CN1863877A - 具有改进的耐擦性的增强涂层 - Google Patents
具有改进的耐擦性的增强涂层 Download PDFInfo
- Publication number
- CN1863877A CN1863877A CNA2004800295638A CN200480029563A CN1863877A CN 1863877 A CN1863877 A CN 1863877A CN A2004800295638 A CNA2004800295638 A CN A2004800295638A CN 200480029563 A CN200480029563 A CN 200480029563A CN 1863877 A CN1863877 A CN 1863877A
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- China
- Prior art keywords
- coating composition
- phenyl
- component
- acid
- ester
- Prior art date
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- 238000000576 coating method Methods 0.000 title claims abstract description 38
- 239000008199 coating composition Substances 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 239000002585 base Substances 0.000 claims description 45
- 150000002148 esters Chemical class 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 41
- 229920005989 resin Polymers 0.000 claims description 39
- 239000011347 resin Substances 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 239000011248 coating agent Substances 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
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- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 5
- 229920006243 acrylic copolymer Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 239000000975 dye Substances 0.000 claims description 5
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- 239000005056 polyisocyanate Substances 0.000 claims description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 229910001507 metal halide Inorganic materials 0.000 claims description 4
- 150000005309 metal halides Chemical class 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012745 toughening agent Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002318 adhesion promoter Substances 0.000 claims description 3
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- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000013008 thixotropic agent Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229920006163 vinyl copolymer Polymers 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229920003180 amino resin Polymers 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000007974 melamines Chemical class 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 abstract description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 abstract 1
- -1 sec.-propyl Chemical group 0.000 description 150
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 48
- 229910052757 nitrogen Inorganic materials 0.000 description 33
- 239000001301 oxygen Substances 0.000 description 30
- 229910052760 oxygen Inorganic materials 0.000 description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 15
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 12
- 229960003742 phenol Drugs 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 239000012964 benzotriazole Substances 0.000 description 11
- 229920005862 polyol Polymers 0.000 description 11
- 150000003254 radicals Chemical class 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 10
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical compound CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 8
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 8
- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 150000003077 polyols Chemical class 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 150000001408 amides Chemical class 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 229940035422 diphenylamine Drugs 0.000 description 7
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 7
- 229940059574 pentaerithrityl Drugs 0.000 description 7
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 7
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 6
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- DKHJONPHCWFBAX-UHFFFAOYSA-N 3-butyl-3h-1-benzofuran-2-one Chemical group C1=CC=C2C(CCCC)C(=O)OC2=C1 DKHJONPHCWFBAX-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
