CN101611101A - 用2-羟基苯基三嗪稳定的着色透明涂层uv - Google Patents
用2-羟基苯基三嗪稳定的着色透明涂层uv Download PDFInfo
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- CN101611101A CN101611101A CNA2007800479048A CN200780047904A CN101611101A CN 101611101 A CN101611101 A CN 101611101A CN A2007800479048 A CNA2007800479048 A CN A2007800479048A CN 200780047904 A CN200780047904 A CN 200780047904A CN 101611101 A CN101611101 A CN 101611101A
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- 239000000049 pigment Substances 0.000 claims abstract description 117
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- 238000010521 absorption reaction Methods 0.000 claims abstract description 36
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- 150000001721 carbon Chemical group 0.000 claims description 169
- -1 2,2,6,6-tetramethyl-piperidyl Chemical group 0.000 claims description 126
- 125000000217 alkyl group Chemical group 0.000 claims description 82
- 125000001118 alkylidene group Chemical group 0.000 claims description 35
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- 239000001257 hydrogen Substances 0.000 claims description 30
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- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 claims description 4
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 4
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
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- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 claims description 3
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- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 2
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- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- MQOCIYICOGDBSG-UHFFFAOYSA-M potassium;hexadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCC([O-])=O MQOCIYICOGDBSG-UHFFFAOYSA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical compound N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 description 1
- LLBIOIRWAYBCKK-UHFFFAOYSA-N pyranthrene-8,16-dione Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C=C4C5=CC=CC=C5C(=O)C5=C4C4=C3C2=C1C=C4C=C5 LLBIOIRWAYBCKK-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
- ORIHZIZPTZTNCU-YVMONPNESA-N salicylaldoxime Chemical compound O\N=C/C1=CC=CC=C1O ORIHZIZPTZTNCU-YVMONPNESA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- IJRHDFLHUATAOS-DPMBMXLASA-M sodium ricinoleate Chemical compound [Na+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O IJRHDFLHUATAOS-DPMBMXLASA-M 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 239000012747 synergistic agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- 125000000297 undecanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([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 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KJPJZBYFYBYKPK-UHFFFAOYSA-N vat yellow 1 Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3N=C4C5=CC=CC=C5C(=O)C5=C4C4=C3C2=C1N=C4C=C5 KJPJZBYFYBYKPK-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- WGVKWNUPNGFDFJ-DQCZWYHMSA-N β-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C WGVKWNUPNGFDFJ-DQCZWYHMSA-N 0.000 description 1
- 239000002478 γ-tocopherol Substances 0.000 description 1
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 description 1
- 239000002446 δ-tocopherol Substances 0.000 description 1
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
本发明涉及着色透明涂料组合物,该组合物包含(a)2-羟基苯基三嗪UV吸收剂、(b)颜料和(c)粘合剂,还涉及通过将这样的组合物施涂到基底上而获得的涂层。
Description
本发明涉及着色透明涂料组合物,该组合物包含(a)2-羟基苯基三嗪UV吸收剂、(b)颜料和(c)粘合剂,还涉及通过将这样的组合物施涂到基底上而获得的涂层。
本发明的着色透明涂层特别是如果与未着色的透明涂层相比,其能够表现出增加的色度、提高的颜色光彩和更佳的耐久性。而且,这些着色透明涂层特别是如果与未着色的透明涂层相比,在经历气候变化之后能够表现出较少的变色。
本发明涉及一种着色透明涂料组合物,其包含:
(a)至少一种2-羟基苯基三嗪UV吸收剂,
