆、喷淋、流涂或浸渍。该组合物最好是采用喷涂法。
适宜的基体包括经过预处理或未经预处理的金属,例如铁、钢、镀锌钢和铝,以及木材、合成材料、纸或皮革。所用涂料的固化,例如,可在0-30℃非常方便地进行。可任意使用高于30℃的固化温度,这样可减少固化时间。如果需要,还可在例如60°~120℃的范围固化组合物。
在下列实例下,将进一步介绍本发明。但不应认为,这些实例是本发明范围的一种限制。所谓“份数”系指“重量份数”,“%”系指重量百分数。粘度是在20℃测定的,除非另有说明。所有的(甲基)丙烯酰基化合物A-F和氨基被保护的化合物A-F的初期加纳尔(Gardner)色数均低于2。
(甲基)丙烯酰基化合物的制备
(甲基)丙烯酰基化合物A
往一个反应器内加入107.5克氢过氧化枯烯和3445克二甲苯,混合物加热至沸腾温度。然后,在90分钟内,加入1560克甲基丙烯酸缩水甘油酯、2807克苯乙烯和1872克丙烯酸丁酯。反应混合物保持在沸腾温度,直至转化率大于98%。然后,加入195克二甲苯。随后,将4252克前面制备的聚合物、320.4克丙烯酸、2.7克2-乙基己酸铬(Ⅲ)和4.57克氢醌加以混合,并通入空气,保持在110℃的温度,直至混合物的酸值将至2以下。然后,加入150克二甲苯,得到(甲基)丙烯酰基化合物A的53.1%溶液,其酸值为0.9,粘度170厘泊(CPa.s)。
(甲基)丙烯酰基化合物B
往一个反应器内加入2400克二甲苯,加热至沸腾温度。随后,在3小时内,加入2160克甲基丙烯酸缩水甘油酯、2112克苯乙烯、528克丙烯酸丁酯和192克过苯甲酸叔丁基酯。反应混合物保持在沸腾温度,直至转化率大于98%。然后,加入258.6克二甲苯。其次,将3183克前面制备的共
聚物、430克丙烯酸、2.15克2-乙基己酸铬(Ⅲ)和3.55克氢醌加以混合,并通入空气,保持在110℃的温度,直至混合物的酸值降低至4以下。然后,添加630克二甲苯,得到(甲基)丙烯酰基化合物B的55.0%溶液,其酸值3.9,粘度176厘泊。
(甲基)丙烯酰基化合物C
往一个反应器内加入12005克二甲苯,加热至沸腾温度。随后,在3小时内,加入600克甲基丙烯酸缩水甘油酯、1476克苯乙烯、324克丙烯酸丁酯和40.8克过苯甲酸叔丁基酯。反应混合物保持在沸腾温度,直至转化率大于98%为止。随后加入108克二甲苯。然后将3201克前面制备的共聚物、235克丙烯酸、0.59克2-乙基己酸铬(Ⅲ)和3.4克氢醌加以混合,并通入空气,保持在110℃的温度,直至该混合物的酸值降至2以下。其后再加入382克二甲苯和171克正丁醇。得到(甲基)丙烯酰基化合物C的57%溶液,其酸值为0.8,粘度186厘泊。
(甲基)丙烯酰基化合物D
往一个反应器内加入310.2克异佛尔酮二异氰酸酯和几滴二月桂酸二丁锡,随后加热至65-70℃。于30分钟内,往此反应器内依次加入720克三(羟甲基)丙烷二丙烯酸酯和550ppm氢醌,向混合物通入空气。反应混合物保持在70℃,直至异氰酸酯含量降至0.1%以下。然后,加入一定量的甲基·异丁基酮,从而得到(甲基)丙烯酰基化合物D的90%溶液,其酸值1.7,粘度62厘泊。
(甲基)丙烯酰基化合物E
往一个反应器内依次加入600克季戊四醇三丙烯酸酯、150克亚二异氰酸酯、250克乙酸丁酯、0.38克氢醌和几滴二月桂酸二丁锡,随后加热至55-60℃,向混合物通入空气。反应混合物保持在60℃,直至异氰酸酯含量低于0.1%以下。得到(甲基)丙烯酰基化合物E的75.0%溶液,其酸值1.1,粘度140厘泊。
(甲基)丙烯酰基化合物F
往一个反应器内加入600克季戊四醇三丙烯酸酯和292.6克六氢化邻苯二甲酸,加热至90-100℃,通入空气,直至混合物的酸值为120。然后把473克氢化双份A的二环氧甘油醚(壳牌化学公司,商标Eponex 1511)、0.71克2-乙基-己酸铬(Ⅲ)和0.68克氢醌依次加入反应混合物中,并加热至130℃。随后将反应混合物保持在该温度下,直至酸值降至5。然后加入一定量甲基·异丁基酮,从而得到(甲基)丙烯酰基化合物F的85%溶液,此溶液的酸值为0.3,粘度20.0厘泊。氰
氨基被保护化合物的制备
氨基被保护化合物A
在氮气氛中,往一个反应器依次加入196.5克二亚丙基三胺、330克甲基·异丁基酮、131.6克甲苯和2.0克甲酸,所得到的混合物加热至沸腾温度,用共沸蒸馏脱除反应生成的水。20小时后,收集到53.9克水(在理论率的99.9%时得到的)。把得到的溶液冷至60℃,然后,于2小时内加入297.7克双酚A的二环氧甘油醚(壳牌化学公司,商标Eponex 828)的甲苯(446.5)溶液。该反应混合物于60℃保持4小时。将所得到的氨基被保护的化合物A的溶液冷却,然后将其贮存而不必纯化。
氨基被保护化合物B
