CN116802227A - 包含非有机锡催化剂的固化性有机硅涂料 - Google Patents
包含非有机锡催化剂的固化性有机硅涂料 Download PDFInfo
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- CN116802227A CN116802227A CN202180093145.9A CN202180093145A CN116802227A CN 116802227 A CN116802227 A CN 116802227A CN 202180093145 A CN202180093145 A CN 202180093145A CN 116802227 A CN116802227 A CN 116802227A
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- amino
- curable composition
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- composition
- metal carboxylate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 239000004447 silicone coating Substances 0.000 title abstract description 8
- -1 carboxylate salt Chemical class 0.000 claims abstract description 125
- 239000000203 mixture Substances 0.000 claims abstract description 78
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 26
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims description 37
- 239000011248 coating agent Substances 0.000 claims description 34
- 239000000758 substrate Substances 0.000 claims description 24
- 150000007942 carboxylates Chemical class 0.000 claims description 23
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 229920001971 elastomer Polymers 0.000 claims description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000005060 rubber Substances 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 9
- 239000004927 clay Substances 0.000 claims description 9
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000454 talc Substances 0.000 claims description 9
- 229910052623 talc Inorganic materials 0.000 claims description 9
- 150000003505 terpenes Chemical class 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 229920002943 EPDM rubber Polymers 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 150000001414 amino alcohols Chemical class 0.000 claims description 7
- 150000004982 aromatic amines Chemical class 0.000 claims description 7
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000010445 mica Substances 0.000 claims description 6
- 229910052618 mica group Inorganic materials 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 239000010456 wollastonite Substances 0.000 claims description 6
- 229910052882 wollastonite Inorganic materials 0.000 claims description 6
- 239000010428 baryte Substances 0.000 claims description 5
- 229910052601 baryte Inorganic materials 0.000 claims description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000123 paper Substances 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- 235000007586 terpenes Nutrition 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052580 B4C Inorganic materials 0.000 claims description 3