(b)至少一种颜料,其选自喹吖啶酮,二酮基-吡咯并吡咯,喹吖啶酮/二酮基-吡咯并吡咯,异吲哚啉酮,酞菁,BiV,苝,蒽醌红,阴丹酮蓝色,偶氮甲碱Cu络合物,单偶氮Ni络合物,喹诺酞酮(quinophthalone),异吲哚啉和萘酚AS及其混合物(例如晶体混合物)和固溶体,和
(c)至少一种粘合剂。
这些颜料的混合物和固溶体(b)被理解为包括两种或者多种的二酮基-吡咯并吡咯颜料的、两种或多种的喹吖啶酮颜料的和两种或多种的喹吖啶酮/二酮基-吡咯并吡咯颜料的混合物例如晶体混合物和固溶体。
着色透明涂料组合物被理解为当施涂到基底时,该着色透明涂层不是如透明涂层那样是完全透明和无色的,也不是如典型的颜料化涂层那样是完全不透明的。着色透明涂层是透明和着色的或者是半透明和着色的。
例如,2-羟基苯基三嗪UV吸收剂(a)是式(I),(II),(III),(IV),(V)或者(VI),优选是式(I),(II)或者(III)
其中
X和Y独立地是苯基、萘基、芘基、菲基或者荧蒽基,或者是被下面的基团取代的所述的苯基、所述的萘基、所述的芘基、所述的菲基或者所述的荧蒽基:被1-3个1-6个碳原子的烷基、卤素、羟基或者用1-6个碳原子的烷氧基或者用其混合物;或者独立地是Z1或者Z2;
X,X′,Y和Y′相同或者不同,并且定义同X和Y;
R1是氢,1-24个碳原子的直链或者支链烷基,5-12个碳原子的环烷基,7-15个碳原子的苯基烷基,卤素,-SR3,-SOR3或者-SO2R3;或者是被下面的基团取代的所述的烷基、所述的环烷基或者所述的苯基烷基:被1-3个卤素,-R4,-OR5,-N(R5)2,-COR5,-COOR5,-OCOR5,-CN,-NO2,-SR5,-SOR5,-SO2R5或者-P(O)(OR5)2,吗啉基,哌啶基,2,2,6,6-四甲基哌啶基,哌嗪基或者N-甲基哌啶基基团或者其组合;或者是被下面的基团间断的所述的烷基或者所述的环烷基:1-4个亚苯基,-O-,-NR5-,-CONR5-,-COO-,-OCO-或者-CO基团或者其组合;或者是被上述基团组合取代和间断取代和间断的所述的烷基或者所述的环烷基;
R1,R1′和R1″相同或者不同,并且定义同R1;
R2是氢,1-24个碳原子的直链或者支链烷基或者5-12个碳原子的环烷基;或者是被下述基团取代的所述的烷基或者所述的环烷基:1-4个卤素,环氧基,缩水甘油氧基,呋喃氧基,-R4,-OR5,-N(R5)2,-CON(R5)2,-COR5,-COOR5,-OCOR5,-OCOC(R5)=C(R5)2,-C(R5)=CCOOR5,-CN,-NCO,或者
或者其组合;或者是被下面的基团间断的所述的烷基或者所述的环烷基:1-4个环氧基,-O-,-NR5-,-CONR5-,-COO-,-OCO-,-CO-,-C(R5)=C(R5)COO-,-OCOC(R5)=C(R5)-,-C(R5)=C(R5)-,亚苯基或者亚苯基-G-亚苯基,其中G是-O-,-S-,-SO2-,-CH2-或者-C(CH3)2-或者其组合,或者是被上述基团的组合取代和间断取代和间断的所述的烷基或者所述的环烷基;或者R2是-SO2R3或者-COR6;
R2,R2′和R2″相同或者不同,并且定义同R2;
R3是1-20个碳原子的烷基,3-18个碳原子的链烯基,5-12个碳原子的环烷基,7-15个碳原子的苯基烷基,6-10个碳原子的芳基或者是被1或2个1-4个碳原子的烷基取代的所述的芳基;
R4是6-10个碳原子的芳基或者是被1-3个卤素,1-8个碳原子的烷基,1-8个碳原子的烷氧基或者其组合取代的所述的芳基;5-12个碳原子的环烷基;7-15个碳原子的苯基烷基或者在该苯环上被1-3个卤素,1-8个碳原子的烷基,1-8个碳原子的烷氧基或者其组合取代的所述的苯基烷基;或者2-18个碳原子的直链或者支链链烯基;
R5的定义同R4;或者R5还是氢或者1-24个碳原子的直链或者支链烷基,2-24个碳原子的链烯基;或者R5是下式的基团:
T是氢,氧基,羟基,-OT1,1-24个碳原子的烷基,被1-3个羟基取代的所述的烷基;苄基或者2-18个碳原子的烷酰基;
T1是1-24个碳原子的烷基,5-12个碳原子的环烷基,2-24个碳原子的链烯基,5-12个碳原子的环烯基,7-15个碳原子的苯基烷基,7-12个碳原子的饱和的或者不饱和的双环或者三环烃基团或者6-10个碳原子的芳基或者被1-3个1-4个碳原子烷基取代的所述的芳基;
R6是1-18个碳原子的直链或者支链烷基,2-12个碳原子的直链或者支链链烯基,苯氧基,1-12个碳原子的烷基氨基,6-12个碳原子的芳基氨基,-R7COOH或者-NH-R8-NCO;
R7是2-14个碳原子的亚烷基,或者亚苯基;
R8是2-24个碳原子的亚烷基,亚苯基,甲代亚苯基,二苯基甲烷或者基团
t是0-9;
L是1-12个碳原子的直链或者支链亚烷基,5-12个碳原子的亚环烷基或者用亚环己基或者亚苯基取代的或者间断的亚烷基;或者L是亚苄基;或者L是-S-,-S-S-,-S-E-S-,-SO-,-SO2-,-SO-E-SO-,-SO2-E-SO2-,-CH2-NH-E-NH-CH2-或者
E是2-12个碳原子的亚烷基,5-12个碳原子的亚环烷基或者被5-12个碳原子的亚环烷基间断或者端接的亚烷基;
n是2,3或者4;
当n是2时;Q是2-16个碳原子的直链或者支链亚烷基;或者是被1-3个羟基基团取代的所述的亚烷基;或者是被1-3个-CH=CH-或者-O-间断的所述的亚烷基;或者是被上述基团的组合取代和间断取代和间断的所述的亚烷基;或者Q是亚二甲苯基或者是基团-CONH-R8-NHCO-,-CH2CH(OH)CH2O-R9-OCH2CH(OH)CH2-,-CO-R10-CO-,或者-(CH2)m-COO-R11-OOC-(CH2)m-,其中m是1-3;或者Q是
R9是2-50个碳原子的亚烷基;或者是被1-10个-O-,亚苯基或者基团-亚苯基-G-亚苯基间断的所述的亚烷基,其中G是-O-,-S-,-SO2-,-CH2-或者-C(CH3)2-;
R10是2-10个碳原子的亚烷基,或者是被1-4个-O-,-S-或者-CH=CH-间断的所述的亚烷基;或者R10是6-12个碳原子的亚芳基;
R11是2-20个碳原子的亚烷基或者是被1-8个-O-间断的所述的亚烷基;
当n是3时,Q是基团-[(CH2)mCOO]3-R12,其中m是1-3,R12是3-12个碳原子的烷三基(alkanetriyl);
当n是4时,Q是基团-[(CH2)mCOO]4-R13,其中m是1-3,R13是4-12个碳原子的烷四基(alkanetetrayl);
Z1是下式的基团:
Z2是下式的基团:
其中
r1和r2彼此独立地是0或者1;
R14,R15,R16,R17,R18,R19,R20,R21,R22和R23彼此独立地是氢,羟基,氰基,1-20个碳原子的烷基,1-20个碳原子的烷氧基,7-15个碳原子的苯基烷基,5-12个碳原子的环烷基,5-12个碳原子的环烷氧基,卤素,1-5个碳原子的卤代烷基,磺基,羧基,2-12个碳原子的酰基氨基,2-12个碳原子的酰氧基,2-12个碳原子的烷氧基羰基,或者氨基羰基;或者R17和R18或者R22和R23与它们连接到其上的苯基一起是被1-3个-O-或者-NR5-间断的环状基团。
例如,如果所述的烷基或者所述的亚烷基是被一个或多个基团(例如亚苯基,-O-,-NR5-,-CONR5-,-COO-,-OCO-,-CO-,环氧基,-C(R5)=C(R5)COO-,-OCOC(R5)=C(R5)-,-C(R5)=C(R5)-或者亚苯基-G-亚苯基基团)间断的,则烷基或者亚烷基包含至少2个碳原子。
当化合物中的一个符号名称(例如R2′或者R2″)出现大于一次(例如两次)时,这个符号名称可以是不同的基团或者相同的基团。
在所述的定义中,术语烷基包含在给定界限范围内的碳原子,例如甲基,乙基,丙基,异丙基,正丁基,仲丁基,异丁基,叔丁基,2-乙基丁基,正戊基,异戊基,1-甲基戊基,1,3-二甲基丁基,正己基,1-甲基己基,正庚基,2-甲基庚基,1,1,3,3-四甲基丁基,1-甲基庚基,3-甲基庚基,正辛基,2-乙基己基,1,1,3-三甲基己基,1,1,3,3-四甲基戊基,壬基,癸基,十一烷基,1-甲基十一烷基或者十二烷基。
链烯基的例子是在所给出的碳原子范围内的乙烯基,烯丙基,1-甲基乙烯基,和支化的和未支化的丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一碳烯基和十二碳烯基的异构体。术语链烯基还包含具有大于一个双键的残基,其可以是共轭或者非共轭的,例如可以包含一个双键。
亚烷基的例子是在给定界限的碳原子范围内的支化的和未支化的亚乙基、亚丙基、亚丁基、亚戊基、亚己基、亚庚基、亚辛基、亚壬基、亚癸基、亚十一烷基和亚十二烷基的异构体。
环烷基的一些例子是环戊基,环己基,甲基环戊基,二甲基环戊基和甲基环己基。