在氮气氛中,往一个反应器中依次加入348.6克1,2-二(3-氨基丙氨基)乙烷、660克甲基·异丁基酮、336克甲苯和3.5克甲酸,随后加热至沸腾温度,用共沸蒸馏除去析出的反应水。6小时后,收集73.9克水(在理论率的100%时得到的)。把得到的溶液冷却至65℃,随后在2小时内,加入124.3克3,4-环氧环己烷羧酸3,4-环氧环己基甲酯。该反应混合物于65℃保持4小时。冷却得到的氨基被保护的化合物B的溶液,然后将其贮存而不必纯化。
氨基被保护化合物C
在氮气氛中,往一个反应器内依次加入255.4克二亚丙基三胺、429克甲基·异丁基酮、228.2克甲苯和2.5克甲酸,随后加热至沸腾,用共沸蒸馏除去析出的反应水。5小时后,收集70.1克水(在理论产率的99.9%时得到的)。将所得到的溶液冷却至40℃,随后,在3小时的时间内加入226克己二醇二丙烯酸酯。该反应混合物于70℃保持2小时。将所得到的氨基被保护的化合物C的溶液冷却,然后将其贮存而不用纯化。
氨基被保护化合物D
在氮气氛中,往一个反应器内依次加入1362.4克异佛尔酮二胺、800克甲基·异丁基酮、720.8克甲苯和27.2克硅铝催化剂,随后加热至沸腾,用共沸蒸馏除去析出的反应水。4小时后,收集144克水(在理论产率的100%时得到的)。所得溶液冷却至60℃,随后,在1小时的时间内加入790.4克三(羟甲基)丙烷三丙烯酸酯。该反应混合物于75℃保持3小时。将得到的氨基被保护的化合物D溶液冷却,然后将其贮存而不用纯化。
氨基被保护的化合物E
在氮气氛中,往一个反应器内依次加入580克1,6-二氨基己烷、434克甲苯和434克正丁醇,随后加热至80℃。在2小时内加入288克马来酸二甲酯。在反应混合物于80℃保持1小时后,将该混合物加热至沸腾温度,用共佛蒸馏除去甲醇。4小时后,收集理论量的甲醇。所得溶液冷却至80℃,随后加入440克甲基·异丁基酮、然后,该反应混合物加热至沸腾温度,用共佛蒸馏除去所生成的水。3小时后,收集72克水(在理论产率的100%的得到的)。将所得到的氨基被保护的化合物F的溶液冷却,然后将其保存而不用纯化。
氨基被保护的化合物F
往一个反应器内依次加入1332克异佛尔酮二异氰酸酯和0.6克二月桂酸二丁锡,随后加热至40℃。加入354克1.6-己二醇的甲基·异丁基酮(531克)溶液。1小时后,得到的产物含异氰酸酯11.5%。在一个单独的
反应周期内,往一个反应器内依次加入707.4克二亚丙基三胺、1188克甲基·异丁基酮、632克甲苯和14.1克硅铝催化剂,随后加热至沸腾温度,用共佛蒸馏除去所产生的反应水。7小时后,收集193.6克水(在理论产率的99.6%时获得的)。所得到的溶液冷却至60℃,然后于2小时内,加入2217克上述单独制备的含有异氰酸酯基的加合物。该反应混合物保持在60℃的温度,然后加入606克正丁醇。最好,将所得到的氨基被保护的化合物F的溶液冷却,过滤后保存。
实例1-13
把表Ⅰ中所列的(甲基)丙烯酸基化合物和氨基被保护的化合物按化学计量混合,配制200份(重量)涂料组合物。表Ⅰ中给出的氨基被保护的化合物G-M分别是异佛尔酮二胺的甲基·异丁基酮亚胺(G)、乙二胺的环己酮酮亚胺(H)、次氮基三(乙胺)的环己酮酮亚胺(K)、3,3′-二甲基-4,4′-二氨基-二环己基甲烷的甲基·异丁基酮亚胺(L)以及异佛尔酮二胺的异丁醛亚胺(M)、表Ⅰ还给出了这些组合物的加工时间(在20℃测量和用小时表示)。然后将这些组合物涂到钢板(Bonder No120)上,其涂层厚度为40毫微米(μm)(干燥后)。得到的涂层不剥落,按表Ⅰ所给的时间固化后,均不留下可见的指压纹(抗指压)。涂层的皮氏(Parsoz)硬度分别在20℃干燥1和7天后测定。涂料抗优质汽油和甲乙酮(MEK)性能的测量是在干燥1周后进行,用少量棉花浸透相应的溶剂放在该涂料板上,随后用硬度2B的铅笔划该涂层。如果只有在与优质汽油接触至少5分钟或3分钟后,才有可见的损伤,则其抗性属于优等或中等。对甲乙酮来说,当在60、45、30和15秒后有可见损伤,则其等级分别为:优秀、良好、较好和一般。
Claims (5)
1、一种液体涂料组合物,它基于至少含2个丙烯酰基或甲基丙烯酰基的化合物和至少含1个由含不多于10个碳原子的醛或酮加以保护的伯氨基的氨基化合物,其特征在于:氨基化合物是含2-24个碳原子的脂族或脂环族胺,或者是环氧氧化合物或异氰酸酯化合物或α,β-烯键不饱和羰基化合物与至少含1个伯氨基及1个能与环氧化合物或异氰酸酯化合物或α,β-烯键不饱和羰基化合物反应的基团的氨基化合物生成的分子量为300-1500的加合物。
2、根据权利要求1的涂料组合物,其特征在于环氧化合物或异氰酸酯化合物或α,β-烯键不饱和羰基化合物是二元的或多元的。