- 229910021532 Calcite Inorganic materials 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 241000588731 Hafnia Species 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 3
- 229910033181 TiB2 Inorganic materials 0.000 claims description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910026551 ZrC Inorganic materials 0.000 claims description 3
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 claims description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 3
- 239000010425 asbestos Substances 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005388 borosilicate glass Substances 0.000 claims description 3
- 235000012241 calcium silicate Nutrition 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010433 feldspar Substances 0.000 claims description 3
- 239000005308 flint glass Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000010440 gypsum Substances 0.000 claims description 3
- 229910052602 gypsum Inorganic materials 0.000 claims description 3
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 239000010434 nepheline Substances 0.000 claims description 3
- 229910052664 nepheline Inorganic materials 0.000 claims description 3
- OOAWCECZEHPMBX-UHFFFAOYSA-N oxygen(2-);uranium(4+) Chemical compound [O-2].[O-2].[U+4] OOAWCECZEHPMBX-UHFFFAOYSA-N 0.000 claims description 3
- 239000010451 perlite Substances 0.000 claims description 3
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- 239000003208 petroleum Substances 0.000 claims description 3
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910052903 pyrophyllite Inorganic materials 0.000 claims description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052895 riebeckite Inorganic materials 0.000 claims description 3
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 3
- 229940075630 samarium oxide Drugs 0.000 claims description 3
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 3
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- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 claims description 3
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 3
- FCTBKIHDJGHPPO-UHFFFAOYSA-N uranium dioxide Inorganic materials O=[U]=O FCTBKIHDJGHPPO-UHFFFAOYSA-N 0.000 claims description 3
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- VNTDZUDTQCZFKN-UHFFFAOYSA-L zinc 2,2-dimethyloctanoate Chemical compound [Zn++].CCCCCCC(C)(C)C([O-])=O.CCCCCCC(C)(C)C([O-])=O VNTDZUDTQCZFKN-UHFFFAOYSA-L 0.000 claims description 3
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical group [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 claims description 3
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- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 2