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- 230000004048 modification Effects 0.000 description 5
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- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical compound C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 5
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- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical compound C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 description 3
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- 125000003277 amino group Chemical group 0.000 description 3
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Abstract
本发明公开了一种涂料组合物,包含a)有机成膜粘结剂,和b)通过包括以下步骤的方法而制备的分散在含水或醇溶剂中的小颗粒尺寸无机添加剂:将金属醇盐,金属卤化物或具有结构式I的化合物用碱水解,其中R1是C1-C8烷基,C5-C8环烷基,苯基或C1-C4烷基取代的苯基;R2是C1-C8烷基,和n是0,1,2或3。这些用于保护表面的涂层被增强和具有改进的耐擦性。
Description
本发明涉及包含有机成膜粘结剂,优选涂料,和分散在含水或醇溶剂中的小颗粒尺寸无机添加剂的涂料组合物,和所述添加剂在涂料组合物中作为涂层的增强剂和用于表面的涂料组合物的耐擦性改进剂的用途。
有机涂层一般容易受到磨损和刮擦的损害。无机添加剂如金属氧化物是硬材料和可用于增强涂层,因此增加其对损害的耐性。但无机添加剂的一个缺点是其低可见光透明度。这可导致基材的不透明性或非所需的颜色移动。该缺点可在无机添加剂足够小而不干涉可见光时被克服,即,低于给定尺寸,光衍射可被抑制。小无机颗粒的制备例如已被Stober,Fink和Bohn描述[J.Colloid Interface Sci.1969,26,62]。颗粒越小,它们越往往附聚和聚集。该倾向必须被抑制以实现预期的有益结果。一般,聚集通过官能化这些颗粒,例如通过用具有与基质体系,例如涂层的高相容性的反应性基团改性颗粒的表面而抑制。实际上已经发现,表面改性对于实现有利的作用是重要的。
已经发现一种基于使用无机添加剂以增强涂层的工艺和组合物。惊人地,该无机颗粒基本上无需在其表面被改性以具有与涂层组分的良好相容性。还引人注目的是,如果与尚未用这些无机添加剂处理的涂层相比,这些涂层在低添加剂浓度下就具有显著增加的在固化之后的耐擦性。最后,根据我们的步骤加入的少量添加剂意外地提高涂层的起始光泽和得到透明涂层。该效果为我们的技术提供进一步的优点。
本发明因此涉及涂料组合物,包含
a)有机成膜粘结剂,和
b)通过包括以下步骤的方法而制备的分散在含水或醇溶剂中的小颗粒尺寸无机添加剂:将金属醇盐,金属卤化物或具有结构式I的化合物用碱水解
其中
R1是C1-C8烷基,C5-C8环烷基,苯基或C1-C4烷基取代的苯基;R2是C1-C8烷基,和n是0,1,2或3。
具有最高8个碳原子的烷基是支链或直链基团如,例如,甲基,乙基,丙基,异丙基,n-丁基,仲-丁基,异丁基,叔丁基,2-乙基-丁基,n-戊基,异戊基,1-甲基戊基,1,3-二甲基丁基,n-己基,1-甲基己基,n-庚基,异庚基,1,1,3,3-四甲基丁基,1-甲基庚基,3-甲基庚基,n-辛基或2-乙基己基。
C5-C8环烷基是例如环戊基,环己基,环庚基或环辛基。优选的是环己基。
包含优选1至3,尤其1或2个烷基基团的C1-C4烷基-取代的苯基是,例如,o-,m-或p-甲基苯基,2,3-二甲基苯基,2,4-二甲基苯基,2,5-二甲基苯基,2,6-二甲基苯基,3,4-二甲基苯基,3,5-二甲基苯基,2-甲基-6-乙基苯基,4-叔丁基苯基,2-乙基苯基或2,6-二乙基苯基。
特别有意义的是在固化之后得到透明涂层的透明涂料组合物。
优选,金属醇盐和金属卤化物中的金属是铍,铝,钛,铬,铁,锌,锆,铌或铈。
卤化物是例如氟化物,氯化物,溴化物或碘化物。
优选,醇溶剂是甲醇,乙醇,n-丙醇,异丙醇,n-丁醇,异丁醇或叔丁醇或其混合物。
有意义的是其中碱是含水碱的涂料组合物。
特别有意义的是涂料组合物其中碱是具有结构式II的胺
其中R3,R4和R5相互独立地是氢或C1-C8烷基。
优选组分(b)[无机添加剂]的颗粒尺寸是2至300纳米。
有意义的是这样的涂料组合物,其中在制备组分(b)时,水解在-20至80摄氏度,尤其-10至50摄氏度,例如10-25摄氏度的温度范围内进行。
特别有意义的是这样的组合物,其中在具有结构式I的化合物中,n是0。
尤其提及这样的涂料组合物,其中组分(b)是使用含水氨的具有结构式I的水解化合物,其中,R2是乙基,和n是0。
用于制备组分(b)例如金属醇盐,金属卤化物或具有结构式I的化合物的起始原料是文献中已知的且它们中的大多数可在Fluka或Aldrich购得。
该涂料组合物优选为涂料或油漆,尤其含水涂料或含水油漆。
涂料的例子是大漆,油漆或清漆。这些总是包含有机成膜粘结剂以及其它可有可无的组分。
优选的有机成膜粘结剂是环氧树脂,聚氨酯树脂,氨基树脂,丙烯酸树脂,丙烯酸共聚物树脂,聚乙烯基树脂,酚类树脂,苯乙烯/丁二烯共聚物树脂,乙烯基/丙烯酸共聚物树脂,聚酯树脂,UV-可固化树脂或醇酸树脂,或两种或多种这些树脂的混合物,或这些树脂或这些树脂的混合物的含水碱性或酸性分散体,或这些树脂或这些树脂的混合物的水乳液。
特别有意义的是用于含水涂料组合物的有机成膜粘结剂,如,例如,醇酸树脂;丙烯酸树脂,双组分环氧树脂;聚氨酯树脂;聚酯树脂,通常是饱和;水可稀释的酚类树脂或衍生的分散体;水可稀释的脲树脂;基于乙烯基/丙烯酸共聚物的树脂;和基于,例如,环氧丙烯酸酯的混合体系。
更具体地,醇酸树脂可以是可以风干形式或烘烤体系的形式,视需要与水可稀释的蜜胺树脂结合使用的水可稀释的醇酸树脂体系;该体系也可以是视需要与基于丙烯酸树脂或其共聚物的水分散体,与乙酸乙烯酯,等结合使用的氧化干燥,风干或烘烤体系。
丙烯酸树脂可以是纯丙烯酸树脂,环氧丙烯酸酯混合体系,丙烯酸或丙烯酸酯共聚物,与乙烯基树脂的组合,或与乙烯基单体如乙酸乙烯酯,苯乙烯或丁二烯的共聚物。这些体系可以是风干体系或烘烤体系。
在与合适的多元胺交联剂组合时,水可稀释的环氧树脂具有优异的机械和耐化学性。如果使用液体环氧树脂,可省略将有机溶剂加入含水体系。固体树脂或固体树脂分散体的使用通常需要加入少量溶剂以提高成膜。
优选的环氧树脂是基于芳族多元醇的那些,尤其基于双酚的那些。环氧树脂与交联剂结合使用。后者可尤其是氨基-或羟基-官能化合物,酸,酸酐或Lewis酸。其例子是多元胺,聚氨基酰胺,聚硫化物-基聚合物,多元酚,氟化硼和其配合物化合物,多羧酸,1,2-二羧酸酐或均苯四酸二酸酐。
聚氨酯树脂一方面衍生自具有端羟基基团的聚醚,聚酯和聚丁二烯,和另一方面衍生自脂族或芳族聚异氰酸酯。
优选,聚氨酯一方面由具有端羟基基团的聚醚,聚酯和聚丁二烯,和另一方面由脂族或芳族聚异氰酸酯现场制备。
合适的聚乙烯基树脂的例子是聚乙烯基缩丁醛,聚乙酸乙烯酯或其共聚物。
合适的酚类树脂是合成树脂,在其构造过程中,酚类是基本组分,即尤其是苯酚-,甲酚-,二甲苯酚-和间苯二酚-甲醛树脂,烷基酚类树脂,和酚类与乙醛,糠醛,丙烯醛或其它醛的缩合产物。改性的酚类树脂也是有意义的。
UV(紫外)可固化树脂可包含一个或多个烯烃双键。它们可具有低(单体)或相对高(低聚物)分子量。包含双键的单体的例子是烷基或羟基丙烯酸烷基酯或甲基丙烯酸酯,如丙烯酸甲基,乙基,丁基,2-乙基己基或2-羟乙基酯,丙烯酸异冰片基酯,甲基丙烯酸甲酯或甲基丙烯酸乙酯。其它例子是丙烯腈,丙烯酰胺,甲基丙烯酰胺,N-取代的(甲基)丙烯酰胺,乙烯基酯如乙酸乙烯酯,乙烯基醚如异丁基乙烯基醚,苯乙烯,烷基苯乙烯和卤代苯乙烯,N-乙烯基吡咯烷酮,氯乙烯或偏二氯乙烯。
包含两个或多个双键的单体的例子是乙二醇,丙二醇,新戊基二醇,六亚甲基二醇和双酚A二丙烯酸酯,4,4′-二(2-丙烯酰氧基乙氧基)二苯基丙烷,三羟甲基丙烷三丙烯酸酯,季戊四醇三丙烯酸酯或四丙烯酸酯,丙烯酸乙烯基酯,二乙烯基苯,琥珀酸二乙烯基酯,邻苯二甲酸二烯丙基酯,磷酸三烯丙基酯,异氰尿酸三烯丙基酯或异氰尿酸三(2-丙烯酰基乙基)酯。
相对高分子量(低聚物)多不饱和化合物的例子是丙烯酸酯环氧树脂和丙烯酸酯或乙烯基醚-或环氧-官能聚酯,聚氨酯和聚醚。不饱和低聚物的其它例子一般是由马来酸,邻苯二甲酸和一种或多种二醇制备和具有分子量约500至3000的不饱和聚酯树脂。除此之外,也可使用乙烯基醚单体和低聚物,以及具有聚酯,聚氨酯,聚醚,聚乙烯基醚和环氧化物主链的马来酸酯-封端的低聚物。尤其合适的是例如描述于WO-A-90/01512的携带乙烯基醚基团的聚合物和低聚物的组合。但还合适的是用马来酸和乙烯基醚官能化的单体的共聚物。