3、根据权利要求1的涂料组合物,其特征在于至少含2个丙烯酰基或甲基丙烯酰基的化合物是一种至少含双官能团的异氰酸酯化合物和一种含2-6个羟基及2-10个碳原子的有羟基官能团的丙烯酸酯的化合物,或者是一种至少含双官能团环氧化合物和一种α,β-烯键不饱和羰基的加合物。
4、根据权利要求3的涂料组合物,其特征在于丙烯酸酯是三(羟甲基)丙烷二丙烯酸酯或季戊四醇三丙烯酸酯。
5、根据权利要求3的涂料组合物,其特征在于至少含双官能团的异氰酸酯化合物是一种含8-36个碳原子的脂族或脂环族二或三异氰酸酯。
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NL8500952 | 1985-03-29 | ||
NL8500952 | 1985-03-29 |
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CN1010318B true CN1010318B (zh) | 1990-11-07 |
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CN86101964A Expired CN1010318B (zh) | 1985-03-29 | 1986-03-27 | 液体涂料组合物和用其涂布基体的方法 |
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US (1) | US4990577A (zh) |
EP (1) | EP0203296B2 (zh) |
JP (1) | JPS61252273A (zh) |
CN (1) | CN1010318B (zh) |
AT (1) | ATE46712T1 (zh) |
AU (1) | AU584689B2 (zh) |
BR (1) | BR8601354A (zh) |
CA (1) | CA1268889A (zh) |
DE (1) | DE3665878D1 (zh) |
DK (1) | DK172448B1 (zh) |
ES (1) | ES8706190A1 (zh) |
FI (1) | FI80468C (zh) |
GR (1) | GR860834B (zh) |
NO (1) | NO175864C (zh) |
ZA (1) | ZA862359B (zh) |
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DE3661834D1 (en) * | 1985-03-29 | 1989-02-23 | Akzo Nv | A liquid coating composition and a process for coating a substrate with such coating composition |
EP0262720B1 (en) * | 1986-09-24 | 1991-04-24 | Akzo N.V. | An aqueous coating composition and a process of coating a substrate with such coating composition |
DE68920665T2 (de) * | 1988-08-09 | 1995-08-31 | Akzo Nobel Nv | Beschichtungsmittel. |
US5177152A (en) * | 1988-08-09 | 1993-01-05 | Akzo N.V. | Water-dilutable, crosslinkable binder resin |
US5071481A (en) * | 1989-01-13 | 1991-12-10 | Akzo N.V. | Low-temperature curable compositions based upon polyaromatic aldehyde group-containing compounds and ketiminized polyamino compounds |
DK0401898T3 (da) * | 1989-06-09 | 1995-01-09 | Akzo Nobel Nv | Flydende belægningspræparat indeholdende en ikke-blokeret monoprimær amin som tværbindingsmiddel |
US5589534A (en) * | 1990-10-16 | 1996-12-31 | Akzo Nobel N.V. | Aqueous coating compositions including a reactive emulsifier |