亚环烷基的一些例子是亚环戊基,亚环己基(例如1,4-亚环己基),甲基亚环戊基,二甲基亚环戊基和甲基亚环己基。
环烯基的一些例子是环戊烯基,环己烯基,甲基环戊烯基,二甲基环戊烯基和甲基环己烯基。环烯基可以包含大于一个双键,其可以是共轭的或者非共轭的,例如可以包含一个双键。
芳基是例如苯基。
亚芳基是例如亚苯基,特别是邻-、间-或者对-亚苯基。
亚苯基的例子是邻-、间-和对-亚苯基。
苯基烷基是例如苄基或者α,α-二甲基苄基。
术语烷氧基可以包含在所给出的数目界限内的碳原子,例如甲氧基和乙氧基,以及丙氧基、丁氧基、戊氧基、己氧基、庚氧基和辛氧基的支化的和未支化的异构体。
在所述的定义中,术语烷酰基包含在给定界限范围内的碳原子,例如乙酰基,丙酰基,以及丁酰基,戊酰基,己酰基,庚酰基,辛酰基,壬酰基,癸酰基,十一烷酰基和十二烷酰基的支化的和未支化的异构体。
术语卤素可以包含氯、溴和碘;例如卤素是氯。
例如,7-12个碳原子的饱和的或者不饱和的双环或者三环烃的基团是十氢化萘。
优选,所述的2-羟基苯基三嗪UV吸收剂(a)是式(I),(II)或者(III),其中X和Y独立地是苯基,或者是被下面的基团取代的所述的苯基:1-3个1-6个碳原子的烷基,羟基或者1-6个碳原子的烷氧基或者其混合物;或者独立地是Z1或者Z2;
R1是氢;
R1′和R1″定义同R1;
R2是氢,1-24个碳原子的直链或者支链烷基;或者是被下面的基团取代的所述的烷基:1-4个-R4,-OR5,-N(R5)2,-CON(R5)2,-COR5,-COOR5,-OCOR5,-OCOC(R5)=C(R5)2,-C(R5)=CCOOR5,或者其组合;或者是被下面的基团间断的所述的烷基:1-4个-O-,-NR5-,-CONR5-,-COO-,-OCO-,-CO-,-C(R5)=C(R5)COO-,-OCOC(R5)=C(R5)-,-C(R5)=C(R5)-,或者其组合,或者是被上述基团的组合取代和间断的所述的烷基;或者R2是-COR6;
R2,R2′和R2″相同或者不同,并且定义同R2;
R4是2-18个碳原子的直链或者支链链烯基;
R5的定义同R4;或者R5还是氢或者1-24个碳原子的直链或者支链烷基,2-24个碳原子的链烯基;
R6是1-18个碳原子的直链或者支链烷基,2-12个碳原子的直链或者支链链烯基,1-12个碳原子的烷基氨基;
Z1是下式的基团:
Z2是下式的基团:
其中
r1和r2彼此独立地是0或者1;
R14,R15,R16,R17,R18,R19,R20,R21,R22和R23彼此独立地是氢,羟基,1-20个碳原子的烷基,1-20个碳原子的烷氧基,羧基,2-12个碳原子的酰基氨基,2-12个碳原子的酰氧基,2-12个碳原子的烷氧基羰基,或者氨基羰基。
更优选,2-羟基苯基三嗪UV吸收剂(a)是式(I),(II)或者(III),特别是式(I)或者(III),其中
X和Y独立地是苯基,或者是被下面的基团取代的所述的苯基:1-2个1个碳原子的烷基、羟基或者1-6个碳原子的烷氧基或者其混合物;或者独立地是Z1或者Z2;
R1是氢;
R1′和R1″定义同R1;
R2是氢,1-15个碳原子的直链或者支链烷基;或者是被下述基团取代的所述的烷基:1或者2个-R4,-OR5,-COOR5,-OCOR5,-OCOC(R5)=C(R5)2,-C(R5)=CCOOR5,或者其组合;或者是被下面的基团间断的所述的烷基:1或者2个-O-,-COO-,-OCO-或者其组合,或者是被上述基团的组合取代和间断的所述的烷基;或者R2是-COR6;
R2,R2′和R2″相同或者不同,并且定义同R2;
R4是2-3个碳原子的直链或者支链链烯基;
R5的定义同R4;或者R5还是氢或者1-15个碳原子的直链或者支链烷基,2-3个碳原子的链烯基;
R6是1-15个碳原子的直链或者支链烷基,2-3个碳原子的直链或者支链链烯基;
Z1是下式的基团:
Z2是下式的基团:
其中
r1和r2是1;
R14,R15,R16,R17,R18,R19,R20,R21,R22和R23是氢。
甚至更优选的,该2-羟基苯基三嗪UV吸收剂(a)是式(I),(II)或者(III),特别是式(I)或者(III),尤其是式(I),其中X和Y是独立的苯基,或者被下面的基团取代的所述的苯基:1-2个1个碳原子的烷基,羟基或者1-6个碳原子的烷氧基或者其混合物;或者独立地是Z1或者Z2;
R1是氢;
R1′和R1″定义同R1;
R2是氢,1-15个碳原子的直链或者支链烷基;或者是被下述基团取代的所述的烷基:1或者2个-OR5,-COOR5,-OCOR5,-OCOC(R5)=C(R5)2或者其组合;或者是被下面的基团间断的所述的烷基:1个-O-,-COO-或者-OCO-,或者是被上述基团的组合取代和间断的所述的烷基;或者R2是-COR6;
R2,R2′和R2″相同或者不同,并且定义同R2;
R5是氢或者1-15个碳原子的直链或者支链烷基,2-3个碳原子的链烯基;
R6是2-3个碳原子的直链或者支链链烯基;
Z1是下式的基团:
Z2是下式的基团:
其中
r1和r2是1;
R14,R15,R16,R17,R18,R19,R20,R21,R22和R23是氢。
例如,2-羟基苯基三嗪UV吸收剂(a)是式(I),其中
X和Y独立地是苯基,或者是被1-2个1个碳原子的烷基取代的所述的苯基;或者独立地是Z1或者Z2;
R1是氢;
R2是1-15个碳原子的直链或者支链烷基;或者是被下述基团取代的所述的烷基:1个-OR5,-COOR5或-OCOR5;或者是被下面的基团间断的所述的烷基:1个-O-,-COO-或者-OCO-,或者是被上述基团的组合取代和间断的所述的烷基;
R5是氢或者1-15个碳原子的直链或者支链烷基;
Z1和Z2定义同上。
例如,2-羟基苯基三嗪UV吸收剂(a)是式(I),其中X和Y是被两个1个碳原子的烷基取代的苯基;或者是Z1或者Z2;
R1是氢;
R2是1-15个碳原子的直链或者支链烷基;或者是被1个-OR5或者-COOR5取代的所述的烷基;或者是被1个-O-或者-COO-间断的所述的烷基,或者是被上述基团的组合取代和间断的所述的烷基;
R5是氢或者1-15个碳原子的直链或者支链烷基;和
Z1和Z2定义同上。
合适的2-羟基苯基三嗪UV吸收剂的例子是:
HPT-8是具有1),2)和3)中所定义的取代基的化合物的混合物
1)G1=G2=CH(CH3-COO-C8H17,G3=G4=H;
2)G1=G2=G3=CH(CH3)-COO-C8H17,G4=H;
3)G1=G2=G3=G4=CH(CH3)-COO-C8H17;
HPT-17:2,4,6-三(2-羟基-4-辛氧基苯基)-1,3,5-三嗪,
HPT-18:2-(2,4-二羟基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,
HPT-19:2,4-双(2-羟基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪,
HPT-20:2-(2-羟基-4-辛氧基苯基)-4,6-双(4-甲基苯基)-1,3,5-三嗪,
HPT-21:2-(2-羟基-4-十二烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,
HPT-22:2-(2-羟基-4-十三烷氧基苯基基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,
HPT-23:2-[2-羟基-4-(2-羟基-3-丁氧基丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪,
HPT-24:2-[2-羟基-4-(2-羟基-3-辛氧基丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪,
HPT-25:2-[2-羟基-4-(2-羟基-3-十二烷氧基丙氧基)苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,
HPT-26:2-(2-羟基-4-己氧基)苯基-4,6-二苯基-1,3,5-三嗪,
HPT-27:2-(2-羟基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪,
HPT-28:2,4,6-三[2-羟基-4-(3-丁氧基-2-羟基-丙氧基)苯基]-1,3,5-三嗪,
HPT-29:2-(2-羟基苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三嗪,
HPT-30:2,4-双(4-[2-乙基己氧基]-2-羟基苯基)-6-(4-甲氧基苯基)-1,3,5-三嗪。
最优选的2-羟基苯基三嗪UV吸收剂是HPT-1到HPT-8,特别是HPT-1到HPT-2。