也合适的是包含一个或多个自由基可聚合双键的化合物。在这些化合物中,自由基可聚合双键优选为(甲基)丙烯酰基基团的形式。(甲基)丙烯酰基和,相应地,(甲基)丙烯酸在此和以下相应是指丙烯酰基和/或甲基丙烯酰基,和丙烯酸和/或甲基丙烯酸。优选,至少两个可聚合双键以(甲基)丙烯酰基基团的形式存在于分子中。所讨论的化合物可包含,例如,聚(甲基)丙烯酸酯的(甲基)丙烯酰基-官能低聚物和/或聚合物化合物。该化合物的数均分子量可以是例如300至10 000,优选800至10 000。优选包含(甲基)丙烯酰基基团形式的自由基可聚合双键的化合物可通过常规方法,例如通过将聚(甲基)丙烯酸酯与(甲基)丙烯酸反应而得到。这些和其它制备方法在文献中描述和是本领域熟练技术人员已知的。这种类型的不饱和低聚物也可被称作预聚物。
官能化丙烯酸酯也是合适的。通常适用于形成这些官能化丙烯酸酯和甲基丙烯酸酯聚合物的主链(基础聚合物)的单体的例子是丙烯酸酯,丙烯酸甲酯,甲基丙烯酸甲酯,丙烯酸乙酯,甲基丙烯酸乙酯,丙烯酸n-丁酯,甲基丙烯酸正丁基酯,丙烯酸异丁酯,甲基丙烯酸异丁酯,丙烯酸2-乙基己酯,甲基丙烯酸2-乙基己酯等另外,合适量的官能单体在聚合反应过程中共聚以得到官能聚合物。酸-官能化丙烯酸酯或甲基丙烯酸酯聚合物使用酸-官能单体如丙烯酸和甲基丙烯酸而得到。
羟基-官能丙烯酸酯或甲基丙烯酸酯聚合物由羟基-官能单体,如甲基丙烯酸2-羟乙基酯,2-甲基丙烯酸羟丙基酯和3,4-二羟基甲基丙烯酸丁酯形成。环氧-官能化丙烯酸酯或甲基丙烯酸酯聚合物使用环氧-官能单体如甲基丙烯酸缩水甘油酯,甲基丙烯酸2,3-环氧丁酯,甲基丙烯酸3,4-环氧丁酯,甲基丙烯酸2,3-环氧环己酯,甲基丙烯酸10,11-环氧十一烷基酯等而得到。类似地,例如,异氰酸酯-官能化聚合物可例如由异氰酸酯-官能化单体,如间异丙烯基-α,α-二甲基苄基异氰酸酯制备。
尤其合适的化合物是,例如,烯属不饱和单官能或多官能羧酸和多元醇或聚环氧化物的酯,和在链中或在侧基中包含烯属不饱和基团的聚合物,如不饱和聚酯,聚酰胺和聚氨酯和其共聚物,醇酸树脂,聚丁二烯和丁二烯共聚物,聚异戊二烯和异戊二烯共聚物,在侧链中包含(甲基)丙烯酸基团的聚合物和共聚物,以及一种或多种这些聚合物的混合物。
合适的单官能或多官能不饱和羧酸的例子是丙烯酸,甲基丙烯酸,巴豆酸,衣康酸,肉桂酸,马来酸,富马酸,不饱和脂肪酸如亚麻酸或油酸。丙烯酸和甲基丙烯酸是优选的。
但也可使用饱和二羧酸或多羧酸与不饱和羧酸的混合物。合适的饱和二羧酸或多羧酸的例子包括四氯邻苯二甲酸,四溴邻苯二甲酸,邻苯二甲酸,1,2,4-苯三酸,庚烷二羧酸,癸二酸,十二烷二羧酸,六氢邻苯二甲酸,等。
合适的多元醇包括芳族和尤其脂族和环脂族多元醇。芳族多元醇的优选例子是对苯二酚,4,4′-二羟基联苯,2,2-二(4-羟基苯基)丙烷,以及线性酚醛清漆和甲阶酚醛树脂。聚环氧化物的例子是基于前述多元醇,尤其芳族多元醇,和表氯醇的那些。
进一步合适的多元醇包括聚合物和在聚合物链中或在侧基中包含羟基基团的共聚物,如聚乙烯醇和其共聚物或聚羟基甲基丙烯酸烷基酯或其共聚物,例如。包含羟基端基的低聚酯是进一步合适的多元醇。
脂族和环脂族多元醇的例子是具有优选2至12个碳原子的亚烷基二醇,如乙二醇,1,2-或1,3-丙烷二醇,1,2-,1,3-或1,4-丁烷二醇,戊烷二醇,己烷二醇,辛烷二醇,十二烷二醇,二乙二醇,三乙二醇,具有分子量优选200至1500的聚乙二醇,1,3-环戊烷二醇,1,2-,1,3-或1,4-环己烷二醇,1,4-二羟基甲基环己烷,甘油,三(β-羟基乙基)胺,三羟甲基乙烷,三羟甲基丙烷,季戊四醇,二季戊四醇和山梨醇。
多元醇可用一种或多种不同的不饱和羧酸部分或完全酯化,其中部分酯中的游离羟基基团可已被改性的,如用其它羧酸醚化或酯化。这些酯的例子是例如三羟甲基丙烷三丙烯酸酯,三羟甲基乙烷三丙烯酸酯,三羟甲基丙烷三甲基丙烯酸酯,三羟甲基乙烷三甲基丙烯酸酯,四亚甲基二醇二甲基丙烯酸酯,三乙二醇二甲基丙烯酸酯,四乙二醇二丙烯酸酯,季戊四醇二丙烯酸酯,季戊四醇三丙烯酸酯,季戊四醇四丙烯酸酯,二季戊四醇二丙烯酸酯,二季戊四醇三丙烯酸酯,二季戊四醇四丙烯酸酯,二季戊四醇五丙烯酸酯,二季戊四醇六丙烯酸酯,三季戊四醇八丙烯酸酯,季戊四醇二甲基丙烯酸酯,季戊四醇三甲基丙烯酸酯,二季戊四醇二甲基丙烯酸酯,二季戊四醇四甲基丙烯酸酯,三季戊四醇八甲基丙烯酸酯,季戊四醇二衣康酸酯,二季戊四醇三衣康酸酯,二季戊四醇五衣康酸酯,二季戊四醇六衣康酸酯,乙二醇二丙烯酸酯,1,3-丁烷二醇二丙烯酸酯,1,3-丁烷二醇二甲基丙烯酸酯,1,4-丁烷二醇二衣康酸酯,山梨醇三丙烯酸酯,山梨醇四丙烯酸酯,改性的季戊四醇三丙烯酸酯,山梨醇四甲基丙烯酸酯,山梨醇五丙烯酸酯,山梨醇六丙烯酸酯,低聚酯丙烯酸酯和甲基丙烯酸酯,甘油二丙烯酸酯和三丙烯酸酯,1,4-环己烷二丙烯酸酯,具有分子量200至1500的聚乙二醇的二丙烯酸酯和二甲基丙烯酸酯,或其混合物。
合适的UV-可固化树脂包括相同的或不同的不饱和羧酸与具有优选2至6,尤其2至4个氨基基团的芳族,环脂族和脂族多元胺的酰胺。这些多元胺的例子是亚乙基二胺,1,2-或1,3-亚丙基二胺,1,2-,1,3-或1,4-亚丁基二胺,1,5-亚戊基二胺,1,6-亚己基二胺,亚辛基二胺,亚十二烷基二胺,1,4-二氨基环己烷,异佛尔酮二胺,亚苯基二胺,二亚苯基二胺,二-(3-氨基乙基醚,二亚乙基三胺,三亚乙基四胺,二(β-氨基乙氧基)-或二(β-氨基丙氧基)乙烷。进一步合适的多元胺是在侧链中可能包含另外的氨基基团的聚合物和共聚物,和具有氨基端基的低聚酰胺。
这些不饱和酰胺的例子是:亚甲基二丙烯酰胺,1,6-六亚甲基二丙烯酰胺,二亚乙基三胺三甲基丙烯酰胺,二(甲基丙烯酰氨基丙氧基)乙烷,β-甲基丙烯酰氨基甲基丙烯酸乙酯,和N-[(β-羟基乙氧基)乙基]丙烯酰胺。
合适的不饱和聚酯和聚酰胺例如衍生自,马来酸和二醇或二胺。马来酸可已部分被其它二羧酸替代。它们可与烯属不饱和共聚单体,如苯乙烯一起使用。
聚酯和聚酰胺也可衍生自二羧酸和烯属不饱和二醇或二胺,尤其衍生自具有,例如,6至20个碳原子的相对长链的那些。聚氨酯的例子是相应由饱和或不饱和二异氰酸酯和不饱和或饱和二醇合成的那些。
聚丁二烯和聚异戊二烯和其共聚物是已知的。合适的共聚单体的例子是烯烃如乙烯,丙烯,丁烯,己烯,(甲基)丙烯酸酯,丙烯腈,苯乙烯或氯乙烯。在侧链中包含(甲基)丙烯酸酯基团的聚合物也是已知的。它们可包含,例如,线性酚醛清漆基环氧树脂与(甲基)丙烯酸的反应产物,已被(甲基)丙烯酸酯化的乙烯醇或其羟基烷基衍生物的均聚物或共聚物,或用(甲基)丙烯酸羟基烷基酯化的(甲基)丙烯酸酯的均聚物和共聚物。
UV-可固化树脂可单独或以任何所需混合物使用。优选使用多元醇(甲基)丙烯酸酯的混合物。
也可将粘结剂加入本发明组合物,这在光可聚合化合物是液体或粘稠物质时是特别合适的。粘结剂的量可以是例如5-95,优选10-90和尤其40-90%重量,基于总体固体。对粘结剂的选择取决于应用领域和该领域所需的性能,如在含水和有机溶剂体系中的可展开性,基材粘附性,和氧敏感度,例如。
不饱和化合物也可与非光可聚合成膜组分混合使用。这些可以是,例如,物理干燥聚合物或其在有机溶剂中的溶液,如硝基纤维素或乙酰丁酸纤维素,例如。但它们也可以是化学和/或热可固化树脂,如聚异氰酸酯,聚环氧化物或蜜胺树脂,例如。蜜胺树脂不仅是指蜜胺(1,3,5-三嗪-2,4,6-三胺)的缩合物而且是指蜜胺衍生物的缩合物。一般来说,该组分包含基于热塑性或可热固性树脂,主要基于可热固性树脂的成膜粘结剂。其例子是醇酸,丙烯酸,聚酯,酚类,蜜胺,环氧和聚氨酯树脂和其混合物。另外使用的热可固化树脂对于在可光聚合以及热交联的所谓混合体系中的应用是重要的。
组分(a)可包括例如,一种涂料组合物,包含(a1)包含一个或多个自由基可聚合双键和进一步包含至少一个在加成反应和/或缩合反应意义上反应性的其它官能团的化合物(以上已给出例子),(a2)包含一个或多个自由基可聚合双键和进一步包含至少一个在加成反应和/或缩合反应意义上反应性的其它官能团的化合物,所述其它的反应性官能团与组分(a1)的所述其它反应性官能团是互补的或反应性的,(a3)如果需要,至少一种包含至少一个在加成反应和/或缩合反应意义上对除自由基可聚合双键之外来自组分(a1)或组分(a2)的官能团反应性的官能团的单体,低聚物和/或聚合物化合物。
组分(a2)在每种情况下携带对组分(a1)反应性或互补性的基团。在此,可在每种情况下在一种组分中存在不同种类的官能团。在组分(a3)中,可存在包含在加成反应和/或缩合反应意义上反应性的和可与除了自由基可聚合双键之外所存在的(a1)或(a2)官能团反应的官能团的其它组分。组分(a3)不含自由基可聚合双键。这些组合(a1),(a2),(a3)的例子可在WO-A-99/55785中找到。合适的反应性官能团的例子例如选自羟基,异氰酸酯,环氧化物,酸酐,羧基或封端氨基基团。例子已在以上描述。
涂料组合物可另外包含一种或多种例如选自颜料,染料,填料,流动控制剂,分散剂,触变剂,粘附性促进剂,抗氧化剂,光稳定剂和固化催化剂的组分如,例如,以下组分:
1.抗氧化剂
1.1.烷基化一元酚,例如2,6-二-叔丁基-4-甲基苯酚,2-叔丁基-4,6-二-甲基苯酚,2,6-二-叔丁基-4-乙基苯酚,2,6-二-叔丁基-4-n-丁基苯酚,2,6-二-叔丁基-4-异丁基苯酚,2,6-二环戊基-4-甲基苯酚,2-(-甲基环己基)-4,6-二甲基-苯酚,2,6-二十八烷基-4-甲基苯酚,2,4,6-三环己基苯酚,2,6-二-叔丁基-4-甲基-氧基甲基苯酚,是线性的或在侧链中支化的壬基酚类,例如,2,6-二-壬基-4-甲基苯酚,2,4-二甲基-6-(1’-甲基十一-1’-基)苯酚,2,4-二甲基-6-(11-甲基十七-1′-基)苯酚,2,4-二甲基-6-(1′-甲基十三-1′-基)苯酚和其混合物。
1.2.烷基硫代甲基酚类,例如2,4-二辛基硫代甲基-6-叔丁基苯酚,2,4-二辛基-硫代甲基-6-甲基苯酚,2,4-二辛基硫代甲基-6-乙基苯酚,2,6-二-十二烷基硫代甲基-4-壬基苯酚。
1.3.对苯二酚和烷基化对苯二酚,例如2,6-二-叔丁基-4-甲氧基-苯酚,2,5-二-叔丁基对苯二酚,2,5-二-叔戊基对苯二酚,2,6-二苯基-4-十八氧基苯酚,2,6-二-叔丁基对苯二酚,2,5-二-叔丁基-4-羟基茴香醚,3,5-二-叔丁基-4-羟基茴香醚,硬脂酸3,5-二-叔丁基-4-羟基苯基酯,己二酸二-(3,5-二-叔丁基-4-羟基苯基)酯。
1.4.生育酚,例如α-生育酚,β-生育酚,γ-生育酚,δ-生育酚和其混合物(维生素E)。
1.5.羟基化硫代二苯基醚,例如2,2′-硫代二(6-叔丁基-4-甲基苯酚),2,2′-硫代二(4-辛基苯酚),4,4′-硫代二(6-叔丁基-3-甲基苯酚),4,4′-硫代二(6-叔丁基-2-甲基苯酚),4,4′-硫代二-(3,6-二-仲戊基苯酚),4,4′-二(2,6-二甲基-4-羟基苯基)二硫化物。
1.6.亚烷基双酚,例如2,2′-亚甲基二(6-叔丁基-4-甲基苯酚),2,2′-亚甲基二(6-叔丁基-4-乙基苯酚),2,2′-亚甲基二[4-甲基-6-(-甲基环己基)-苯酚],2,2′-亚甲基二(4-甲基-6-环己基苯酚),2,2′-亚甲基二(6-壬基-4-甲基苯酚),2,2′-亚甲基二(4,6-二-叔丁基苯酚),2,2′-乙叉基二(4,6-二-叔丁基苯酚),2,2′-乙叉基二(6-叔丁基-4-异丁基苯酚),2,2′-亚甲基二[6-(α-甲基苄基)-4-壬基苯酚],2,2′-亚甲基二[6-(α,α-二甲基苄基)-4-壬基苯酚],4,4′-亚甲基二-(2,6-二-叔丁基苯酚),4,4′-亚甲基二(6-叔丁基-2-甲基苯酚),1,1-二(5-叔丁基-4-羟基-2-甲基苯基)丁烷,2,6-二(3-叔丁基-5-甲基-2-羟基苄基)-4-甲基-苯酚,1,1,3-三(5-叔丁基-4-羟基-2-甲基苯基)丁烷,1,1-二(5-叔丁基-4-羟基-2-甲基-苯基)-3-n-十二烷基巯基丁烷,乙二醇二(3,3-二(3′-叔丁基-4′-羟基苯基)丁酸酯),二(3-叔丁基-4-羟基-5-甲基-苯基)二环戊二烯,二[2-(1,1-二(3,5-二甲基-2-羟基苯基)丁烷,2,2-二-(3,5-二-叔丁基-4-羟基苯基)丙烷,2,2-二-(5-叔丁基-4-羟基-2-甲基苯基)-4-n-十二烷基巯基丁烷,1,1,5,5-四-(5-叔丁基-4-羟基-2-甲基苯基)戊烷。
1.7.O-,N-和S-苄基化合物,例如3,5,3′,5′-四-叔丁基-4,4′-二羟基二-苄基醚,巯基乙酸十八烷基-4-羟基-3,5-二甲基苄基酯巯基乙酸,十三烷基-4-羟基-3,5-二-叔丁基苄基酯,三(3,5-二-叔丁基-4-羟基苄基)胺,二硫代对苯二甲酸二(4-叔丁基-3-羟基-2,6-二甲基苄基)酯,二(3,5-二-叔丁基-4-羟基苄基)硫化物,巯基乙酸异辛基-3,5-二-叔丁基-4-羟基苄基酯。
1.8.羟基苄基化丙二酸酯,例如丙二酸二-十八烷基-2,2-二-(3,5-二-叔丁基-2-羟基苄基)酯,丙二酸二-十八烷基-2-(3-叔丁基-4-羟基-5-甲基苄基)酯,丙二酸二-十二烷基巯基乙基-2,2-二-(3,5-二-叔丁基-4-羟基苄基)酯,丙二酸二[4-(1,1,3,3-四甲基丁基)苯基]-2,2-二(3,5-二-叔丁基-4-羟基苄基)酯。
1.9.芳族羟基苄基化合物,例如1,3,5-三-(3,5-二-叔丁基-4-羟基-苄基)-2,4,6-三甲基苯,1,4-二(3,5-二-叔丁基-4-羟基苄基)-2,3,5,6-四甲基苯,2,4,6-三(3,5-二-叔丁基-4-羟基苄基)苯酚。
1.10.三嗪化合物,例如2,4-二(辛基巯基)-6-(3,5-二-叔丁基-4-羟基-苯氨基)-1,3,5-三嗪,2-辛基巯基-4,6-二(3,5-二-叔丁基-4-羟基苯氨基)-1,3,5-三嗪,2-辛基巯基-4,6-二(3,5-二-叔丁基-4-羟基苯氧基)-1,3,5-三嗪,2,4,6-三-(3,5-二-叔丁基-4-羟基苯氧基)-1,2,3-三嗪,1,3,5-三-(3,5-二-叔丁基-4-羟基苄基)异氰尿酸酯,1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰尿酸酯,2,4,6-三-(3,5-二-叔丁基-4-羟基苯基乙基)-1,3,5-三嗪,1,3,5-三(3,5-二-叔丁基-4-羟基-苯基丙酰基)-六氢-1,3,5-三嗪,1,3,5-三(3,5-二环己基-4-羟基苄基)异氰尿酸酯。
1.11.苄基膦酸酯,例如二甲基-2,5-二-叔丁基-4-羟基苄基膦酸酯,二乙基-3,5-二-叔丁基-4-羟基苄基膦酸酯,二十八烷基3,5-二叔丁基-4-羟基苄基膦酸酯,二-十八烷基-5-叔丁基-4-羟基-3-甲基苄基膦酸酯,3,5-二-叔丁基-4-羟基苄基膦酸的单乙基酯的钙盐。
1.12.酰基氨基酚类,例如4-羟基金酰苯胺,4-羟基硬脂酰苯胺,N-(3,5-二-叔丁基-4-羟基苯基)氨基甲酸辛基酯.
1.13.β-(3,5-二-叔丁基-4-羟基苯基丙酸与单-或多元醇,如与甲醇,乙醇,n-辛醇,i-辛醇,十八醇,1,6-己烷二醇,1,9-壬烷二醇,乙二醇,1,2-丙烷二醇,新戊二醇,硫代二乙二醇,二乙二醇,三乙二醇,季戊四醇,三(羟基乙基)异氰尿酸酯,N,N′-二(羟基乙基)草酰胺,3-硫代十一醇,3-噻十五醇,三甲基己烷二醇,三羟甲基丙烷,4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯。
1.14.β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与单-或多元醇,如与甲醇,乙醇,n-辛醇,i-辛醇,十八醇,1,6-己烷二醇,1,9-壬烷二醇,乙二醇,1,2-丙烷二醇,新戊二醇,硫代二乙二醇,二乙二醇,三乙二醇,季戊四醇,三(羟基乙基)异氰尿酸酯,N,N′-二-(羟基乙基)草酰胺,3-硫代十一醇,3-噻十五醇,三甲基己烷二醇,三甲基丙烷,4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯。
1.15.β-(3,5-二环己基-4-羟基苯基)丙酸与单-或多元醇,如与甲醇,乙醇,辛醇,十八醇,1,6-己烷二醇,1,9-壬烷二醇,乙二醇,1,2-丙烷二醇,新戊二醇,硫代二乙二醇,二乙二醇,三乙二醇,季戊四醇,三(羟基乙基)异氰尿酸酯,N,N′-二(羟基乙基)草酰胺,3-硫代十一醇,3-噻十五醇,三甲基己烷二醇,三羟甲基丙烷,4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯。
1.16.3,5-二-叔丁基-4-羟基苯基乙酸与单-或多元醇,如与甲醇,乙醇,辛醇,十八醇,1,6-己烷二醇,1,9-壬烷二醇,乙二醇,1,2-丙烷二醇,新戊二醇,硫代二乙二醇,二乙二醇,三乙二醇,季戊四醇,三(羟基乙基)异氰尿酸酯,N,N′-二(羟基乙基)草酰胺,3-硫代十一醇,3-噻十五醇,三甲基己烷二醇,三羟甲基丙烷,4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯。
1.17.β-(3,5-二-叔丁基-4-羟基苄基)丙酸的酰胺如N,N′-二(3,5-二-叔丁基-4-羟基苯基丙酰基)六亚甲基二酰胺,N,N′-二(3,5-二-叔丁基-4-羟基-苯基丙酰基)三亚甲基二酰胺,N,N′-二(3,5-二-叔丁基-4-羟基苯基丙酰基)酰肼,N,N′-二[2-(3-[3,5-二-叔丁基-4-羟基苯基]丙酰基氧基)乙基]草酰胺(由Uniroyal供给的NaugardXL-1)。
1.18.抗坏血酸(维生素C)