DE4137615A1 (de) * | 1991-11-15 | 1993-05-19 | Herberts Gmbh | Bindemittelzusammensetzung, deren herstellung, diese enthaltende ueberzugsmittel und deren verwendung |
MY108731A (en) * | 1992-04-16 | 1996-11-30 | Akzo Nv | Aqueous coating compositions |
CA2153317A1 (en) * | 1993-01-06 | 1994-07-21 | Arie Noomen | Oligomeric sterically hindered polyamide crosslinkers and coating compositions containing the same |
WO1995007951A1 (en) * | 1993-09-17 | 1995-03-23 | Akzo Nobel N.V. | Aqueous coating compositions including an amphiphatic emulsifier |
CA2164994A1 (en) * | 1994-12-24 | 1996-06-25 | Heinz Dietholf Becker | Binder composition, coating agents containing it, and use thereof |
US6187374B1 (en) | 1998-09-02 | 2001-02-13 | Xim Products, Inc. | Coatings with increased adhesion |
US6228971B1 (en) * | 1999-06-21 | 2001-05-08 | Ppg Industries Ohio, Inc. | Polymeric imine functional compositions and their use in film-forming compositions |
WO2003074620A1 (en) * | 2002-03-07 | 2003-09-12 | Akzo Nobel Coatings International B.V. | Coating composition comprising an acetal-functional binder |
JP2005535450A (ja) * | 2002-08-13 | 2005-11-24 | アクゾ ノーベル コーティングス インターナショナル ビー ヴィ | チオール官能性化合物を含む多層コーティング系 |
CN102770499B (zh) * | 2010-03-26 | 2015-05-13 | 日本油漆株式会社 | 水性涂料组合物及涂膜形成方法 |
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CA1132289A (en) * | 1977-12-29 | 1982-09-21 | William D. Emmons | Coating, impregnating and adhesive compositions curable at ambient temperature and methods of using them |
JPS5787473A (en) * | 1980-10-07 | 1982-05-31 | Akzo Nv | Ultraviolet curable coating composition |
NZ214999A (en) * | 1985-02-06 | 1988-09-29 | Albright & Wilson Australia | Polyurethane coating composition |
GB2172292A (en) * | 1985-03-08 | 1986-09-17 | Mitsubishi Rayon Co | Acrylic copolymer coatings |
DE3661834D1 (en) * | 1985-03-29 | 1989-02-23 | Akzo Nv | A liquid coating composition and a process for coating a substrate with such coating composition |
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1986