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- 125000003277 amino group Chemical group 0.000 description 6
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Abstract
本文显示并描述涂料组合物。所述涂料组合物是包含无锡催化剂的基于溶剂的有机硅涂料。在实施方案中，所述组合物包含(a)羟基封端的聚二有机基硅氧烷；(b)在有机基聚硅氧烷分子中具有至少两个与硅原子键合的氢原子的有机基聚硅氧烷；(c)包含金属羧酸盐的催化剂，其中所述催化剂不含锡；(d)溶剂；(e)任选地氨基化合物；(f)任选地粘附促进剂；以及(g)任选地填料。
Description
对相关申请的交叉引用
本申请要求于2020年12月6日提交的题为“包含非有机锡催化剂的固化性有机硅涂料(CURABLE SILICONE COATING COMPRISING A NON-ORGANO TIN CATALYST)”的印度专利注册临时申请第202021053086号的优先权和权益，其公开内容通过引用整体并入本文。
技术领域
本发明涉及基于溶剂的有机硅涂料组合物和用其涂布的制品。该组合物使用不含锡的催化剂。该组合物提供基于锡的组合物的替代品，同时提供具有优异性质(包括例如耐磨性和减少的表面摩擦)的涂层。
背景技术
各种类型的基于有机硅的组合物已被用于处理基底表面，以赋予表面各种性质。使用聚有机基硅氧烷处理表面例如橡胶表面(例如，乙烯-丙烯-二烯三元共聚物(EPDM)橡胶)，以提供具有性质例如低(或甚至非)粘性、拒水性、耐磨性和润滑性质的表面。此类涂料可用于各种应用，包括但不限于防风雨条(密封条，weather-strip)应用。在使用基于有机硅涂料中必须考虑的一个问题是提供对基底呈现出良好粘附性(adhesion)和膜强度的材料。
基于锡的材料广泛用于促进基于有机硅的组合物的缩合固化。二月桂酸二丁基锡(DBTDL)由于其与组合物中多种添加剂的相容性以及其在各种固化条件下的催化活性而广受欢迎。然而，基于锡的化合物的使用由于其毒性而正变得受到限制。虽然使用非锡材料来促进涂料组合物的固化可为有益的，但无锡催化剂可能不够通用而无法在不同配制物(配方，formulations)中工作。该催化剂可能未给予这样的替代物：其仍然提供具有合适粘附性以及所需性质(例如耐磨性、减少的摩擦和其它表面改性)的组合物。
发明内容
下面给出本公开的概要以提供对一些方面的基本认识。该概要既不旨在确认核心或关键要素也不旨在定义对实施方案或权利要求的任何限制。此外，该概要可提供对可在本公开的其它部分中更详细描述的一些方面的简化概述。
在一个方面，提供使用无锡催化剂的基于溶剂的有机硅涂料组合物。本催化剂已被发现提供优异的固化并提供具有良好粘附性和耐磨性的涂层。
在一个方面，提供固化性有机硅组合物，其包含：(a)羟基封端的聚二有机基硅氧烷；(b)在有机基聚硅氧烷分子中具有至少两个与硅原子键合的氢原子的有机基聚硅氧烷；(c)包含金属羧酸盐的催化剂，其中所述催化剂不含锡；(d)溶剂；(e)任选地氨基化合物；(f)任选地粘附促进剂；以及(g)任选地填料。
在一个实施方案中，所述金属羧酸盐包含选自锌、铋、钛或者其两种或更多种的混合的金属。
在一个实施方案中，所述金属羧酸盐为羧酸锌。
在一个实施方案中，所述金属羧酸盐为钛酸羧酸盐。
在一个实施方案中，所述金属羧酸盐为羧酸铋。
在一个实施方案中，所述金属羧酸盐选自2-乙基己酸锌、新癸酸锌或其组合。
在根据任意前述实施方案的一个实施方案中，所述氨基化合物(e)选自脂族胺、环状胺、氨基醇、芳族胺、β-氨基羰基化合物、β-氨基腈化合物、氨基有机硅化合物、具有伯氨基的氨基硅烷化合物、或者其两种或更多种的组合。
在根据任意前述实施方案的一个实施方案中，(c)中的金属羧酸盐与氨基化合物(e)的重量比为1:1至约8:1。
在根据任意前述实施方案的一个实施方案中，(c)中的金属羧酸盐与氨基化合物(e)的重量比为2:1至约7:1。
在根据任意前述实施方案的一个实施方案中，(c)中的金属羧酸盐与氨基化合物(e)的重量比为3:1至约5:1。
在根据任意前述实施方案的一个实施方案中，所述催化剂以如下量提供：约0.005(份或重量％)至约10(份或重量％)；约0.01(份或重量％)至约8(份或重量％)；约0.1(份或重量％)至约5(份或重量％)；约0.5(份或重量％)至约5(份或重量％)；或者约1(份或重量％)至约2.5(份或重量％)。
在根据任意前述实施方案的一个实施方案中，所述催化剂以如下量提供：约0.005(份或重量％)至约0.5(份或重量％)；约0.01(份或重量％)至约0.4(份或重量％)；约0.05(份或重量％)至约0.3(份或重量％)；或者约0.1(份或重量％)至约0.25(份或重量％)。
在根据任意前述实施方案的一个实施方案中，所述溶剂选自C1-6烷醇、C1-6二醇、亚烷基二醇的C1-10烷基醚、C3-24亚烷基二醇醚、聚亚烷基二醇、C1-C6羧酸、C1-C6酯、异链烷烃、矿物油(松香水，mineral spirit)、烷基芳族化合物(alkylaromatic)、萜烯、类萜(terpenoid)、甲醛、石脑油、石油馏分、吡咯烷酮、或者其两种或更多种的组合。
在根据任意前述实施方案的一个实施方案中，所述粘附促进剂选自氨基硅烷、环氧基硅烷、巯基硅烷、环氧基官能的聚二甲基硅氧烷流体、或氨基官能的聚二甲基硅氧烷流体、或者其两种或更多种的组合。
在根据任意前述实施方案的一个实施方案中，填料(g)选自矾土(氧化铝，alumina)，氧化镁，二氧化铈，二氧化铪，氧化镧，氧化钕，氧化钐，氧化镨，氧化钍，二氧化铀，氧化钇，氧化锌，氧化锆，氮氧化硅铝，硼硅酸盐玻璃，钛酸钡，碳化硅，硅石，碳化硼，碳化钛，碳化锆，氮化硼，氮化硅，氮化铝，氮化钛，氮化锆，硼化锆，二硼化钛，十二硼化铝，含钡轻火石玻璃(重晶石，baryte)，硫酸钡，石棉，重晶石，硅藻土，长石，石膏，纤维棒石(hormite)，高岭土，云母，霞石正长岩，珍珠岩，叶蜡石，蒙皂石，滑石，蛭石，沸石，方解石，碳酸钙，硅灰石，偏硅酸钙，粘土，硅酸铝，滑石，硅酸镁铝，水合矾土，水合氧化铝，硅石，二氧化硅，二氧化钛，玻璃纤维，玻璃片(鳞片，flake)，粘土，片状剥离粘土(exfoliated)，或者其它高纵横比纤维、棒或片，碳酸钙，氧化锌，氧化镁，二氧化钛，碳酸钙，滑石，云母，硅灰石，石墨，膨胀石墨，金属粉末，碳纤维或晶须，石墨，纳米级纤维，或者其两种或更多种的混合物。