1.19.胺类抗氧化剂,例如N,N′-二-异丙基-p-亚苯基二胺,N,N′-二-仲丁基-p-亚苯基二胺,N,N′-二(1,4-二甲基戊基)-p-亚苯基二胺,N,N′-二(1-乙基-3-甲基戊基)-p-亚苯基二胺,N,N′-二(1-甲基庚基)-p-亚苯基二胺,N,N′-二环己基-p-亚苯基二胺,N,N′-二苯基-p-亚苯基二胺,N,N′-二(2-萘基)-p-亚苯基二胺,N-异丙基-N′-苯基-p-亚苯基二胺,N-(1,3-二甲基丁基)-N′-苯基-p-亚苯基二胺,N-(1-甲基庚基)-N′-苯基-p-亚苯基二胺,N-环己基-N′-苯基-p-亚苯基二胺,4-(p-甲苯氨磺酰基)二苯基胺,N,N′-二-甲基-N,N′-二-仲丁基-p-亚苯基二胺,二苯基胺,N-烯丙基二苯基胺,4-异丙氧基二苯基胺,N-苯基-1-萘基胺,N-(4-叔辛基苯基)-1-萘基胺,N-苯基-2-萘基胺,辛基化二苯基胺,例如p,p′-二-叔辛基二苯基胺,4-n-丁基氨基苯酚,4-丁酰基氨基苯酚,4-壬酰基氨基苯酚,4-十二酰基氨基苯酚,4-十八酰基氨基苯酚,二(4-甲氧基苯基)胺,2,6-二-叔丁基-4-二甲基氨基甲基苯酚,2,4′-二氨基二苯基甲烷,4,4′-二氨基二苯基甲烷,N,N,N′,N′-四甲基-4,4′-二氨基二苯基甲烷,1,2-二[(2-甲基苯基)氨基]乙烷,1,2-二(苯基氨基)丙烷,(o-甲苯基)双胍,二[4-(1′,3′-二甲基丁基)苯基]胺,叔辛基化N-苯基-1-萘基胺,单-和二烷基化叔丁基/叔辛基二苯基胺的混合物,单-和二烷基化壬基二苯基胺的混合物,单-和二烷基化十二烷基二苯基胺的混合物,单-和二烷基化异丙基/异己基二苯基胺的混合物,单-和二烷基化叔丁基二苯基胺的混合物,2,3-二氢-3,3-二甲基-4H-1,4-苯并噻嗪,吩噻嗪,单-和二烷基化叔丁基/叔辛基吩噻嗪的混合物,单-和二烷基化叔辛基-吩噻嗪的混合物,N-烯丙基吩噻嗪,二壬基吩噻嗪,单壬基吩噻嗪,单-和二烷基化壬基吩噻嗪的混合物,N,N,N′,N′-四苯基-1,4-二氨基丁-2-烯,一种上述未取代的或取代的二苯基胺与一种上述的未取代或取代的吩噻嗪的混合物。
2.UV吸收剂和光稳定剂
2.1.2-(2′-羟基苄基)苯并***,例如2-(2′-羟基-5′-甲基苯基)-苯并***,2-(3′,5′-二-叔丁基-2′-羟基苯基)苯并***,2-(5′-叔丁基-2′-羟基苯基)苯并***,2-(2′-羟基-5′-(1,1,3,3-四甲基丁基)苯基)苯并***,2-(3′,5′-二-叔丁基-2′-羟基苯基)-5-氯-苯并***,2-(3′-叔丁基-2′-羟基-5′-甲基苯基)-5-氯-苯并***,2-(3′-仲丁基-5′-叔丁基-2′-羟基苯基)苯并***,2-(2′-羟基-4′-辛基氧基苯基)苯并***,2-(3′,5′-二-叔戊基-2′-羟基苯基)苯并***,2-(3′,5′-二-(α,α-二甲基苄基)-2′-羟基苯基)苯并***,2-(3′-叔丁基-2′-羟基-5′-(2-辛基氧基羰基乙基)苯基)-5-氯-苯并***,2-(3′-叔丁基-5′-[2-(2-乙基己基-氧基)-羰基乙基]-2′-羟基苯基)-5-氯-苯并***,2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰基乙基)苯基)-5-氯-苯并***,2-(3′-叔丁基-2′-羟基-5′-(2-甲基-氧基羰基乙基)苯基)苯并***,2-(3′-叔丁基-2′-羟基-5′-(2-辛基氧基羰基-乙基)苯基)苯并***,2-(3′-叔丁基-5′-[2-(2-乙基己基氧基)羰基乙基]-2′-羟基-苯基)苯并***,2-(3′-十二烷基-2′-羟基-5′-甲基苯基)苯并***,2-(3′-叔丁基-2′-羟基-5′-(2-异辛基氧基羰基乙基)苯基苯并***,2,2′-亚甲基-二(4-(1,1,3,3-四甲基丁基)-6-苯并***-2-基苯酚);2-(3′-叔丁基-5′-(2-甲氧基羰基乙基)-2′-羟基苯基)-2H-苯并***与聚乙二醇300的酯交换反应产物;
其中R=3′叔丁基-4′-羟基-5′-2H-苯并***-2-基苯基,2-[2′-羟基-3′-(α,α-二甲基苄基)-5′-(1,1,3,3-四甲基丁基)-苯基]-苯并***;2-[2′-羟基-3′-(1,1,3,3-四甲基丁基)-5′-(α,α-二甲基苄基)-苯基]苯并***。
2.2.2-羟基二苯酮,例如4-羟基,4-甲氧基,4-辛基氧基,4-癸基氧基,4-十二烷基氧基,4-苄基氧基,4,2′,4′-三羟基和2′-羟基-4,4′-二甲氧基衍生物。
2.3.取代的和未取代的苯甲酸的酯,例如水杨酸4-叔丁基苯基酯,水杨酸苯基酯,水杨酸辛基苯基酯,二苯甲酰基间苯二酚,二(4-叔丁基苯甲酰基)间苯二酚,苯甲酰基间苯二酚,3,5-二-叔丁基-4-羟基苯甲酸2,4-二-叔丁基苯基酯,3,5-二-叔丁基-4-羟基苯甲酸十六烷基酯,3,5-二-叔丁基-4-羟基苯甲酸十八烷基酯,3,5-二-叔丁基-4-羟基苯甲酸2-甲基-4,6-二-叔丁基苯基酯。
2.4.丙烯酸酯,例如α-氰基-β,β-二苯基丙烯酸乙基酯,α-氰基-β,β-二苯基丙烯酸异辛基酯,α-甲酯基肉桂酸甲基酯,α-氰基-β-甲基-p-甲氧基-肉桂酸甲基酯,α-氰基-β-甲基-p-甲氧基-肉桂酸丁基酯,α-甲酯基-p-甲氧基内桂酸甲基酯和N-(β-甲酯基-β-氰基乙烯基)-2-甲基二氢吲哚。
2.5.镍化合物,例如2,2′-硫代-二-[4-(1,1,3,3-四甲基-丁基)苯酚])的镍配合物如1∶1或1∶2配合物(有或没有其它的配体如n-丁基胺,三乙醇胺或N-环己基二乙醇胺),镍二丁基二硫代氨基甲酸酯,4-羟基-3,5-二-叔丁基苄基膦酸的单烷基酯,如甲基或乙基酯的镍盐,酮肟,如2-羟基-4-甲基苯基十一烷基酮肟的镍配合物,1-苯基-4-月桂酰基-5-羟基吡唑在有或没有其它配体时的镍配合物。
2.6.空间位阻胺,例如癸二酸二(2,2,6,6-四甲基-4-哌啶基)酯,琥珀酸二(2,2,6,6-四甲基-4-哌啶基)酯,癸二酸二(1,2,2,6,6-五甲基-4-哌啶基)酯,癸二酸二(1-辛基氧基-2,2,6,6-四甲基-4-哌啶基)酯,丙二酸二(1,2,2,6,6-五甲基-4-哌啶基)n-丁基-3,5-二-叔丁基-4-羟基苄基酯,1-(2-羟基乙基)-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的缩合物,N,N′-二(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-叔辛基氨基-2,6-二氯-1,3,5-三嗪的线性或环状缩合物,次氨基三乙酸三(2,2,6,6-四甲基-4-哌啶基)酯,1,2,3,4-丁烷-四羧酸四(2,2,6,6-四-甲基-4-哌啶基)酯,1,1′-(1,2-乙烷二基)-二(3,3,5,5-四甲基哌嗪酮),4-苯甲酰基-2,2,6,6-四甲基哌啶,4-硬脂基氧基-2,2,6,6-四甲基哌啶,丙二酸二(1,2,2,6,6-五甲基哌啶基)-2-n-丁基-2-(2-羟基-3,5-二-叔丁基苄基)酯,3-n-辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮,癸二酸二(1-辛基氧基-2,2,6,6-四甲基哌啶基)酯,琥珀酸二(1-辛基氧基-2,2,6,6-四甲基哌啶基)酯,N,N′-二-(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-吗啉代-2,6-二氨-1,3,5-三嗪的线性或环状缩合物,2-氯-4,6-二(4-n-丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪和1,2-二(3-氨基丙基氨基)-乙烷的缩合物,2-氯-4,6-二-(4-n-丁基氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪和1,2-二-(3-氨基丙基氨基)乙烷的缩合物,8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮,3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮,3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯烷-2,5-二酮,4-十六烷基氧基-和4-硬脂基氧基-2,2,6,6-四甲基哌啶的混合物,N,N′-二(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-环己基氨基-2,6-二氯-1,3,5-三嗪的缩合产物,1,2-二(3-氨基丙基氨基)乙烷和2,4,6-三氨-1,3,5-三嗪的缩合产物以及4-丁基氨基-2,2,6,6-四甲基哌啶(CAS R如No.[136504-96-6]);N-(2,2,6,6-四甲基-4-哌啶基)-n-十二烷基琥珀酰亚胺,N-(1,2,2,6,6-五甲基-4-哌啶基)-n-十二烷基琥珀酰亚胺,2-十一烷基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代-螺[4,5]癸烷,7,7,9,9-四甲基-2-环十一-1-氧杂-3,8-二氮杂-4-氧代螺[4,5]癸烷和表氯醇的反应产物,1,1-二(1,2,2,6,6-五甲基-4-哌啶基氧基羰基)-2-(4-甲氧基苯基)乙烯,N,N′-二-甲酰基-N,N′-二(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺,4-甲氧基-亚甲基-丙二酸与1,2,2,6,6-五甲基-4-羟基哌啶的二酯,聚[甲基丙基-3-氧基-4-(2,2,6,6-四甲基-4-哌啶基)]硅氧烷,马来酸酐-α-烯烃-共聚物与2,2,6,6-四甲基-4-氨基哌啶或1,2,2,6,6-五甲基-4-氨基哌啶的反应产物。