- 1986-03-20 AT AT86103844T patent/ATE46712T1/de not_active IP Right Cessation
- 1986-03-20 DE DE8686103844T patent/DE3665878D1/de not_active Expired
- 1986-03-20 EP EP86103844A patent/EP0203296B2/en not_active Expired - Lifetime
- 1986-03-25 DK DK198601385A patent/DK172448B1/da not_active IP Right Cessation
- 1986-03-25 NO NO861222A patent/NO175864C/no unknown
- 1986-03-26 BR BR8601354A patent/BR8601354A/pt not_active IP Right Cessation
- 1986-03-26 CA CA000505213A patent/CA1268889A/en not_active Expired - Fee Related
- 1986-03-26 ES ES553476A patent/ES8706190A1/es not_active Expired
- 1986-03-27 ZA ZA862359A patent/ZA862359B/xx unknown
- 1986-03-27 FI FI861346A patent/FI80468C/fi not_active IP Right Cessation
- 1986-03-27 CN CN86101964A patent/CN1010318B/zh not_active Expired
- 1986-03-27 AU AU55366/86A patent/AU584689B2/en not_active Ceased
- 1986-03-28 JP JP61068829A patent/JPS61252273A/ja active Granted
- 1986-03-28 GR GR860834A patent/GR860834B/el unknown
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Also Published As
Publication number | Publication date |
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EP0203296B2 (en) | 1997-09-03 |
DK138586D0 (da) | 1986-03-25 |
JPH0553186B2 (zh) | 1993-08-09 |
FI80468C (fi) | 1990-06-11 |
NO175864C (no) | 1994-12-21 |
DE3665878D1 (en) | 1989-11-02 |
CA1268889A (en) | 1990-05-08 |
EP0203296A1 (en) | 1986-12-03 |
US4990577A (en) | 1991-02-05 |
FI80468B (fi) | 1990-02-28 |
ES553476A0 (es) | 1987-06-01 |
FI861346A0 (fi) | 1986-03-27 |
EP0203296B1 (en) | 1989-09-27 |
GR860834B (en) | 1986-07-29 |
DK172448B1 (da) | 1998-07-13 |
DK138586A (da) | 1986-09-30 |
ES8706190A1 (es) | 1987-06-01 |
FI861346L (fi) | 1986-09-30 |
NO861222L (no) | 1986-09-30 |
BR8601354A (pt) | 1986-12-02 |
JPS61252273A (ja) | 1986-11-10 |
AU5536686A (en) | 1986-10-02 |
ATE46712T1 (de) | 1989-10-15 |
NO175864B (zh) | 1994-09-12 |
AU584689B2 (en) | 1989-06-01 |
ZA862359B (en) | 1986-11-26 |
CN86101964A (zh) | 1986-09-24 |
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