在另一个方面，提供制品，其包含具有表面的主体和设置在所述表面的至少一部分上的涂层，所述涂层由根据任意前述方面和实施方案的固化性有机硅组合物形成。
在一个实施方案中，所述制品的主体由纸、橡胶、塑料或金属形成。
在一个实施方案中，所述制品的主体由EPDM橡胶形成。
在一个实施方案中，所述制品为汽车防风雨条、打印机刀片(printer blade)、橡胶隔振器、或垫圈的形式。
在另一个方面，提供涂覆制品的方法，其包括：将根据权利要求1-14任一项所述的固化性有机硅组合物施加到基底的表面；以及使所述组合物固化以形成涂层。
在一个实施方案中，将固化性水性有机硅组合物在约80℃至180℃的温度下固化。
在一个实施方案中，所述固化性水性有机硅组合物是通过浸涂、喷涂、刷涂、刀涂或辊涂施加的。
以下描述公开了多个说明性方面。一些改进和新的方面可被明确地确认，而其它的可从所述描述明晰。
具体实施方式
现在将介绍示例性实施方案，其实例在附图中说明。将理解，可利用其它实施方案并且可进行结构和功能变化。此外，各种实施方案的特征可被组合或改变。因此，以下描述仅是作为举例说明而呈现的并且决不应限制可对所举例说明的实施方案进行的各种替代和改动。在本公开内容中，众多具体细节提供主题公开内容的透彻理解。应理解，本公开内容的方面可用未必包括本文中描述的所有方面的其它实施方案等实践。
如本文中使用的，措辞“实例”和“示例性(的)”意指例子、或举例说明。措辞“实例”或“示例性(的)”不表示关键或优选的方面或实施方案。措辞“或”意图是包容性的而不是排他性的，除非上下文另有说明。作为一个实例，短语“A使用B或C”包括任何包容性排列(例如，A使用B；A使用C；或A使用B和C)。作为另一件事，冠词“一个”和“一种”通常意图意指“一个(种)或多个(种)”，除非上下文另有说明。
本发明提供基于溶剂的有机硅涂料组合物。该组合物可呈现出良好的对基底表面的粘附性和良好的耐磨性。该组合物使用不含锡的催化剂或固化促进剂。特别地，本组合物提供一种催化剂，该催化剂为金属羧酸盐和任选的氨基化合物的混合物。
所述涂料组合物包含：(a)羟基封端的聚二有机基硅氧烷；(b)在有机基聚硅氧烷分子中具有至少两个与硅原子键合的氢原子的有机基聚硅氧烷；(c)包含金属羧酸盐的催化剂；(d)溶剂；(e)任选地氨基化合物作为助催化剂；(f)任选地粘附促进剂；以及(g)任选地填料。包含金属羧酸盐和潜在的氨基化合物的催化剂已被发现提供良好的固化以及良好的对基底的粘附性和良好的耐磨性。
所述羟基封端的聚二有机基硅氧烷包括参与固化反应的在聚二有机基硅氧烷末端的羟基。附接到硅原子的有机基团(自由基，radical)可独立地选自烷基基团、烯基基团、芳基基团、芳烷基基团、和烃基基团，其具有一个或多个被卤素原子、腈基等替换的氢原子。合适的烷基的实例包括但不限于C1-C10烷基基团。在实施方案中，烷基基团选自甲基、乙基、丙基、丁基、戊基和己基。
所述羟基封端的聚二有机基硅氧烷具有如下粘度：在25℃下50至10,000,000mPa·s；在25℃下100至9,000,000mPa·s；在25℃下250至8,000,000mPa·s；在25℃下500至7,500,000mPa·s；在25℃下1,000至5,000,000mPa·s；在25℃下2,500至2,500,000mPa·s等。在实施方案中，所述羟基封端的聚二有机基硅氧烷具有在25℃下1,000至2,000,000mPa·s的粘度。这里如说明书和权利要求书中其它地方一样，数值可组合形成新的和未具体说明的范围。在25℃下粘度低于50mPa·s的聚二有机基硅氧烷在固化时往往是脆的。在25℃下粘度高于10,000,000mPa·s的聚二有机基硅氧烷增加组合物的整体粘度，这可能导致乳液不太稳定且对于工作起来不实用。粘度是使用Hoepler粘度计或Brookfield粘度计(转子LV 1-6，10rpm)在25℃下评价的。
所述组合物还包括聚有机基氢硅氧烷(b)。聚有机基氢硅氧烷(b)是在有机基聚硅氧烷分子中具有至少两个与硅原子键合的氢原子的有机基聚硅氧烷，并且与聚二有机基硅氧烷(a)的末端羟基进行脱氢缩合以形成硅氧烷网络。聚有机基氢硅氧烷(b)的有机基团可选自关于聚二有机基硅氧烷(a)讨论的有机基团。在实施方案中，聚有机基氢硅氧烷包含甲基基团。聚有机基氢硅氧烷可为线型的、支化的、环状的、或者其两种或更多种的混合。聚有机基氢硅氧烷可具有如下粘度：在25℃下约1至约1000mPa·s；在25℃下约5至约300mPa·s；或在25℃下约10至约100mPa·s。这里如说明书和权利要求书中其它地方一样，数值可组合形成新的和未具体说明的范围。粘度是使用Hoepler粘度计或Brookfield粘度计(转子LV1-6，10rpm)在25℃下评价的。
所述聚有机基氢硅氧烷可以如下量提供：约0.5至20重量份，相对于100重量份的聚二有机基硅氧烷(a)。在实施方案中，所述聚有机基氢硅氧烷以如下量提供：约1至约15重量份，相对于100重量份的聚二有机基硅氧烷(a)；约2.5至约12重量份，相对于100重量份的聚二有机基硅氧烷(a)；或者约5至约10重量份，相对于100重量份的聚二有机基硅氧烷(a)。这里如说明书和权利要求书中其它地方一样，数值可组合形成新的和未具体说明的范围。
所述组合物包括固化催化剂(c)。催化剂(c)包含金属羧酸盐。金属羧酸盐催化剂提供在固化时呈现出良好的粘附性和良好的耐磨性的组合物。在实施方案中，所述金属羧酸盐包括选自锌、铋和/或钛的金属。
在一个实施方案中，所述羧酸盐是衍生自含有至少两个碳原子的单羧酸或羧酸阴离子的羧酸盐。在一个实施方案中，所述金属羧酸盐衍生自式R1COO-的羧酸；其中R1为线型或支化的C1-C30烷基、C6-C10环状基团或C6-C10芳族基团。在一个实施方案中，R1为线型或支化的C10-C30烷基。固化催化剂(c)中合适的锌化合物的非限制性实例包括但不限于2-乙基己酸锌、新癸酸锌、己酸锌，硬脂酸锌、苯甲酸锌、环烷酸锌、月桂酸锌等。合适的铋化合物的非限制性实例包括乙酸铋、油酸铋、辛酸铋或新癸酸铋。合适的钛化合物的非限制性实例包括四正癸酸钛；四正十一烷酸钛；四异丁酸钛；四-2-乙基己酸钛；四-2,2-二甲基丙酸钛；四新癸酸钛；四-3-乙基戊酸钛；四香茅酸钛；四环烷酸钛等。