2-羟基苯基三嗪UV吸收剂可以直接使用其本身或者可以作为包含该2-羟基苯基三嗪UV吸收剂的浓缩的含水聚合物分散体来使用。这样的包含2-羟基苯基三嗪UV吸收剂的浓缩含水聚合物分散体可以是如WO-A-05/023878所述的,并且能够如WO-A-05/023878所述来获得。优选这些包含2-羟基苯基三嗪UV吸收剂的浓缩的含水聚合物分散体可以是与此处所述的产物本身是相同的。
本发明一种另外的实施方案是组份(a),其是两种或多种不同的2-羟基苯基三嗪UV吸收剂的混合物。
例如,组份(a)是两种不同的2-羟基苯基三嗪UV吸收剂的混合物。优选的混合物是HPT-1和HPT-2;HPT-2和HPT-6;HPT-2和HPT3;HPT-2和HPT-4;HPT-2和HPT-5;HPT-1和HPT-7;HPT-1和HPT-7;HPT-3和HPT-7;HPT-4和HPT-7;HPT-5和HPT-7;HPT-6和HPT-7;HPT-1和HPT-8;HPT-3和HPT-8;HPT-4和HPT-8;HPT-5和HPT-8;HPT-6和HPT-8。特别优选的是HPT-1和HPT-2的混合物。在所述混合物中两种不同的2-羟基苯基三嗪UV吸收剂的重量比是例如4∶1-1∶4,优选是3∶1-1∶3,甚至更优选的2.5∶1-1∶2.5。
一种更适合的具体的例子是例如下面的重量比的HPT-1与HPT-2的混合物:4∶1-1∶4,优选4∶1-1∶1,甚至更优选的2.5∶1-1.5∶1,最优选的大约2∶1。
例如,组份(a)是三种不同的2-羟基苯基三嗪UV吸收剂的混合物(例如HPT-1,HPT-2和HPT-7;HPT-2,HPT-3和HPT-7;HPT-2,HPT-4和HPT-7;HPT-2,HPT-5和HPT-7;HPT-2,HPT-6和HPT-7;HPT-1,HPT-2和HPT-8;HPT-2,HPT-3和HPT-8;HPT-2,HPT-4和HPT-8;HPT-2,HPT-5和HPT-8;HPT-2,HPT-6和HPT-8)。第一和第二2-羟基苯基三嗪UV吸收剂的重量比例是例如4∶1-1∶4,优选3∶1-1∶3,甚至更优选的2.5∶1-1∶2.5。第一和第三2-羟基苯基三嗪UV吸收剂的重量比例是例如4∶1-1∶4,优选3∶1-1∶3,甚至更优选2.5∶1-1∶2.5。
2-羟基苯基三嗪UV吸收剂是部分市售的。另外它们和它们的起始材料可以通过本领域已知的方法来制备。例如,2-羟基苯基三嗪UV吸收剂是将卤代三嗪通过弗瑞德-克莱福特(Friedel-Crafts)加成反应生成相应的芳族化合物和苯酚来制备的,其类似于在EP-A-434608中或者在开始时提到的公开文献中所述的方法之一或者类似于H.Brunetti和C.E.HeIv.Chim.Acta 55,1566(1972)公开文献中所述的方法之一;还可以参见US专利No.5726310,6057444,6225468和EP-A-941989,WO00/29392。这样的方法之后可以是根据已知方法的另外一种反应;这样的反应和方法描述在例如EP-A-434608中。羟基苯基三嗪UV吸收剂被描述在例如GB-A-975966,EP-A-434608,US-4619956,US-5298067,EP-A-530135,EP-A-520938,EP-A-531258,US-5556973,US-5959008,US-6184375,US-6117997中;例如描述在US-5998116,US-6255483,US-6060543中。
颜料(b)可以任何颜色,包括黑色和白色。有机颜料可以是通常用于使用颜料的工业,例如涂料工业中,来产生颜色的这些颜料:即,黑色,蓝色,红色,绿色,橙色和黄色。
关于有机颜料进一步的详细内容,可以参考Industrial Organic Pigments,W.Herbst,K.Hunger,第2版,VCH Verlagsgesellschaft,Weinheim,1997。
特别优选的颜料包括C.I.颜料红170,177,179,202,254,264,C.I.颜料紫19,23,C.I.颜料蓝15,15:1,15:2,15:3,15:4,15:6,16,60,C.I.颜料黄109,110,129,138,139,150,184,C.I.颜料绿7,36,C.I.颜料橙48,73,二酮基-吡咯并吡咯颜料,喹吖啶酮颜料,喹吖啶酮/二酮基-吡咯并吡咯颜料;以及其混合物和其固溶体。
颜色索引(C.I.)是由英国染色工作者协会(the Society of Dyers and Colourists)和美国纺织染化工作者协会(the American Association of Textile Chemists andColorists)编撰的。
更特别优选的颜料包括C.I.颜料红170,177,179,202,254,264,C.I.颜料紫19,23,C.I.颜料蓝15,15:1,15:2,15:3,15:4,15:6,16,60,C.I.颜料黄109,110,129,138,139,150,184,C.I.颜料绿7,36,C.I.颜料橙48,73;以及其混合物和固溶体。
同样更特别优选作为颜料(b)的是喹吖啶酮/二酮基-吡咯并吡咯颜料。
这样的颜料主要是市售的。另外这样的颜料可以根据本领域已知的方法来制备。
粘合剂(c)原则上可以是工业上常用的任何粘合剂,例如描述在Ullmann′sEncyclopedia of Industrial Chemistry,第5版第A18卷第368-426页,VCH,Weinheim 1991中的这些粘合剂。通常,它是一种基于热塑性或者热固性树脂的成膜粘合剂,主要是基于热固性树脂。其的例子是醇酸树脂,丙烯酸,丙烯酸醇酸,聚酯,酚醛,蜜胺,环氧和聚氨酯树脂及其混合物。
组份(c)可以是冷固性或者热固性粘合剂;加入固化催化剂是有利的。加速粘合剂固化的合适的催化剂被描述在例如Ullmann′s Encyclopedia of IndustrialChemistry,第A18卷第469页,VCH Verlagsgesellschaft,Weinheim 1991中。
本发明的着色透明涂层例如是用作汽车的面漆。
含有特定的粘合剂的涂料组合物的例子是:
1.油漆,其基于冷-或者热-可交联的醇酸,丙烯酸酯,聚酯,环氧或者蜜胺树脂或者这样的树脂的混合物,如果期望,则加入固化催化剂;
2.双组份聚氨酯油漆,其基于含羟基丙烯酸酯,聚酯或者聚醚树脂和脂肪族或芳香族异氰酸酯,异氰脲酸酯或者多异氰酸酯;
3.单组份聚氨酯油漆,其基于封闭的异氰酸酯,异氰脲酸酯或者多异氰酸酯(其在焙烤过程中解封闭),如果期望,则加入蜜胺树脂;
4.单组份聚氨酯油漆,其基于三烷氧基羰基三嗪交联剂和含羟基树脂例如丙烯酸酯,聚酯或者聚醚树脂;
5.单组份聚氨酯油漆,其基于在氨基甲酸酯结构中具有自由氨基基团的脂肪族或者芳香族氨基甲酸酯丙烯酸酯或者聚氨酯丙烯酸酯,和蜜胺树脂或者聚醚树脂,如果需要带有固化催化剂;
6.双组份油漆,其基于(聚)酮亚胺和脂肪族或者芳香族异氰酸酯,异氰脲酸酯或者多异氰酸酯;
7.双组份油漆,其基于(聚)酮亚胺和不饱和的丙烯酸酯树脂或者聚乙酰乙酸酯树脂或者甲基丙烯酰胺乙醇酸甲酯;
8.双组份油漆,其基于含羧基-或者氨基-的聚丙烯酸酯和聚环氧化物;
9.双组份油漆,其基于含有酸酐基团的丙烯酸酯树脂和基于多羟基或者多氨基组份;
10.双组份油漆,其基于含有酸酐的丙烯酸酯和聚环氧化物;
11.双组份油漆,其基于(聚)噁唑啉和含有酸酐基团的丙烯酸酯树脂,或者不饱和的丙烯酸酯树脂,或者脂肪族或者芳香族异氰酸酯,异氰脲酸酯或者多异氰酸酯;
12.双组份油漆,其基于不饱和的聚丙烯酸酯和聚丙二酸酯;
13.热塑性聚丙烯酸酯油漆,其基于热塑性丙烯酸酯树脂或者外部交联的丙烯酸酯树脂以及相组合的醚化蜜胺树脂;
14.油漆系,其基于硅氧烷改性的或者氟改性的丙烯酸酯树脂。
例如,组份(c)是一种用于表面涂层的粘合剂,特别是一种用于面漆的粘合剂。这样的粘合剂的例子是醇酸树脂、聚酯树脂、丙烯酸树脂、环氧树脂、聚氨酯树脂、蜜胺/甲醛树脂、脲/甲醛树脂、封闭的异氰酸酯树脂及其组合,特别是丙烯酸树脂、聚氨酯树脂、封闭的异氰酸酯树脂及其组合,尤其是聚氨酯树脂。
可能的干燥催化剂或者固化催化剂是例如有机金属化合物,胺类,含氨基的树脂和/或膦。有机金属化合物的例子是金属羧酸盐,特别是金属Pb,Mn,Co,Zn,Zr或者Cu的这些羧酸盐,或者金属螯合物,特别是金属Al,Ti或者Zr的这些螯合物,或者有机金属化合物是例如诸如有机锡化合物。
金属羧酸盐的例子是Pb,Mn或者Zn的硬脂酸盐,Co,Zn或者Cu的辛酸盐,Mn和Co的环烷酸盐或者相应的亚油酸盐,树脂酸盐(resinates或者tallates)。
金属螯合物的例子是乙酰丙酮,乙酰乙酸乙酯,水杨醛,水杨醛肟,邻羟基苯乙酮或者三氟乙酰乙酸乙酯的铝、钛或者锆螯合物,以及这些金属的醇盐。