2.7.草酰胺,例如4,4′-二辛基氧基草酰苯胺,2,2′-二乙氧基草酰苯胺,2,2′-二辛基氧基-5,5′-二-叔丁酰苯胺,2,2′-二十二烷基氧基-5,5′-二-叔丁酰苯胺,2-乙氧基-2′-乙基草酰苯胺,N,N′-二(3-二甲基氨基丙基)草酰胺,2-乙氧基-5-叔丁基-2′-乙酰苯胺和其与2-乙氧基-2′-乙基-5,4′-二-叔丁酰苯胺的混合物,o-和p-甲氧基-二取代的草酰苯胺的混合物和o-和p-乙氧基-二取代的草酰苯胺的混合物。
2.8.2-(2-羟基苯基)-1,3,5-三嗪,例如2,4,6-三(2-羟基-4-辛基氧基苯基)-1,3,5-三嗪,2-(2-羟基-4-辛基氧基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,2-(2,4-二羟基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,2,4-二(2-羟基-4-丙基-氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-辛基氧基苯基)-4,6-二(4-甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-十二烷基氧基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-十三烷基氧基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-丁基氧基-丙氧基)苯基]-4,6-二(2,4-二甲基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-辛基氧基-丙基氧基)苯基]-4,6-二(2,4-二甲基)-1,3,5-三嗪,2-[4-(十二烷基氧基/十三烷基氧基-2-羟基丙氧基)-2-羟基-苯基]-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,2-[2-羟基-4-(2-羟基-3-十二烷基氧基-丙氧基)苯基]-4,6-二(2,4-二甲基-苯基)-1,3,5-三嗪,2-(2-羟基-4-己基氧基)苯基-4,6-二苯基-1,3,5-三嗪,2-(2-羟基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪,2,4,6-三[2-羟基-4-(3-丁氧基-2-羟基-丙氧基)苯基]-1,3,5-三嗪,2-(2-羟基苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三嗪,2-{2-羟基-4-[3-(2-乙基己基-1-氧基)-2-羟基丙基氧基]苯基}-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪。
3.金属减活化剂,例如N,N′-二苯基草酰胺,N-水杨基-N′-水杨酰基肼,N,N′-二(水杨酰基)肼,N,N′-二(3,5-二-叔丁基-4-羟基苯基丙酰基)肼,3-水杨酰基氨基-1,2,4-***,二(亚苄基)草酰基二酰肼,草酰苯胺,间苯二甲酰二酰肼,癸二酰基二苯基酰肼,N,N′-二乙酰基己二酰基二酰肼,N,N′-二(水杨酰基)草酰基二酰肼,N,N′-二(水杨酰基)硫代丙酰基二酰肼.
4.亚磷酸酯和亚膦酸酯,例如亚磷酸三苯酯,亚磷酸二苯基烷基酯,亚磷酸苯基二烷基酯,亚磷酸三(壬基苯基)酯,亚磷酸三月桂基酯,亚磷酸三-十八烷基酯,二硬脂基季戊四醇二亚磷酸酯,亚磷酸三(2,4-二-叔丁基苯基)酯,二异癸基季戊四醇二亚磷酸酯,二(2,4-二-叔丁基苯基)季戊四醇二亚磷酸酯,二(2,6-二-叔丁基-4-甲基苯基)-季戊四醇二亚磷酸酯,二异癸基氧基季戊四醇二亚磷酸酯,二(2,4-二-叔丁基-6-甲基苯基)季戊四醇二亚磷酸酯,二(2,4,6-三(叔丁基-苯基)季戊四醇二亚磷酸酯,三硬脂基山梨醇三亚磷酸酯,二亚磷酸四(2,4-二-叔丁基-苯基)4,4′-亚联苯基酯,6-异辛基氧基-2,4,8,10-四-叔丁基-12H-二苯并-[d,g]-1,3,2-二氧杂phosphocin,亚磷酸二(2,4-二-叔丁基-6-甲基苯基)甲基酯,亚磷酸二(2,4-二-叔丁基-6-甲基苯基)乙基酯,6-氟-2,4,8,10-四-叔丁基-12-甲基-二苯并[,g]-1,3,2-二氧杂phosphocin,2,2′,2″-次氨基[三乙基三(3,3′,5,5′-四-叔丁基-1,1′-联苯-2,2′-二基)亚磷酸酯],亚磷酸2-乙基己基(3,3′,5,5′-四-叔丁基-1,1′-联苯-2,2′-二基)酯,5-丁基-5-乙基-2-(2,4,6-三-叔丁基苯氧基)-1,3,2-二氧杂phosphirane。
5.羟基胺,例如,N,N-二苄基羟基胺,N,N-二乙基羟基胺,N,N-二辛基羟基胺,N,N-二月桂基羟基胺,N,N-二十四烷基羟基胺,N,N-二十六烷基羟基胺,N,N-二十八烷基羟基胺,N-十六烷基-N-十八烷基羟基基胺,N-十七烷基-N-十八烷基羟基胺,衍生自氢化牛油胺的N,N-二烷基羟基胺。
6.硝酮,例如,N-苄基-α-苯基-硝酮,N-乙基-α-甲基-硝酮,N-辛基-α-庚基-硝酮,N-月桂基-α-十一烷基-硝酮,N-十四烷基-α-十三烷基-硝酮,N-十六烷基-α-十五烷基-硝酮,N-十八烷基-α-十七烷基-硝酮,N-十六烷基-α-十七烷基-硝酮,N-十八基-α-十五烷基-硝酮,N-十七烷基-α-十七烷基-硝酮,N-十八烷基-α-十六烷基-硝酮,衍生自氢化牛油胺的N,N-二烷基羟基胺所衍生的硝酮。
7.硫代增效剂,例如,硫代二丙酸二月桂基酯或硫代二丙酸二硬脂基酯。
8.过氧化物清除剂,例如β-硫代二丙酸的酯,例如月桂基,硬脂基,肉豆寇基或十三烷基酯,巯基苯并咪唑或2-巯基-苯并咪唑的锌盐,二丁基二硫代氨基甲酸锌,二十八烷基二硫化物,季戊四醇四(β-十二烷基巯基)丙酸酯。
9.碱性共稳定剂,例如,蜜胺,聚乙烯基吡咯烷酮,双氰胺,三烯丙基氰尿酸酯,脲衍生物,肼衍生物,胺,聚酰胺,聚氨酯,高级脂肪酸的碱金属盐和碱土金属盐例如硬脂酸钙,硬脂酸锌,榆树酸镁,硬脂酸镁,蓖麻油酸钠和棕榈酸钾,焦儿茶酚锑或焦儿茶酚锌。
10.填料和增强剂,例如,碳酸钙,硅酸盐,玻璃纤维,玻璃球,石棉,滑石,高岭土,云母,硫酸钡,金属氧化物和氢氧化物,炭黑,石墨,木粉和其它天然产物的粉末或纤维,合成纤维。
11.其它添加剂,例如,增塑剂,润滑剂,乳化剂,颜料,流变添加剂,催化剂,流动控制剂,荧光增白剂,阻燃剂,抗静电剂和发泡剂。
12.苯并呋喃酮和吲哚啉酮,例如公开于U.S.4,325,863;U.S.4,338,244;U.S.5,175,312;U.S.5,216,052;U.S.5,252,643;DE-A-4316611;DE-A-4316622;DE-A-4316876;EP-A-0589839;EP-A-0591102或EP-A-1291384的那些或3-[4-(2-乙酰氧基乙氧基)-苯基]-5,7-二-叔丁基-苯并呋喃-2-酮,5,7-二-叔丁基-3-[4-(2-硬脂酰基氧基乙氧基)苯基]苯并呋喃-2-酮,3,3′-二[5,7-二-叔丁基-3-(4-[2-羟基乙氧基]苯基)苯并呋喃-2-酮],5,7-二-叔丁基-3-(4-乙氧基苯基)苯并呋喃-2-酮,3-(4-乙酰氧基-3,5-二甲基苯基)-5,7-二-叔丁基-苯并呋喃-2-酮,3-(3,5-二甲基-4-戊叔酰氧基苯基)-5,7-二-叔丁基-苯并呋喃-2-酮,3-(3,4-二甲基苯基)-5,7-二-叔丁基-苯并呋喃-2-酮,3-(2,3-二-甲基苯基)-5,7-二-叔丁基-苯并呋喃-2-酮。
其它添加剂例如以浓度0.01至10%加入,相对涂料组合物的总重。
颜料是,例如,二氧化钛,氧化铁,铝青铜或酞菁蓝。
填料的例子是滑石,矾土,硅酸铝,重晶石,云母,和硅石。
流动控制剂和触变剂例如基于改性的膨润土。
粘附性促进剂例如基于改性的硅烷。
合适的固化催化剂是例如光引发剂。适用于根据本发明的工艺的光引发剂原则上是在被电磁力波照射时形成一个或多个自由基的任何化合物和混合物。这些包括由多种引发剂组成的引发剂体系和相互独立地或协同地作用的体系。除了共引发剂,例如胺,硫醇,硼酸盐,烯醇物,膦,羧酸盐和咪唑,也可使用敏感剂,例如吖啶,咕吨,噻嗪烯,香豆素,硫代氧杂蒽酮,三嗪和染料。对这些化合物和引发剂体系的描述可如在Crivello J.V.,Dietliker K.K.,(1999):用于涂层,油墨&油漆的UV & EB配方的化学&技术,和在Bradley G.(编辑)Vol.3:用于自由基和阳离子聚合反应的光引发剂(第二版,JohnWiley & Son Ltd.)中找到。这些化合物和衍生物例如衍生自以下种类的化合物:苯偶姻,苯偶酰缩酮,二苯酮,苯乙酮,羟基烷基苯酮,氨基烷基苯酮,酰基氧化膦,二酰基氧化膦,酰基膦硫化物,二酰基膦硫化物酰基氧基亚氨基酮,烷基氨基-取代的酮,如Michier′s酮,过氧化合物,二腈化合物,卤化苯乙酮,乙醛酸苯基酯,二聚乙醛酸苯基酯,二苯酮,肟和肟酯,硫代氧杂蒽酮,香豆素,二茂铁,钛茂,盐,锍盐,碘盐,重氮盐,硼酸盐,三嗪,二咪唑,聚硅烷和染料。也可使用来自上述种类化合物的化合物相互间的组合和与相应的共引发剂体系和/或敏感剂的组合。