所述组合物任选地包含胺化合物(e)。虽然不受任何特定理论的约束，但胺化合物(e)可对所述金属羧酸盐(c)起助催化剂的作用，以促进组合物的固化。在一个实施方案中，胺化合物(e)选自伯胺、仲胺、取代的胺、或者其两种或更多种的组合。在实施方案中，胺可选自线型或环状脂族胺、芳族胺、杂环胺、氨基酯化合物、或者其两种或更多种的组合。合适的胺的非限制性实例包括脂族胺、环状胺、氨基醇、芳族胺、β-氨基羰基化合物、β-氨基腈化合物、或者其两种或更多种的组合。伯胺和/或仲胺可指包含烃基(其可为饱和的或不饱和的)的胺化合物。如本文中使用的术语“取代的胺”是指包含如下的胺：附接到胺氮的除烃基之外的基团或附接到胺氮的烃基。
在一个实施方案中，所述催化剂包含选自如下的脂族胺：线型、支化、环状、饱和、不饱和、多官能胺、或者其两种或更多种的组合。胺可以包含一个或多个其它官能团作为化合物的一部分。
在一个实施方案中，所述催化剂包含芳族胺，其中胺官能团直接附接到芳族环、经由间隔物附接、并入到所述环中、或者其两种或更多种的组合。
在一个实施方案中，胺化合物包含一个或多个下式的胺官能团：
其中式(I)为伯胺或仲胺，并且R2选自氢；C1-C15线型、支化、或环状烷基；包含一个或多个选自卤素、N、O或S的取代基的C1-C15线型、支化、或环状烷基；C6-C10芳基；C7-C16线型或支化烷基芳基；C2-C4多亚烷基醚；或者线型或支化的C7-C16杂芳烷基、杂烷基、杂环烷基或杂芳基；并且其中R3和R4独立地选自氢；C1-C15线型、支化、或环状烷基；包含一个或多个选自卤素、N、O或S的取代基的C1-C15线型、支化、或环状烷基；C6-C10芳基；C7-C16线型或支化烷基芳基；C2-C4多亚烷基醚；线型或支化的C7-C16杂芳烷基；杂烷基、杂环烷基、杂芳基，条件是：(i)式(I)的化合物为伯胺或仲胺，以及(ii)氮原子被R3、R4或者R3和R4双取代。
在一个实施方案中，氨基化合物选自脂族胺、环状胺、氨基醇、芳族胺、β-氨基羰基化合物、β-氨基腈化合物、氨基有机硅化合物、具有伯氨基的氨基硅烷化合物、或者其两种或更多种的组合。
在一个实施方案中，所述组合物包含作为伯胺的胺化合物(e)。合适的伯胺的实例包括但不限于烷基胺、取代的烷基胺、环烷基胺、芳族胺等。合适的伯胺的实例包括，但不限于甲胺；乙胺；正丙胺；正己胺；异丙胺；叔辛胺；硬脂胺；环己胺；3-氯-2-羟丙基胺；苄胺；正丁胺；仲丁胺；异丁胺；叔丁胺；三(羟甲基)甲胺；乙醇胺；3-羟基-2-甲基丙胺；异丙醇胺。
在一个实施方案中，胺化合物(e)选自二烷基和取代的二烷基胺、二甲胺、二异丙胺、二丁胺、N-甲基丁基胺、N,N-二烯丙基三亚甲基二胺、二戊胺、二己胺、二辛胺、N-乙基鲸蜡基胺、双十二烷基胺、双十四烷基胺、二蓖麻油基胺、N-异丙基硬脂基胺、N-异戊基己胺、N-乙基辛胺、双十八烷基胺、它们的同系物和类似物、或者其两种或更多种的组合。
在一个实施方案中，胺化合物(e)选自仲环烷基胺，该仲环烷基胺选自二环己胺、N-甲基环己胺、二环戊胺、N-辛基环己胺、N-辛基-3,5,5-三甲基环己胺、及它们的同系物和类似物；以及不饱和仲胺，如二烯丙基胺、N-乙基烯丙基胺、N-辛基烯丙基胺、二油烯基胺、N-异丙基油烯基胺、N-甲基-3,3,5-三甲基-5-环己烯基胺、N-戊基-亚油基胺(linoleylamine)、N-甲基-炔丙基胺、二苯胺、它们的类似物和同系物、或者其两种或更多种的组合。
在一个实施方案中，胺化合物(e)选自氨基醇。氨基醇可为伯胺或仲胺。合适的氨基醇的实例包括但不限于乙醇胺、3-氨基-1-丙醇、2-氨基-1-丙醇、1-氨基-2-丙醇、4-氨基-1-丁醇、2-氨基-1-丁醇、2-氨基-2-甲基-1-丙醇、5-氨基-1-戊醇、2-氨基1-戊醇、6-氨基-2-甲基-2-庚醇、1-氨基-1-环庚烷甲醇、2-氨基环己醇、4-氨基环己醇、1-氨基甲基-1-环己醇、2-(2-氨基乙氧基)乙醇、2-(甲基氨基)乙醇、2-(乙基氨基)乙醇、2-(丙基氨基)乙醇、二乙醇胺、二异丙醇胺、丝氨醇、2-氨基-2-乙基-1,3-丙醇、2-氨基-2-甲基-1,3-丙醇、3-吡咯烷醇、2-哌啶甲醇、2-哌啶乙醇、3-羟基哌啶、4-羟基哌啶、4-氨基苯乙醇、2-氨基-间甲酚、2-氨基-邻甲酚、2-氨基-对甲酚、5-氨基-2-甲氧基苯酚、2-氨基-4-氯苯酚、4-氨基-3-氯苯酚、4-氨基-2,5-二甲基苯酚、酪胺、2-氨基4-苯基苯酚、1-氨基-2-萘酚、4-氨基-1-萘酚、5-氨基-1-萘烷醇(napthanol)、多巴胺等。
在一个实施方案中，胺化合物(e)选自杂环胺，该杂环胺选自哌啶、吡啶、甲基哌嗪、2,2,4,6-四甲基哌啶、2,2,4,6-四甲基四氢吡啶、N-乙基-2,2,4,6-四甲基哌啶、2-氨基嘧啶、2-氨基吡啶、2-(二甲基氨基)吡啶、4-(二甲基氨基)吡啶、2-羟基吡啶、咪唑、2-乙基-4-甲基咪唑、吗啉、N-甲基吗啉、哌啶、2-哌啶甲醇、2-(2-哌啶基)乙醇、哌啶酮、1,2-二甲基-1,4,5,6-四氢嘧啶、氮丙啶、甲氧基甲基二苯胺、尼古丁、戊巴比妥、或者其两种或更多种的组合。
在一个实施方案中，胺化合物(e)选自二乙醇胺、三乙醇胺、N-甲基-1,3-丙二胺、N,N′-二甲基-1,3-丙烷二胺、二亚乙基三胺、三亚乙基四胺、2-(2-氨基乙基氨基)乙醇、3-二甲基氨基丙胺、3-二乙基氨基丙胺、3-二丁基氨基丙胺、3-吗啉丙胺、2-(1-哌啶基)乙胺、和2,4,6-三(二甲基氨基甲基)苯酚、或者其两种或更多种的组合。