有机锡化合物的例子是***,二月桂酸二丁基锡或者二辛酸二丁基锡。
胺类的例子是特别是叔胺,例如三丁基胺,三乙醇胺,N-甲基二乙醇胺,N-二甲基乙醇胺,N-乙基吗啉,N-甲基吗啉或者二氮杂双环辛烷(三亚乙基二胺)及其盐。另外的例子是季铵盐,例如三甲基苄基氯化铵。
含氨基的树脂是配合粘合剂和固化催化剂。其例子是含氨基的丙烯酸酯共聚物。
所用的固化催化剂还可以是膦,例如三苯基膦。
所述的涂料组合物也可以是可辐射固化涂料组合物。在这种情况中,粘合剂本质上包含含有烯键式不饱和键的单体或者低聚物化合物,其在施涂后通过光化学辐射来固化,即被转化为一种交联的高分子量形式。其中该体系是UV固化的,它通常还包含光引发剂。相应的体系描述在上述的公开文献Ullmann′sEncyclopedia of Industrial Chemistry,第5版第A18,卷第451-453页。
本发明的涂料组合物可以施涂到任何所期望的基底上,例如施涂到金属、塑料或者陶瓷材料上。它们被例如用作汽车最后的面漆。
本发明的涂料组合物可以通过常规方法施涂到基底上,例如通过刷涂、喷涂、倾到、浸涂或者电泳涂覆;同样参见Ullmann′s Encyclopedia of IndustrialChemistry,第5版第A18卷第491-500页。
取决于粘合剂体系,所述的涂层可以在室温固化或者通过加热固化。该涂层可以例如在50-150℃固化,并且在粉末涂料或者卷材涂料的情况中,甚至在更高的温度固化。
所述的涂料组合物可以包含粘合剂在其中可溶的有机溶剂或者溶剂混合物。涂料组合物还可以是水性溶液或者分散体。载色剂也可以是有机溶剂和水的混合物。该涂料组合物可以是高固体分油漆或者可以是无溶剂的(例如粉末涂料)。粉末涂料是例如描述在Ullmann′s Encyclopedia of Industrial Chemistry,第5版第A18卷第438-444页中的这些。粉末涂料还可以具有粉末浆体的形式(优选粉末在水中的分散体)。
优选的,此处所述的着色透明涂料组合物是汽车涂料组合物。
组份(a)典型的存在量是固体粘合剂(c)重量的0.2-20重量%,优选是0.2-10重量%,更优选是0.5-5重量%,最优选是1.0-3.5重量%。
组份(b)典型的存在量是固体粘合剂(c)重量的0.2-10重量%,优选是0.2-5重量%,更优选是0.4-3重量%,最优选是0.5-1.5重量%。
通常,组份(a)与组份(b)的重量比是10∶1-1∶1,优选是6∶1-1.3∶1,更优选是5∶1-1.5∶1,最优选是4∶1-2∶1。
例如,所述的着色透明涂料组合物包含另外的添加剂。
这样的添加剂的例子是:
1.抗氧化剂
1.1.烷基化一元酚类,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-正丁基苯酚,2,6-二叔丁基-4-异丁基苯酚,2,6-二环戊基-4-甲基苯酚,2-(α-甲基环己基)-4,6-二甲基苯酚,2,6-双十八烷基-4-甲基苯酚,2,4,6-三环己基苯酚,2,6-二叔丁基-4-甲氧基甲基苯酚;在侧链中是直链或支链的壬基苯酚,例如2,6-二壬基-4-甲基苯酚,2,4-二甲基-6-(1′-甲基十一烷-1′-基)苯酚,2,4-二甲基6-(1′-甲基十七烷-1′-基)苯酚,2,4-二甲基-6-(1′-甲基十三烷-1′-基)苯酚以及它们的混合物。
1.2.烷基硫基甲基酚类,例如2,4-二辛基硫基甲基-6-叔丁基苯酚,2,4-二辛基硫基甲基-6-甲基苯酚,2,4-二辛基硫基甲基6-乙基苯酚,2,6-双十二烷基硫基甲基-4-壬基苯酚。
1.3.氢醌类或烷基化氢醌类,例如,2,6-二叔丁基-4-甲氧基苯酚,2,5-二叔丁基氢醌,2,5-二叔戊基氢醌,2,6-二苯基-4-十八烷氧基苯酚,2,6-二叔丁基氢醌,2,5-二叔丁基-4-羟基苯甲醚,3,5-二叔丁基-4-羟基苯甲醚,硬脂酸3,5-二叔丁基-4-羟基苯基酯,己二酸双(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-生育酚和它们的混合物(维生素E)。
1.5.羟基化硫基二苯基醚类,例如,2,2′-硫基双(6-叔丁基-4-甲基苯酚),2,2′-硫基双(4-辛基苯酚),4,4′-硫基双(6-叔丁基-3-甲基苯酚),4,4′-硫基双(6-叔丁基-2-甲基苯酚),4,4′-硫基双(3,6-二仲戊基苯酚),4,4′-双(2,6-二甲基-4-羟基苯基)二硫醚。
1.6.亚烷基双酚类,例如,2,2′-亚甲基双(6-叔丁基-4-甲基苯酚),2,2′-亚甲基双(6-叔丁基-4-乙基苯酚),2,2′-亚甲基双[4-甲基-6-(α-甲基环己基)苯酚],2,2′-亚甲基双(4-甲基-6-环己基苯酚),2,2′-亚甲基双(6-壬基-4-甲基苯酚),2,2′-亚甲基双(4,6-二叔丁基苯酚),2,2′-亚乙基双(4,6-二叔丁基苯酚),2,2′-亚乙基双(6-叔丁基-4-异丁基苯酚),2,2′-亚甲基双[6-(α-甲基苄基)-4-壬基苯酚],2,2′-亚甲基双[6-(α,α-二甲基苄基)4-壬基苯酚],4,4′-亚甲基双(2,6-二叔丁基苯酚),4,4′-亚甲基双(6-叔丁基-2-甲基苯酚),1,1′-双(5-叔丁基-4-羟基-2-甲基苯基)丁烷,2,6-双(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-双(5-叔丁基-4-羟基-2-甲基苯基)-3-正十二烷基巯基丁烷,双[3,3-双(3′-叔丁基-4′-羟基苯基)丁酸]乙二醇酯,双(3-叔丁基-4-羟基-5-甲基-苯基)双环戊二烯,对苯二甲酸双[2-(3′-叔丁基-2′-羟基5′-甲基苄基)-6-叔丁基-4-甲基苯基]酯,1,1-双-(3,5-二甲基-2-羟基苯基)丁烷,2,2-双-(3,5-二叔丁基-4-羟基苯基)丙烷,2,2-双-(5-叔丁基-4-羟基-2-甲基苯基)-4-正十二烷基巯基丁烷,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-苄基化合物类,例如3,5,3′,5′-四叔丁基-4,4′-二羟基二苄基醚,4-羟基-3,5-二甲基苄基巯基乙酸十八烷基酯,4-羟基-3,5-二叔丁基苄基巯基乙酸十三烷基酯,三(3,5-二叔丁基-4-羟基苄基)胺,二硫基对苯二甲酸双(4-叔丁基-3-羟基-2,6-二甲基苄基)酯,双(3,5-二叔丁基-4-羟基苄基)硫醚,3,5-二叔丁基-4-羟基苄基巯基乙酸异辛酯。
1.8.羟苄基化丙二酸酯类,例如,2,2-双-(3,5-二叔丁基2-羟基苄基)丙二酸二(十八烷基)酯,2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸二(十八烷基)酯,2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸二(十二烷基巯基乙基)酯,2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸双[4-(1,1,3,3-四甲基丁基)苯基]酯。
1.9.芳族羟苄基化合物类,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-双(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。
1.10.三嗪化合物类,例如2,4-双(辛基巯基)-6-(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪,2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪,2-辛基巯基-4,6-双(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)异氰脲酸酯,1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-异氰脲酸酯,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)异氰脲酸酯。
1.11.苄基膦酸酯类,例如2,5-二叔丁基-4-羟基苄基膦酸二甲酯,3,5-二叔丁基-4-羟基苄基膦酸二乙酯,3,5-二叔丁基-4-羟基苄基膦酸二(十八烷基)酯,5-叔丁基-4-羟基-3-甲基苄基膦酸二(十八烷基)酯,3,5-二叔丁基-4-羟基苄基膦酸的单乙酯的钙盐。
1.12.酰基氨基酚类,例如4-羟基月桂酰苯胺,4-羟基硬脂酰苯胺,N-(3,5-二叔丁基-4-羟基苯基)氨基甲酸辛酯。