特别有意义的是这样的涂料组合物,其中组分(b)的固体含量是0.01至20%,优选0.05至5%重量,尤其是0.1至5%重量,和最优选0.1至4%重量,基于涂料组合物的总体固体含量的重量。
本发明还涉及一种用于制备涂料组合物的方法,包括将第一组分(a)与组分(b)混合;在正常压力下在温度范围50至140摄氏度下蒸馏溶剂直至最或所有的溶剂被蒸发;和视需要,加入第二组分(a)。
特别有意义的是一种用于制备其中第一组分(a)是多元醇和第二组分(a)是聚异氰酸酯;或第一组分(a)是聚丙烯酸酯和第二组分(a)是蜜胺的涂料组合物的方法。
该涂料可通过常规技术,例如通过喷雾,浸渍,铺展或电沉积而施用到基材单。在许多情况下,使用多个涂层。根据粘结剂是否是物理,化学或氧化干燥树脂或热固化或辐射固化树脂,涂层在室温下下或通过加热(烘烤)或通过照射而固化。
该涂料优选为用于金属基材如,例如,铁,钢,铜,锌或铝,和其合金;塑料;或汽车基材的透明涂层或面涂层。
还有意义的是多组分复合涂料组合物,包括由着色涂料组合物沉积的底涂层,和作为面涂层在底涂层形成的任何一种根据本发明的前述固化组合物。
组分(b)另外具有这样的优点,它有利地影响涂层和金属之间的粘附性,对该新型涂料组合物的储存稳定性没有不利影响,和具有与粘结剂的良好的相容性。
本发明的一个优选的实施方案因此是组分(b)作为涂层的增强剂和用于表面的涂料组合物的耐擦性改进剂的用途。
本发明还涉及一种用于保护基材的方法,包括向其上施用一种包含组分(a)和(b)的涂料组合物并随后干燥和/或固化。
本发明同样涉及一种用于在表面上制备具有改进的耐擦性的增强涂层的方法,包括将该表面用包含组分(a)和(b)的涂料组合物处理,并随后干燥和/或固化。
以下实施例更详细说明本发明。份数和百分数是重量计的。
实施例1:制备Sol 101。
a)制备多元醇组分P1。
54.8g Macrynal SM 510n(60%供给形式,来自Solutia),11.5g乙酸丁基二醇酯,4.70g Solvesso 100(得自Exxon),5.68g甲基异丁基酮,0.07g辛酸锌和0.15g BYK 300(Byk-Chemie,德国,消泡剂)混合得到76.9多元醇组分P1。
b)制备Sol 101。
将64.6g四乙氧基硅烷(Fluka AG,Switzerland)用甲醇稀释至总体积500ml中。将透明溶液与都溶解在总共500ml甲醇中的12.5g氨和37.5g水的溶液同时加入到1升圆底烧瓶中。将溶液搅拌2小时。在该时间之后,动态光散射显示颗粒尺寸23nm。将21.55g该溶液加入29.98g根据实施例1a制备的多元醇组分P1并充分搅拌混合。将混合物通过蒸馏挥发份至最终重量28.06g的具有35.8%残余固体的Sol 101而浓缩。
实施例2:制备Sol 102。
将3.17g根据实施例1b制备的甲醇溶液加入30.02g根据实施例1a制备的多元醇组分P1并充分搅拌混合。将混合物通过蒸馏挥发份至最终重量30.78g的具有40.6%残余固体的Sol 102而浓缩。
实施例3:制备Sol 103。
将11.2g四乙氧基硅烷(Fluka AG,Switzerland)用乙醇稀释至总体积90ml。将透明溶液与都溶解在总共90ml乙醇中的2.59g氨和7.77g水的溶液同时加入到250毫升圆底烧瓶中。将溶液搅拌5小时。在该时间之后,动态光散射/透射电子显微镜检查显示颗粒尺寸100nm。将60.05g该溶液加入51.30g根据实施例1a制备的多元醇组分P1并充分搅拌混合。将混合物通过在42摄氏度下在225mmbar下蒸发而浓缩,得到56.68g具有49.8%残余固体的Sol 103。
实施例4:制备Sol 104。
将27.50g四乙氧基硅烷(Fluka AG,Switzerland)用甲醇稀释至总体积250ml。将透明溶液与都溶解在总共250m甲醇中的8.75g氨和26.25g水的溶液同时加入到500ml圆底烧瓶中。将溶液搅拌2小时。在该时间之后,动态光散射显示颗粒尺寸162nm。将3.43g该溶液加入40.04g根据实施例1a制备的多元醇组分P1并充分搅拌混合。该混合物的重量通过蒸馏挥发份而调节,得到25.75g具有43.1%残余固体的Sol104。
实施例5:制备Sol 105。
将1.2升乙醇和70ml含水氨(25%)在1.5升烧瓶中混合和搅拌5分钟。随后一次加入167.1g(180ml)四乙氧基硅烷并将该溶液在环境温度下搅拌2天。将1升该溶液转移至另一1.5升烧瓶并一次加入31.35g(30ml)3-甲基丙烯酰基氧基丙基-三甲氧基硅烷(Silan A174,Fluka,purum)和搅拌1小时。将氮气首先在室温下下在2小时内吹入该″溶胶″并随后在75摄氏度下吹入直至溶胶的体积降至约250ml。加入100ml己烷并将白色沉淀物通过离心(2000rpm,7min)而分离。沉淀物通过在100ml己烷和30ml乙醇的混合物中再悬浮而纯化和如上通过离心而分离。加入50ml乙酸n-丁酯并将混合物剧烈振荡2小时直至得到硅石纳米颗粒的均相的,稳定的,稍微不透明的分散体。颗粒尺寸是132nm,例如通过透射电子显微镜检查(TEM)测定和固体含量是35wt.%。
实施例6:聚氨酯涂层的耐擦性。
将特定量(参见表1)根据实施例1-4制备的Sols 101-104用2.31gDesmodur N 75(RTM)(异氰酸酯,来自Bayer)处理。将所得透明涂层配方(固体含量50%)随后作为透明面涂层在干膜厚度40μm下施用到预涂有黑色底涂层的铝板(10cm×30cm)上。在施用之后,将透明涂层在80摄氏度下固化45分钟。
涂覆板的耐擦性使用以下方法测定:板的20光泽在固化之后48小时测定(DIN 67 530)。板随后用Amtec Kistler装置进行表1所示周期数的刮擦。在每个试验板的剖擦区域再次测定20光泽。结果汇总于表1。
表1:
实施例 | Sol | wt.-%硅石 | 颗粒尺寸(nm) | 起始光泽 | 在10个周期之后的光泽 | 在20个周期之后的光泽 |
6aa) | - | - | - | 83 | 57 | 34 |
6bb) | 7.80g 101 | 3.7 | 23 | 91 | n.m.c) | 40 |
6cb) | 8.57g 102 | 0.53 | 23 | 90 | 69 | 49 |
6db) | 7.20g 103 | 13.5 | 100 | 74 | 62 | 54 |
6eb) | 7.70g 104 | 0.52 | 162 | 89 | 73 | 69 |
a)对比实施例。
b)根据本发明的实施例。
c)没有测定。
实施例7:UV-可固化涂层的耐擦性。
将特定量(参见表3)的根据实施例5制备的Sol 105加入50g根据表2的树脂混合物中。
表2:
重量份 | 树脂 |
57.3 | Ebecryl 284(RTM)a) |
41.4 | Roskydal UA VP L52308(RTM)b) |
1.3 | Glide 100(RTM)c) |
0.3 | Irgacure 184(RTM)d) |
a)Ebecryl 284(RTM)(UCB化学品),包含88份脂族氨基甲酸乙酯丙烯酸酯和12份己烷二醇二丙烯酸酯。
b)Roskydal UA VP LS2308(RTM)(Bayer AG)是一种脂族氨基甲酸乙酯三/四丙烯酸酯。
c)Glide 100(RTM)(Tego化学品)是一种流动剂。
d)Irgacure 184(RTM)(Ciba Special Chemicals Inc.)是一种α-羟基酮光引发剂。
将包含20wt%硅石的所得透明涂层配方随后作为透明面涂层在干膜厚度40μm下施用到预涂有黑色底涂层的铝板(10cm×30cm)上。在施用之后,将溶剂在80摄氏度下在10分钟内在炉中闪蒸掉。将透明涂层在两个分别120W/cm的汞中压灯下在传送带带度5m/分钟下固化。
涂覆板的耐擦性类似于实施例6测定。结果汇总于表3。
表3:
实施例 | Sol | wt.-%硅石 | 颗粒尺寸(nm) | 起始光泽 | 在10个周期之后的光泽 | 在20个周期之后的光泽 |
7aa) | - | - | - | 86 | 71 | 44 |
7bb) | 11.8g 105 | 20 | 132 | 86 | 74 | 47 |
a)对比实施例。
b)根据本发明的实施例。
Claims (19)
1.一种涂料组合物,包含
a)有机成膜粘结剂,和
b)通过包括以下步骤的方法而制备的分散在含水或醇溶剂中的小颗粒尺寸无机添加剂:将金属醇盐,金属卤化物或具有结构式I的化合物用碱水解
其中
R1是C1-C8烷基,C5-C8环烷基,苯基或C1-C4烷基取代的苯基;R2是C1-C8烷基,和n是0,1,2或3。
2.根据权利要求1的涂料组合物,其中涂层是透明的。
3.根据权利要求1的涂料组合物,其中金属是铍,铝,钛,铬,铁,锌,锆,铌或铈。
4.根据权利要求1的涂料组合物,其中醇溶剂是甲醇,乙醇,n-丙醇,异丙醇,n-丁醇,异丁醇或叔丁醇。
5.根据权利要求1的涂料组合物,其中碱是具有结构式II的胺
其中R3,R4和R5相互独立地是氢或C1-C8烷基。
6.根据权利要求1的涂料组合物,其中无机添加剂的颗粒尺寸是2至300纳米。
7.根据权利要求1的涂料组合物,其中水解在温度-20至80摄氏度下进行。
8.根据权利要求1的涂料组合物,其中n是0。
9.根据权利要求1的涂料组合物,其中组分(b)是使用含水氨的具有结构式I的水解化合物,其中,R2是乙基和n是0。