在实施方案中，胺化合物(e)选自氨基有机硅或具有氨基的硅烷化合物。在一个实施方案中，氨基有机硅可为式MDxD*yM的化合物，其中M为(R5)(R6)(R7)SiO1/2，D为(R8)(R9)SiO2/2，并且D*为(H2N(CH2)2NH(CH2)3)(CH3)SiO2/2，其中R5、R6、R7、R8和R9独立地选自C1-C30一价烃，x为0-1000，并且y为1-200。在一个实施方案中，氨基有机硅为例如由平均式：(CH3)3SiO[{H2N(CH2)2NH(CH2)3}CH3SiO]100(CH3)3表示的聚有机基硅氧烷。具有氨基的硅烷化合物为具有经由至少一个碳原子与硅原子键合的取代或未取代的氨基的烷氧基硅烷。取代或未取代的氨基的实例包括但不限于，氨基甲基、β-氨基乙基、γ-氨基丙基、δ-氨基丁基、γ-(甲基氨基)丙基、γ-(乙基氨基)丙基、N-(β-氨基乙基)-γ-氨基丙基、N-(β-二甲基氨基乙基)-γ-氨基丙基等。
在一个实施方案中，所述组合物包含金属羧酸盐(c)和氨基化合物(e)两者。在实施方案中，金属羧酸盐(c)和氨基化合物(e)以如下重量比提供：约1:1至约20:1；1.5:1至约15:1；2:1至约10:1；或者约3:1至约5:1。
溶剂(d)可针对具体目的或预期应用按需进行选择。合适溶剂的实例包括烷烃、芳族化合物、C1-6烷醇、C1-6二醇、亚烷基二醇的C1-10烷基醚、C3-24亚烷基二醇醚、聚亚烷基二醇、短链(C1-C6)羧酸、短链(C1-C6)酯、异链烷烃、矿物油、烷基芳族化合物、萜烯、萜烯衍生物、类萜、类萜衍生物、甲醛、石脑油、石油馏分、吡咯烷酮等。合适的烷烃包括但不限于戊烷、己烷、庚烷、癸烷、十二烷等。合适的芳族溶剂包括但不限于苯、甲苯、二甲苯等。合适的烷醇包括但不限于甲醇、乙醇、正丙醇、异丙醇、丁醇、戊醇和己醇、及其异构体。合适的二醇包括但不限于亚甲基、亚乙基、亚丙基和亚丁基二醇。合适的亚烷基二醇醚的实例包括但不限于乙二醇单丙基醚、乙二醇单丁基醚、乙二醇单己基醚、一缩二乙二醇单丙基醚、一缩二乙二醇单丁基醚、一缩二乙二醇单己基醚、丙二醇甲醚、丙二醇乙醚、丙二醇正丙基醚、丙二醇单丁基醚、丙二醇叔丁基醚、一缩二或二缩三丙二醇甲基或乙基或丙基或丁基醚、二醇醚的乙酸酯和丙酸酯。合适的短链羧酸的实例包括但不限于乙酸、乙醇酸、乳酸和丙酸。合适的短链酯的实例包括但不限于乙二醇乙酸酯、和环状或线型挥发性甲基硅氧烷。
所述催化剂可以如下量提供：约0.005(份或重量％)至约10(份或重量％)；约0.01(份或重量％)至约8(份或重量％)；约0.1(份或重量％)至约5(份或重量％)；约0.5(份或重量％)至约5(份或重量％)；或者约1(份或重量％)至约2.5(份或重量％)。在一个实施方案中，所述催化剂以如下量提供：约0.005(份或重量％)至约0.5(份或重量％)；约0.01(份或重量％)至约0.4(份或重量％)；约0.05(份或重量％)至约0.3(份或重量％)；或者约0.1(份或重量％)至约0.25(份或重量％)。所述重量％是基于组合物的总重量。
所述组合物可按需包括其它组分，以为涂料提供额外的益处或性质。在一个实施方案中，所述组合物包含粘附促进剂。合适的粘附促进剂的实例包括但不限于氨基硅烷、环氧基硅烷、环氧基流体、氨基流体等。
所述粘附促进剂可针对具体目的或预期应用按需进行选择。在一个实施方案中，所述粘附促进剂是基于硅烷的粘附促进剂。合适的粘附促进剂的实例包括但不限于氨基硅烷、环氧基硅烷、巯基硅烷、环氧基流体、氨基流体等、或者其两种或更多种的组合。
在一个实施方案中，所述粘附促进剂包含或者选自氨基硅烷。合适的氨基硅烷粘附促进剂的实例包括但不限于，γ-氨基丙基三乙氧基硅烷、γ-氨基丙基三甲氧基硅烷、N-(β-氨基乙基)-γ-氨基丙基三甲氧基硅烷、三氨基-有机官能硅烷、双-[γ-(三甲氧基甲硅烷基)丙基]胺、聚氮酰胺(polyazamide)硅烷、N-(β-氨基乙基)-γ-氨基丙基甲基二甲氧基硅烷、N-苯基-γ-氨基丙基三甲氧基硅烷、N-乙基-γ-氨基异丁基三甲氧基硅烷、4-氨基-3,3-二甲基丁基三甲氧基硅烷、4-氨基-3,3-二甲基丁基甲基三甲氧基硅烷、和4-氨基-3,3-二甲基丁基甲基二甲氧基硅烷。合适的氨基硅烷的一些实例包括可从MomentivePerformance Materials Inc.以商品名SilquestTM A-1100TM、A-1102、A-1106、A-1110、A-1120、A-1130、A-1170、A-1387、A-2120、A-9669、A-LinkTM 15、A-1637、A-2639等获得的那些。
在一个实施方案中，所述粘附促进剂选自环氧基硅烷。合适的环氧基硅烷的实例包括但不限于β-(3,4-环氧基环己基)乙基三甲氧基硅烷、γ-缩水甘油氧基丙基三甲氧基硅烷、β-(3,4-环氧基环己基)-乙基三乙氧基硅烷和γ-缩水甘油氧基丙基甲基二乙氧基硅烷。合适的环氧基硅烷的一些实例包括但不限于可从Momentive Performance Inc.以商品名SilquestTM A-186、A-187TM、CoatosilTM 1770和WetlinkTM 78获得的那些。
在一个实施方案中，粘附促进剂选自巯基硅烷。合适的巯基硅烷的实例包括但不限于3-巯基丙基三甲氧基硅烷、3-巯基丙基三乙氧基硅烷和3-巯基丙基-甲基-二甲氧基硅烷等。
在一个实施方案中，粘附促进剂可选自环氧基流体。合适的环氧基流体的实例包括式Si(Me)3O-(Si(Me)2O)x-(Si(Me)(R10)O)y-Si(Me)3的环氧基改性硅氧烷，其中x为0-1000，y为1-100，且R10为环氧官能团。在一个实施方案中，R5为缩水甘油氧基官能团，并且在实施方案中为
用于粘附促进剂的合适材料的实例为二甲基,甲基3-(环氧乙烷基甲氧基)丙基硅氧烷、γ-氨基丙基三乙氧基硅烷、γ-巯基丙基三甲氧基硅烷及其混合物。
在一个实施方案中，所述粘附促进剂可选自氨基流体。合适的氨基流体的实例包括但不限于3-氨基丙基三乙氧基硅烷、3-(2-氨基乙基氨基)丙基三甲氧基硅烷的低聚物、3-(2-氨基乙基氨基)丙基三甲氧基硅烷和3-缩水甘油基氧基丙基三甲氧基硅烷的反应产物等。
所述涂料组合物可涂覆在任何合适的基底上。合适的基底的实例包括但不限于纸、橡胶、塑料或金属。所述组合物可使用任何合适的方法涂覆，例如但不限于浸涂、喷涂、刷涂、刀涂或辊涂。然后，将涂覆的基底在室温下放置数小时，或者根据基底的耐热性适当加热，以使涂膜固化。对于纸基底，加热条件优选设置为120至180℃的温度10至30秒；对于橡胶基底，80至180℃的温度1至5分钟；以及对于塑料基底，70至150℃的温度30秒至2分钟。