1.13.β-(3,5-二叔丁基-4-羟基苯基)丙酸的酯类,构成酯基的是单羟基或多羟基醇类,例如甲醇,乙醇,正辛醇,异辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫基二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟基乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫杂十一烷醇,3-硫杂十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。
1.14.β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸的酯类,构成酯基的是单羟基或多羟基醇类,例如甲醇,乙醇,正辛醇,异辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫基二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟基乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫杂十一烷醇,3-硫杂十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷;3,9-双[2-{3-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基}-1,1-二甲基乙基]-2,4,8,10-四氧杂螺[5.5]十一烷。
1.15.β-(3,5-二环己基-4-羟基苯基)丙酸的酯类,构成酯基的是单羟基或多羟基醇类,例如甲醇,乙醇,辛醇,十八烷醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫基二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟基乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫杂十一烷醇,3-硫杂十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷。
1.16.3,5-二叔丁基-4-羟基苯基乙酸的酯类,构成酯基的是单羟基或多羟基醇类,例如甲醇,乙醇,辛醇,十八醇,1,6-己二醇,1,9-壬二醇,乙二醇,1,2-丙二醇,新戊二醇,硫基二甘醇,二甘醇,三甘醇,季戊四醇,异氰脲酸三(羟乙基)酯,N,N′-双(羟乙基)草酰胺,3-硫杂十一烷醇,3-硫杂十五烷醇,三甲基己二醇,三羟甲基丙烷,4-羟甲基-1-磷杂-2,6,7-三氧杂二环[2.2.2]辛烷。
1.17.β-(3,5-二叔丁基-4-羟基苯基)丙酸的酰胺类,例如N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)己二酰胺,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)丙二酰胺,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)肼,N,N′-双[2-(3-[3,5-二叔丁基-4-羟基苯基]丙酰氧基)乙基]草酰胺(XL-1,由Uniroyal提供)。
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-对苯二胺、N,N′-二-仲丁基-对苯二胺、N,N′-双(1,4-二甲基戊基)对苯二胺、N,N′-双(1-乙基-3-甲基戊基)对苯二胺、N,N′-双(1-甲基庚基)对苯二胺、N,N′-双环己基对苯二胺、N,N′-二苯对苯二胺、N,N′-双(2-萘基)对苯二胺、N-异丙基-N′-苯基-对苯二胺、N-(1,3-二甲基丁基)-N′-苯基-对苯二胺、N-(1-甲基庚基)-N′-苯基-对苯二胺、N-环己基-N′-苯基-对苯二胺、4-(对甲苯氨磺酰)二苯胺、N,N′-二甲基-N,N′-二-仲丁基-对苯二胺、二苯胺、N-烯丙基二苯胺、4-异丙氧基二苯胺、N-苯基-1-萘胺、N-(4-叔辛基苯基)-1-萘胺、N-苯基-2-萘胺、辛基化二苯胺、例如对,对′-二叔辛基二苯胺、4-正丁基氨基苯酚、4-丁酰基氨基苯酚、4-壬酰氨基苯酚、4-十二烷酰氨基苯酚、4-十八烷酰氨基苯酚、双(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′-二氨基二苯甲烷、4,4′-二氨基二苯甲烷、N,N,N′,N′-四甲基-4,4′-二氨基二苯甲烷、1,2-双[(2-甲基苯基)氨基]乙烷、1,2-双(苯基氨基)丙烷、(邻甲苯基)缩二胍、双[4-(1′,3′-二甲基丁基)苯基]胺、叔辛基化N-苯基-1-萘胺、单和二烷基化叔丁基/叔辛基二苯胺的混合物、单和二烷基化壬基二苯胺的混合物、单和二烷基化十二烷基二苯胺的混合物、单和二烷基化异丙基/异己基二苯胺的混合物、单和二烷基化叔丁基二苯胺的混合物、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、N,N,N′,N′-四苯基-1,4-二氨基丁-2-烯。
2.UV吸收剂和光稳定剂
2.1.2-(2′-羟基苯基)苯并***类,例如2-(2′-羟基-5′-甲基苯基)-苯并***、2-(3′,5′-二叔丁基-2′-羟苯基)苯并***、2-(5′-叔丁基-2′-羟苯基)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′-羟苯基)苯并***、2-(2′-羟基-4′-辛氧基苯基)苯并***、2-(3′,5′-二叔戊基-2′-羟苯基)苯并***、2-(3′,5′-双(α,α-二甲基苄基)-2′-羟苯基)苯并***、2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰基乙基)苯基)-5-氯-苯并***、2-(3′-叔丁基-5’-[2-(2-乙基己氧基)-羰基乙基]-2′-羟苯基)-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-甲氧基羰基乙基)苯基)苯并***、2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰基乙基)苯基)苯并***、2-(3′-叔丁基-5’-[2-(2-乙基己氧基)羰基乙基]-2′-羟苯基)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-异辛氧基羰基乙基)苯基苯并***、2,2’-亚甲基双[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′-羟苯基]-2H-苯并***与聚乙二醇300的酯交换产物;
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-羟基二苯甲酮类,例如4-羟基、4-甲氧基、4-辛氧基、4-癸氧基、4-十二烷氧基、4-苄氧基、4,2′,4′-三羟基和2′-羟基-4,4′-二甲氧基衍生物。
2.3.苯甲酸酯类,例如取代的和未取代的苯甲酸的酯类,例如水杨酸4-叔丁基-苯基酯,水杨酸苯酯,水杨酸辛基苯酯,二苯甲酰基间苯二酚,双(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.丙烯酸酯类,例如α-氰基-β,β-二苯基丙烯酸乙酯,α-氰基-β,β-二苯基丙烯酸异辛酯,α-甲氧羰基肉桂酸甲酯,α-氰基-β-甲基-对甲氧基肉桂酸甲酯,α-氰基-β-甲基-对甲氧基肉桂酸丁酯,α-甲氧羰基-对甲氧基肉桂酸甲酯、N-(β-甲氧羰基-β-氰基乙烯基)-2-甲基二氢吲哚,四(α-氰基-β,β-二苯基丙烯酸新戊酯。
2.5.镍化合物类,例如2,2′-硫代-双-[4-(1,1,3,3-四甲基丁基)苯酚]的镍配合物,如1∶1或1∶2配合比,有或没有附加的配位体如正丁基胺,三乙醇胺或N-环己基二乙醇胺,二丁基二硫代氨基甲酸镍,4-羟基-3,5-二叔丁基苄基膦酸的单烷基酯(例如甲酯或乙酯)类的镍盐,酮肟例如2-羟基-4-甲基苯基十一烷基酮肟的镍配合物类,1-苯基-4-月桂酰基-5-羟基吡唑的镍配合物,有或没有附加的配位体。