10.根据权利要求1的涂料组合物,其中涂料组合物是油漆。
11.根据权利要求1的涂料组合物,其中涂料组合物是含水油漆。
12.根据权利要求1的涂料组合物,其中组分(a)是环氧树脂,聚氨酯树脂,氨基树脂,丙烯酸树脂,丙烯酸共聚物树脂,聚乙烯基树脂,酚类树脂,苯乙烯/丁二烯共聚物树脂,乙烯基/丙烯酸共聚物树脂,聚酯树脂,UV-可固化树脂,醇酸树脂,或两种或多种这些树脂的混合物,或这些树脂或这些树脂的混合物的含水碱性或酸性分散体,或这些树脂或这些树脂的混合物的水乳液。
13.根据权利要求1的涂料组合物,另外包含一种或多种选自颜料,染料,填料,流动控制剂,分散剂,触变剂,粘附性促进剂,抗氧化剂,光稳定剂和固化催化剂的组分。
14.根据权利要求1的涂料组合物,其中组分(b)的固体含量是0.01至20%,基于涂料组合物的总体固体含量的重量。
15.一种用于制备根据权利要求1的涂料组合物的方法,包括将第一组分(a)与组分(b)混合;在正常压力下在温度范围50至140摄氏度下蒸馏溶剂直至最或所有的溶剂被蒸发;和视需要,加入第二组分(a)。
16.根据权利要求15的方法,其中第一组分(a)是多元醇和第二组分(a)是聚异氰酸酯;或第一组分(a)是聚丙烯酸酯和第二组分(a)是蜜胺。
17.一种用于保护基材的方法,包括向其中施用根据权利要求1的涂料组合物并随后干燥和/或固化。
18.一种用于在表面上制备具有改进的耐擦性的增强涂层的方法,包括将该表面用根据权利要求1的涂料组合物处理并随后干燥和/或固化。
19.权利要求1所定义的组分(b)作为涂层的增强剂和用于表面的涂料组合物的耐擦性改进剂的用途。
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DE102005014958A1 (de) * | 2005-03-30 | 2006-10-05 | Sensient Imaging Technologies Gmbh | Deckschicht für eletrophotografische Druckwalzen |
KR100744156B1 (ko) | 2006-05-08 | 2007-08-01 | 삼진변압기 주식회사 | 아연 피막제를 이용한 변압기 외함의 방청방법 |
US20090149591A1 (en) * | 2007-12-07 | 2009-06-11 | Yong Yang | Paint Compositions With Low- or Zero-VOC Coalescence Aids and Nano-Particle Pigments |
BRPI0908173A2 (pt) | 2008-02-21 | 2016-12-06 | Basf Se | composição para cuidado pessoal, e, método para fabricar uma composição ou uma formulação antimicrobiana para cuidado pessoal |
KR101142268B1 (ko) * | 2009-12-23 | 2012-05-07 | 주식회사 현대엘이디 | 엘이디 방열체용 백색 전착도료 조성물 및 상기 조성물로 형성된 방열체용 전착 도막 |
US8389591B2 (en) * | 2010-08-10 | 2013-03-05 | Valspar Sourcing, Inc. | Opaque waterborne UV scratch resistant coatings |
FR3045626A1 (fr) * | 2015-12-22 | 2017-06-23 | Michelin & Cie | Bande de roulement comprenant au moins un chelate metallique et/ou un pigment |
US10662273B2 (en) | 2016-12-19 | 2020-05-26 | Celanese International Corporation | Waterborne acrylic dispersions with high biorenewable content |
CN111893783B (zh) * | 2019-05-06 | 2023-01-10 | 台湾永光化学工业股份有限公司 | 水性颜料纺织印花用前处理液及于织物上形成图案的方法 |
TWI766161B (zh) * | 2019-05-06 | 2022-06-01 | 臺灣永光化學工業股份有限公司 | 水性顏料紡織印花用前處理液及於織物上形成圖案的方法 |
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US4439557A (en) * | 1981-05-08 | 1984-03-27 | Toray Industries, Incorporated | Coating compositions |
US4526910A (en) * | 1983-09-06 | 1985-07-02 | Ppg Industries, Inc. | High-solids coating composition for improved rheology control containing inorganic microparticles |
US4522958A (en) * | 1983-09-06 | 1985-06-11 | Ppg Industries, Inc. | High-solids coating composition for improved rheology control containing chemically modified inorganic microparticles |
US4981729A (en) * | 1989-05-25 | 1991-01-01 | Man-Gill Chemical Company | Electroconductive aqueous coating compositions, process, and coated substrates |
US5780525A (en) * | 1997-02-14 | 1998-07-14 | Reliance Electric Industrial Company | Photocurable composition for electrical insulation |
US6169119B1 (en) * | 1997-02-14 | 2001-01-02 | Reliance Electric Technologies, Llc | Metal oxide sols and process for making the same |
US6008291A (en) * | 1997-11-28 | 1999-12-28 | Vianova Resins Ag | Aqueous polyester dispersions of stabilized viscosity, their preparation and their use as binders for water-thinnable coatings |
DE19811790A1 (de) * | 1998-03-18 | 1999-09-23 | Bayer Ag | Nanopartikel enthaltende transparente Lackbindemittel mit verbesserter Verkratzungsbeständigkeit, ein Verfahren zur Herstellung sowie deren Verwendung |
DE19933098A1 (de) * | 1999-07-15 | 2001-01-18 | Herberts Gmbh & Co Kg | Mit Nanopartikeln modifizierte Bindemittel für Überzugsmittel und deren Verwendung |
EP1236765A1 (de) * | 2001-02-28 | 2002-09-04 | hanse chemie GmbH | Siliciumdioxiddispersion |
US6770705B2 (en) * | 2002-02-20 | 2004-08-03 | Ppg Industries Ohio, Inc. | Curable film-forming composition exhibiting improved impact strength and chip resistance |
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BRPI0415378A (pt) | 2006-12-12 |
CA2541996A1 (en) | 2005-05-06 |
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