为了改善涂膜对基底的粘着性(adhesiveness)，可将各种类型的硅烷偶联剂单独或作为具有或不具有部分缩合的混合物添加到实施方案的涂料组合物中。
可将其它添加剂或材料添加到所述组合物。此外，相应地，可添加无机或有机紫外线吸收剂以改善耐候性。具有高粘度的聚二甲基硅氧烷可有助于润滑性质。可添加由聚烷基倍半硅氧烷、聚烯烃如聚乙烯、聚碳酸酯树脂等形成的平均粒径为0.01至100μm的有机或无机填料，以提供哑光质地和改善润滑性质。可添加无机颜料以向涂层提供期望的颜色。如有必要，可适当地混合增稠剂、消泡剂和防腐剂。
所述组合物还可包括填料(g)。填料(g)没有特别限制，并且可针对具体目的或预期应用按需进行选择。合适填料的实例包括但不限于聚烯烃，聚氨酯，矾土，氧化镁，二氧化铈，二氧化铪，氧化镧，氧化钕，氧化钐，氧化镨，氧化钍，二氧化铀，氧化钇，氧化锌，氧化锆，氮氧化硅铝，硼硅酸盐玻璃，钛酸钡，碳化硅，硅石，碳化硼，碳化钛，碳化锆，氮化硼，氮化硅，氮化铝，氮化钛，氮化锆，硼化锆，二硼化钛，十二硼化铝，含钡轻火石玻璃，硫酸钡，石棉，重晶石，硅藻土，长石，石膏，纤维棒石，高岭土，云母，霞石正长岩，珍珠岩，叶蜡石，蒙皂石，滑石，蛭石，沸石，方解石，碳酸钙，硅灰石，偏硅酸钙，粘土，硅酸铝，滑石，硅酸镁铝，水合矾土，水合氧化铝，硅石，二氧化硅，二氧化钛，玻璃纤维，玻璃片，粘土，片状剥离粘土，或者其它高纵横比纤维、棒或片，碳酸钙，氧化锌，氧化镁，二氧化钛，碳酸钙，滑石，云母，硅灰石，矾土，氮化铝，石墨，膨胀石墨，金属粉末例如铝、铜、青铜、黄铜等，碳纤维或晶须，石墨，碳化硅，氮化硅，矾土，氮化铝，氧化锌，纳米级纤维例如碳纳米管、氮化硼纳米片、氧化锌纳米管等，以及其两种或更多种的混合物。
还有其它填料包括橡胶状弹性体的球形颗粒。形成细球形颗粒的橡胶状弹性体不限于特定类型，而是使用根据JIS K 6253测量的硬度值(橡胶硬度)小于90、更优选在60至80范围内的弹性材料。当使用硬度为90或更大的硬质或半硬质材料的细颗粒时，不能令人满意地获得在上述漏水状态下防止吱吱声和防止对涂覆的金属表面的损坏的效果。
作为组分(g)的橡胶状弹性体的细球形颗粒，考虑到易于获得和合成，合意地使用交联的基于氨基甲酸酯、交联的基于聚甲基丙烯酸甲酯、交联的基于聚丙烯酸酯、交联的基于聚甲基丙烯酸丁酯和基于有机硅的聚合物。并且，这样的细球形颗粒合意地具有约0.1至约100μm、且更优选约1至约20μm的平均粒径。当平均粒径小于0.1μm时，涂膜具有较差的润滑性质，且当平均粒径超过100μm时，耐磨性变差。
相对于100重量份的羟基封端的聚二有机基硅氧烷(a)，橡胶状弹性体(E)的细球形颗粒的共混量为约10至约150重量份，且更优选约30至约75重量份。将组分(E)的共混量限制到上述范围，因为当共混量小于约10重量份时，涂膜具有差的润滑性质，并且当共混量超过150重量份时，由于涂覆性质劣化，颗粒聚集并且涂膜具有粗糙感。
所述涂料组合物可用于处理基底的表面，以提供固化的涂膜，该固化的涂膜与通过常规的有机硅组合物进行处理相比，对基底具有优异的粘着性和耐磨性。在一个实施方案中，可在橡胶或塑料基底，特别是由发泡或非发泡的EPDM橡胶形成的基底上，形成具有优越的粘着性和耐磨性的涂膜，在所述基底上无法通过使用用于形成非粘着涂膜的常规有机硅组合物来形成具有足够粘着性的涂膜。
具有本催化剂体系的涂料组合物提供可在室温或相对低的温度下形成的固化的涂膜。因此，形成这样的固化的涂膜：其可形成在具有低耐热性的基底以及大的且难以热处理的基底上，并且其对其它物质具有低粘性或不粘性，其具有拒水性和优越的耐磨性。
本发明的涂覆剂组合物可适合用作橡胶部件(例如由EPDM橡胶形成的汽车防风雨条、打印机刀片、橡胶隔振器、建筑材料垫圈等)的表面处理剂。此外，本发明的涂覆剂组合物用于使各种类型的橡胶、塑料等基底具有低/不粘性和良好的拒水性。
以上已经描述的内容包括本说明书的实例。当然，不可能为了描述本说明书的目的而描述组分或方法的每一个可想到的组合，但是本领域普通技术人员可认识到，本说明书的许多其它组合和排列是可能的。因此，本说明书意图涵盖落在所附权利要求的精神和范围内的所有此类改变、改动和变型。此外，就术语“包括”用于详细的描述或权利要求中而言，此类术语意图以与术语“包含”类似的方式而为包容性的，如同“包含”当在权利要求中作为过渡词使用时所解释的那样。
实施例
在非水性防风雨条涂料配制物中评价非有机锡催化剂
实施例1-22：评价作为催化剂(c)的二异丙氧二(乙氧乙酰乙酰)合酞(diisopropoxy-bisethylacetoacetatotitanate)和K-KAT XK-661(羧酸锌)
在非水性防风雨条涂料配制物中测试非有机锡催化剂二异丙氧二(乙氧乙酰乙酰)合酞(Tyzor PITA)。将100份配制物1与4份配制物2混合，所述配制物1包含73％的二甲苯、17％的粘度为15Pa.s的硅烷醇封端的聚二甲基硅氧烷、8％的粒度为5微米的甲基倍半硅氧烷球形颗粒、1.5％的石墨和0.5％的炭黑，所述配制物2包含在90％二甲苯中的10％的粘度为25mPa.s的甲基氢聚硅氧烷。向其中加入粘附促进剂配制物3并再混合，所述粘附促进剂配制物3包含70％异丙醇、5％的γ-巯基丙基三甲氧基硅烷、15％的γ-氨基丙基三乙氧基硅烷和10％的分子量为20,000的环氧基官能的聚二甲基硅氧烷。在该配制物中以不同浓度(作为实施例2-16)使用钛酸羧酸盐Tyzor PITA(100％活性物)作为非有机锡催化剂的实例。Tyzor PITA可在市场上由Dorf Ketal Specialty Catalyst Private Limited供应获得。在该配制物中以不同浓度(作为实施例17-22)测试羧酸锌K-KAT XK-661(在乙酸正丁酯中的80％活性物)。K-KAT XK-661可从King Industries获得。将各配制物在储存2小时后喷涂在预热的EPDM橡胶基底(80℃)上。将经涂覆的橡胶基底在80℃下固化10分钟，并在24小时后测试性质。将测试结果与实施例1进行比较，实施例1是包含式4的有机锡催化剂的标准配制物，所述有机锡催化剂包含在63％的作为溶剂的甲苯中的37％的二乙酸二丁基锡。