2.6.空间位阻胺稳定剂,例如双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(2,2,6,6-四甲基-4-哌啶基)琥珀酸酯、双(1,2,2,6,6-五甲基4-哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(1,2,2,6,6-五甲基4-哌啶基)正丁基-3,5-二叔丁基-4-羟基苄基丙二酸酯、1-(2-羟乙基)-2,2,6,6-四甲基-4-羟基哌啶和丁二酸的缩合物、N,N′-双(2,2,6,6-四甲基-4-哌啶基)己二胺和4-叔辛基氨基-2,6-二氯1,3,5-三嗪的线性或环状缩合物、三(2,2,6,6-四甲基-4-哌啶基)次氮基三乙酸酯、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、1,1′-(1,2-乙烷二基)-双(3,3,5,5-四甲基哌嗪酮)、4-苯甲酰基2,2,6,6-四甲基哌啶、4-十八烷氧基-2,2,6,6-四甲基哌啶、双(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮、双(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基哌啶基)琥珀酸酯、N,N′-双(2,2,6,6-四甲基-4-哌啶基)己二胺和4-吗啉代-2,6-二氯-1,3,5-三嗪的线性或环状缩合物、2-氯-4,6-双(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨基丙基氨基)乙烷的缩合物、2-氯-4,6-二-(4-正丁基氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪和1,2-双(3-氨基丙基氨基)乙烷的缩合物、8-乙酰-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、4-十六烷氧基-和4-十八烷氧基-2,2,6,6-四甲基哌啶的混合物、N,N′-双(2,2,6,6-四甲基-4-哌啶基)己二胺和4-环己基氨基-2,6-二氯-1,3,5-三嗪的缩合物、1,2-双(3-氨基丙基氨基)乙烷和2,4,6-三氯-1,3,5-三嗪以及4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物(CAS登记号[136504-96-6]);1,6-己二胺和2,4,6-三氯-1,3,5-三嗪以及N,N-二丁胺和4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物(CAS登记号[192268-64-7]);N-(2,2,6,6-四甲基-4-哌啶基)正十二烷基琥珀酰亚胺、N-(1,2,2,6,6-五甲基-4-哌啶基)正十二烷基琥珀酰亚胺、2-十一基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧-螺[4,5]癸烷、7,7,9,9-四甲基-2-环十一烷基-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-双(1,2,2,6,6-五甲基4-哌啶基氧基羰基)-2-(4-甲氧苯基)乙烯、N,N′-双甲酰基-N,N′-双(2,2,6,6-四甲基-4-哌啶基)己二胺、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、2,4-双[N-(1-环己基氧基-2,2,6,6-四甲基哌啶-4-基)-N-丁氨基]-6-(2-羟乙基)氨基-1,3,5-三嗪、1-(2-羟基-2-甲基丙氧基)-4-十八烷酰氧基-2,2,6,6-四甲基哌啶、5-(2-乙基己酰基)氧基甲基-3,3,5-三甲基-2-吗啉酮、Sanduvor(Clariant;CAS登记号106917-31-1)、5-(2-乙基己酰基)氧基甲基-3,3,5-三甲基-2-吗啉酮、2,4-双[(1-环己基氧基-2,2,6,6-哌啶-4-基)丁氨基]-6-氯-s-三嗪与N,N′-双(3-氨基丙基)乙二胺)的反应产物、1,3,5-三(N-环己基-N-(2,2,6,6-四甲基哌嗪-3-酮-4-基)氨基)-s-三嗪、1,3,5-三(N-环己基-N-(1,2,2,6,6-五甲基哌嗪-3-酮-4-基)氨基)-s-三嗪。
2.7.草酰胺,例如4,4′-二辛氧基草酰替苯胺、2,2′-二乙氧基草酰替苯胺、2,2’-二辛氧基-5,5′-二叔丁基草酰替苯胺、2,2′-双十二烷氧基-5,5′-二叔丁基草酰替苯胺、2-乙氧基-2′-乙基草酰替苯胺、N,N′-双(3-二甲基氨基丙基)草酰胺、2-乙氧基-5-叔丁基-2′-乙基草酰替苯胺和其与2-乙氧基2′-乙基-5,4′-二叔丁基草酰替苯胺的混合物、邻-和对-甲氧基二取代的草酰替苯胺的混合物和邻-和对-乙氧基二取代的草酰替苯胺的混合物。
3.金属钝化剂,例如N,N′-二苯基草酰胺、N-水杨醛-N′-水杨酰肼、N,N′-双(水杨酰)肼、N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)肼、3-水杨酰氨基-1,2,4-***、双(亚苄基)草酰二肼、草酰替苯胺、间苯二甲酰二肼、癸二酰二苯基酰肼、N,N′-双乙酰己二酰二肼、N,N′-双(水杨酰)草酰二肼、N,N′-双(水杨酰)硫基丙酰二肼。
4.亚磷酸酯类和亚膦酸酯类,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、三(壬基苯基)亚磷酸酯、三(十二烷基)亚磷酸酯、三(十八烷基)亚磷酸酯、二硬脂基季戊四醇二亚磷酸酯、三(2,4-二叔丁基苯基)亚磷酸酯、二异癸基季戊四醇二亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、双(2,4-二-枯基苯基)季戊四醇二亚磷酸酯、双(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、双(2,4-二叔丁基-6-甲基苯基)季戊四醇二亚磷酸酯、双(2,4,6-三叔丁基苯基)季戊四醇二亚磷酸酯、三硬脂基山梨糖醇三亚磷酸酯、四(2,4-二叔丁基苯基)4,4′-亚联苯基二膦酸酯、6-异辛基氧基-2,4,8,10-四叔丁基-12H-二苯[d,g]-1,3,2-二氧杂磷杂环辛烯、双(2,4-二叔丁基-6-甲基苯基)甲基亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)乙基亚磷酸酯、6-氟-2,4,8,10-四叔丁基-12-甲基-二苯[d,g]-1,3,2-二氧杂磷杂环辛烯、2,2′,2″-次氮基[三乙基三(3,3′,5,5′-四叔丁基-1,1′-联苯-2,2′-二基)亚磷酸酯]、2-乙基己基(3,3′,5,5′-四叔丁基-1,1′-联苯-2,2′-二基)亚磷酸酯、5-丁基-5-乙基-2-(2,4,6-三叔丁基苯氧基)-1,3,2-二氧杂磷杂环丙烷。
下列亚磷酸酯是尤其优选的:
5.羟基胺类,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-双十二烷基羟基胺、N,N-双十四烷基羟基胺、N,N-双十六烷基羟基胺、N,N-双十八烷基羟基胺、N-十六烷基-N-十八烷基羟基胺、N-十七烷基-N-十八烷基羟基胺、衍生自氢化牛脂胺的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-十八基-α-十七烷基-硝酮、N-十六烷基-α-十七烷基-硝酮、N-十八烷基-α-十五烷基-硝酮、N-十七烷基-α-十七烷基-硝酮、N-十八基-α-十六烷基-硝酮、衍生自N,N-二烷基羟基胺(其衍生自氢化牛脂胺)的硝酮。
7.硫基增效剂,例如硫代二丙酸二月桂酯、硫代二丙酸二肉豆蔻基(dimistryl)酯、硫代二丙酸二硬脂酰酯或二硬脂基二硫化物。
8.过氧化物清除剂,例如β-硫代二丙酸的酯类,例如月桂基、硬脂基、十四烷基或十三烷基酯类,巯基苯并咪唑或2-巯基苯并咪唑的锌盐,二丁基二硫基氨基甲酸锌,二(十八烷基)二硫醚,四(β-十二烷基巯基)丙酸季戊四醇酯。
9.聚酰胺稳定剂,例如铜盐与碘化物和/或磷化合物的混合物,和二价锰的盐。
10.碱性助稳定剂,例如三聚氰胺,聚乙烯吡咯烷酮,双氰胺,氰脲酸三烯丙酯,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,二十二烷酸镁,硬脂酸镁,蓖麻油酸钠和棕榈酸钾,邻苯二酚(pyrocatecholate)锑或邻苯二酚(pyrocatecholate)锌。
11.成核剂,例如无机物质,如滑石,金属氧化物类如二氧化钛或氧化镁,优选碱土金属的磷酸盐、碳酸盐或硫酸盐;有机化合物如单或多羧酸类和它们的盐类,例如4-叔丁基苯甲酸,己二酸,二苯基乙酸,琥珀酸钠或苯甲酸钠;聚合化合物如离子共聚物(“离聚物”)。尤其优选的是1,3:2,4-双(3’,4’-二甲基苄叉基)山梨糖醇,1,3:2,4-二(对甲基二苄叉基)山梨糖醇,和1,3:2,4-二(苄叉基)山梨糖醇。
12.填料和增强剂,例如碳酸钙,硅酸盐,玻璃纤维,玻璃珠,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,和其它天然产物的粉末或纤维,合成纤维。