测试结果汇总在表1和表2中。实施例2-6是高度反应性的，并且在180分钟内形成凝胶。实施例1和7-14稳定≥180分钟，且因此测试了固化性、耐磨性、表面光洁度(surfacefinish)和摩擦时的噪音水平。如表1中所示的实施例通过用浸泡在甲苯中的棉花芽轻轻摩擦涂层来评价其固化。如果涂层完全固化，其将不会被棉花芽除去且不会有任何黑色痕迹。将两块经涂覆的橡胶基底相互摩擦，并观察是否存在划痕和产生吱吱声噪音。类似地，将经涂覆的表面与湿的玻璃片摩擦并倾听吱吱声。包含优化浓度的Tyzor PITA和K-KAT XK-661的实施例显示出与包含锡催化剂的参考实施例1类似的性质。结果表明，非有机锡催化剂例如金属羧酸盐如钛酸羧酸盐和羧酸锌是适用于非水性防风雨条涂料的非有机锡催化剂。
表1.包含二异丙氧二(乙氧乙酰乙酰)合酞作为催化剂的非水性防风雨条涂料实施例的组成和性质
(*)外观是与已知标准物的目视比较。
(**)固化测试根据ASTM-D4752进行
(***)摩擦掉色测定(crockmeter)根据ISO 105D02/SAE J861进行
(****)光泽根据ASTM-D523进行
(*****)噪音是在所产生的样品和由顾客用实施例1中描述的参考涂料在线产生的剖面(profile)之间的比较。
表2.包含K-KAT XK-661(羧酸锌)作为催化剂的非水性防风雨条涂料实施例的组成和性质
K-KAT XK-661在己烷中稀释1:10
(*)外观是与已知标准物的目视比较。
(**)固化测试根据ASTM-D4752进行
(***)摩擦掉色测定根据ISO 105D02/SAE J861进行
(****)光泽根据ASTM-D523进行
(*****)噪音是在所产生的样品和由顾客用实施例1中描述的参考涂料在线产生的剖面之间的比较。
催化剂命名
(3)DCHA：二环己胺
(4)HDDAc-2EHAm：1,6己二醇二丙烯酸酯-2-乙基己胺(β-氨基酯)
(5)2EHAc-BAm：2-乙基己基丙烯酸酯-丁胺(β-氨基酯)
(6)K-KAT XK-661：羧酸锌-络合物
(7)Tyzor PITA：二异丙氧二(乙氧乙酰乙酰)合酞
前面的描述确定涂料组合物的各种非限制性实施方案。本领域技术人员和可实施和利用本发明的人们可想到多种改动。所公开的实施方案仅用于说明目的并且不意图限制本发明的范围或者权利要求中阐述的主题。
Claims (20)
1.固化性有机硅组合物，其包含：
(a)羟基封端的聚二有机基硅氧烷；
(b)在有机基聚硅氧烷分子中具有至少两个与硅原子键合的氢原子的有机基聚硅氧烷；
(c)包含金属羧酸盐的催化剂，其中所述催化剂不含锡；
(d)溶剂；
(e)任选地氨基化合物；
(f)任选地粘附促进剂；以及
(g)任选地填料。
2.根据权利要求1所述的固化性组合物，其中所述金属羧酸盐包含选自锌、铋、钛或者其两种或更多种的混合的金属。
3.根据权利要求1所述的固化性组合物，其中所述金属羧酸盐为羧酸锌。
4.根据权利要求1所述的固化性组合物，其中所述金属羧酸盐为钛酸羧酸盐。
5.根据权利要求1所述的固化性组合物，其中所述金属羧酸盐为羧酸铋。
6.根据权利要求1所述的固化性组合物，其中所述金属羧酸盐选自2-乙基己酸锌、新癸酸锌或其组合。
7.根据权利要求1-6任一项所述的固化性组合物，其中所述氨基化合物(e)选自脂族胺、环状胺、氨基醇、芳族胺、β-氨基羰基化合物、β-氨基腈化合物、氨基有机硅化合物、具有伯氨基的氨基硅烷化合物、或者其两种或更多种的组合。
8.根据权利要求1-7任一项所述的固化性组合物，其中(c)中的金属羧酸盐与氨基化合物(e)的重量比为1:1至约8:1。
9.根据权利要求1-7任一项所述的固化性组合物，其中(c)中的金属羧酸盐与氨基化合物(e)的重量比为2:1至约7:1。
10.根据权利要求1-7任一项所述的固化性组合物，其中(c)中的金属羧酸盐与氨基化合物(e)的重量比为3:1至约5:1。
11.根据权利要求1-10任一项所述的固化性组合物，其中所述溶剂选自C1-6烷醇、C1-6二醇、亚烷基二醇的C1-10烷基醚、C3-24亚烷基二醇醚、聚亚烷基二醇、C1-C6羧酸、C1-C6酯、异链烷烃、矿物油、烷基芳族化合物、萜烯、类萜、甲醛、石脑油、石油馏分、吡咯烷酮、或者其两种或更多种的组合。
12.根据权利要求1-11任一项所述的固化性组合物，其中所述粘附促进剂选自氨基硅烷、环氧基硅烷、巯基硅烷、环氧基官能的聚二甲基硅氧烷流体、或氨基官能的聚二甲基硅氧烷流体、或者其两种或更多种的组合。
13.根据权利要求1-12任一项所述的固化性组合物，其包含选自如下的填料(g)：矾土，氧化镁，二氧化铈，二氧化铪，氧化镧，氧化钕，氧化钐，氧化镨，氧化钍，二氧化铀，氧化钇，氧化锌，氧化锆，氮氧化硅铝，硼硅酸盐玻璃，钛酸钡，碳化硅，硅石，碳化硼，碳化钛，碳化锆，氮化硼，氮化硅，氮化铝，氮化钛，氮化锆，硼化锆，二硼化钛，十二硼化铝，含钡轻火石玻璃，硫酸钡，石棉，重晶石，硅藻土，长石，石膏，纤维棒石，高岭土，云母，霞石正长岩，珍珠岩，叶蜡石，蒙皂石，滑石，蛭石，沸石，方解石，碳酸钙，硅灰石，偏硅酸钙，粘土，硅酸铝，滑石，硅酸镁铝，水合矾土，水合氧化铝，硅石，二氧化硅，二氧化钛，玻璃纤维，玻璃片，粘土，片状剥离粘土，或者其它高纵横比纤维、棒或片，碳酸钙，氧化锌，氧化镁，二氧化钛，碳酸钙，滑石，云母，硅灰石，石墨，膨胀石墨，金属粉末，碳纤维或晶须，石墨，纳米级纤维，或者其两种或更多种的混合物。
14.制品，其包含具有表面的主体和设置在所述表面的至少一部分上的涂层，所述涂层由根据权利要求1-13任一项所述的固化性组合物形成。
15.根据权利要求14所述的制品，其中所述制品的主体由纸、橡胶、塑料或金属形成。
16.根据权利要求14所述的制品，其中所述制品的主体由EPDM橡胶形成。
17.根据权利要求14所述的制品，其中所述制品为汽车防风雨条、打印机刀片、橡胶隔振器、或垫圈的形式。
18.涂覆制品的方法，其包括：
将根据权利要求1-14任一项所述的固化性有机硅组合物施加到基底的表面；以及使所述组合物固化以形成涂层。
19.根据权利要求18所述的方法，其中将固化性水性有机硅组合物在约80℃至180℃的温度下固化。
20.根据权利要求18或19所述的方法，其中所述固化性水性有机硅组合物是通过浸涂、喷涂、刷涂、刀涂或辊涂施加的。
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