13.其它添加剂,例如增塑剂,润滑剂,乳化剂,流变助剂,催化剂,流动调节剂,荧光增白剂,耐焰剂,抗静电剂和发泡剂。
14.苯并呋喃酮类和二氢吲哚酮类,例如公开在US4325863;US4338244;US5175312;US5216052;US5252643;DE-A-4316611;DE-A-4316622;DE-A-4316876;EP-A-0589839,EP-A-0591102;EP-A-1291384中的那些或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-硬脂酰氧基乙氧基)苯基]苯并呋喃-2酮,3,3′-双[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-新戊酰氧基苯基)-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,3-(2-乙酰-5-异辛基苯基)-5-异辛基-苯并呋喃-2-酮。
这些另外的添加剂通常的用量是固体粘合剂(c)的0.01-25重量%,特别是0.1-10重量%,尤其是0.5-5重量%。
优选的是另外的添加剂选自酚类和胺类抗氧化剂,空间位阻胺稳定剂,不同于此处所述的2-羟基苯基三嗪类的这些的UV吸收剂,亚磷酸酯,亚膦酸酯,苯并呋喃酮,金属硬脂酸盐,金属氧化物,有机磷化合物,羟基胺,阻燃剂及其混合物。
更优选的是另外的添加剂选自空间位阻胺稳定剂和UV吸收剂。UV吸收剂优选是选自草酰胺,2-羟基苯甲酮,安息香酸酯,丙烯酸酯和2-(2′-羟基苯基)苯并***。例如,该草酰胺是第2.7项所列出的,该2-羟基苯甲酮是第2.2项所列出的,苯甲酸酯是如第2.3项所列出的,丙烯酸酯是如第2.4项所列出的以及2-(2′-羟基苯基)苯并***是如第2.1项所列出的。
特别优选作为添加剂的是空间位阻胺稳定剂例如在上面所列举的第2.6项所列出的及其混合物。特别优选的是癸二酸双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)酯。空间位阻胺稳定剂另外的例子是在GB-A-2347928中从第4页第6行-第27页倒数第2段,WO-A-01/92392从第1页第8行-第49页倒数第2段和在WO-A-03/076505中从第10页第6段-第39页第5段所列出的,并且可以如其中所述来制备。
该空间位阻胺稳定剂的存在量是固体粘合剂(c)的0.01-10重量%,优选是0.1-5重量%,更优选是0.5-3重量%,最优选是0.5-2重量%。
典型的,将添加剂(例如颜料,2-羟基苯基三嗪,空间位阻胺稳定剂)分散在粘合剂和溶剂的分散体中,然后加入到涂料组合物中或者将添加剂直接分散到涂料组合物中。
本发明另外一个实施方案是一种着色透明涂层,其通过将此处所述的着色透明涂料组合物施涂到基底上来获得。
优选的,该着色透明涂层是面涂层。例如,基底是另外一种涂层(其在此表示为“基底涂层”),金属,塑料或者陶瓷材料。
例如,该基底涂层被施加到另外一个涂层,金属,塑料或者陶瓷材料上,特别是另外一个涂层或者金属上。优选,该基底涂层包含至少一种粘合剂和至少一种颜料;例如,该颜料与固体粘合剂的重量比是1∶1-1∶8,优选是1∶2-1∶6。典型的,该基底涂层不包含UV吸收剂和空间位阻胺稳定剂。该基底涂层通常是不透明的。基底涂层的粘合剂是例如同上述的粘合剂(c),并且可以是粘合剂的混合物。
例如,颜料可以是任何一种颜色,包括黑色和白色。通常,该颜料是颜料或者颜料的混合物,其选自有机颜料和无机颜料。该有机颜料可以是使用颜料的工业,例如涂料工业中,通常使用的产生颜色的这些颜料:即,黑色,蓝色,红色,绿色,橙色和黄色。有机颜料包含例如多环、偶氮和金属络合物颜料。更特别的,有机颜料包含例如单偶氮、双偶氮、β-萘酚、萘酚AS、色淀偶氮、苯并咪唑酮、偶氮缩合物、金属络合物偶氮、偶氮甲碱、异吲哚啉酮、异吲哚啉、金属络合物例如酞菁、喹吖啶酮、苝、紫环酮、靛蓝、硫代靛蓝、蒽醌、阴丹酮、蒽素嘧啶、黄烷士林、皮蒽酮、三苯并吡二酮、二噁嗪、三芳基碳鎓、喹诺酞酮、二酮吡咯并吡咯、硝基染料、喹啉、异蒽酮紫、蝶啶和碱性染料络合物颜料。该颜料可以是固溶体颜料。还可以使用颜料的混合物。可以使用颜料的晶体组合的混合物。优选的颜料选自苯并咪唑酮,异吲哚啉酮,异吲哚啉,金属络合物例如酞菁,喹吖啶酮,苝,蒽醌,阴丹酮和二酮吡咯并吡咯。对于全部这些有机颜料进一步详细的内容,可以参考Industrial Organic Pigments,W.Herbst,K.Hunger,第2版,VCH Verlagsgesellschaft,Weinheim,1997。
无机颜料包括除了别的以外的二氧化钛颜料,氧化铁和氢氧化物颜料,氧化铬颜料,类晶石型煅烧颜料,铬酸铅颜料,炭黑和普鲁士蓝。薄片颜料,特别是干涉薄片颜料,例如金属薄片颜料是优选的。特别合适的颜料是在颜色索引(C.I.)中所列出的这些,该颜色索引是由英国染色工作者协会和美国纺织染化工作者协会编撰的。
例如,颜料是如上述的颜料(b)的定义。颜料还可以是效应颜料,例如云母珠光颜料,铝片颜料及其组合。颜料可以是颜料的混合物。
这样的颜料主要是市售的。另外这样的颜料可以是根据本领域已知的方法制备的。
例如,如果基底是基底涂层,则着色透明涂层的颜料(b)是高度透明的或者半不透明颜料或者其混合物,基底涂层的颜料是金属的或者不透明颜料。
例如,着色透明涂层的颜料或者颜料混合物(b)的色调类似于基底涂层的颜料混合物的颜料。
优选,该着色透明涂层是一种汽车涂层。
更优选,该着色透明涂层是一种汽车涂层,其包含下面的层:
(d)阴极沉积的涂层,其粘附到金属基底上;
(e)至少一个随后的涂层,其粘附到所述的阴极沉积涂层上;
(f至少一个含有颜料或者颜料混合物的底涂层;和
(g)此处所定义的着色透明涂层。
例如,涂层(e)紧邻着涂层(d),涂层(f)紧邻着涂层(e),涂层(g)紧邻着涂层(f)。
底涂层(f)典型的是如上面的基底涂层的定义。优选的层(f)和(g)典型的是如上面定义的在基底涂层上的着色透明涂层。
例如,在这样的汽车涂层中,将金属基底在例如常规的磷酸锌浴中进行预热。
本发明另外一种实施方案是一种制备着色透明涂层的方法,所述方法包括将本文所定义的着色透明涂料组合物施涂到基底上。
例如,该基底是汽车。例如该着色透明涂层是汽车涂层。
优选的是一种方法,其中基底包含下面的层:
(d)阴极沉积的涂层,其粘附到金属基底上;
(e)至少一个随后的涂层,其粘附到所述的阴极沉积涂层上;和
(f)至少一个含有颜料或者颜料混合物的底涂层。
优选的这些方法在上述的着色透明涂层和着色透明涂料组合物中大致给出了。
除非另有指示,否则全部的%是重量%。除非另有指示,否则全部的比例是重量比。
缩写:
” 英寸
C.I. 颜色索引
DFT 干燥膜厚
P/B 颜基比
用于应用实施例中的产物缩写:
应用实施例:着色透明涂层与未着色透明涂层的对比
实施例1
将一种颜料化底涂层配料(见下)喷涂到背衬(Q-Panel型:Special QTY125:镀铝盘管0.025”x4”x12”)上,并且空气中干燥30min。所形成的颜料化底涂层的干燥膜厚大约是16μm。将一种着色透明涂层配料(根据本发明)或者一种未着色透明涂层配料(对比;即一种透明涂层)喷涂到所述的颜料化底涂层上,并且在空气中干燥30min,在130℃的炉子中干燥30min。所形成着色的或者未着色透明涂层的干燥膜厚是35μm-40μm。
颜料化底涂层配料
表1:底涂层配料:
原材料:
1)Maprenal MF 900:蜜胺树脂HMMM
2)Surfynol 104E:炔属二醇,消泡/润湿剂
3)EnviroGem AE 02:表面活性剂,消泡/润湿剂
4)Proglyde DMM:一缩二丙二醇二甲基醚,非质子聚结剂
5)DOWANOL PnP:丙二醇正丙基醚,快速蒸发偶联剂
6)DOWANOL DPnP:一缩二丙二醇正丙基醚,蒸发聚结剂或者偶联剂
7)VISCALEX HV 30:丙烯酸共聚物水乳液,增稠和流变剂
8)APU 10120VP:丙烯酸-聚氨酯共聚物,粘合剂
9)ACTICIDE MBS:甲基-4-异噻唑啉,杀菌剂
表2:用于底涂层的颜料的研磨料
颜料 | %*颜料 | %*固体粘接剂 |
C.I.颜料红202 | 24.00 | 13.20 |
C.I.颜料红179 | 17.00 | 39.90 |
铝 | 22.46 | 34.54 |
C.I.颜料黑7 | 6.00 | 16.50 |
*研磨料的重量%,分别用于每个颜料
表3:用于底涂层的颜料混合物的比例
红色金属颜料混合物 | 比例 |
C.I.颜料红202 | 26.40 |
C.I.颜料红179 | 33.43 |
铝 | 39.56 |
C.I.颜料黑7 | 0.61 |
颜料化底涂层配料的制备:
将每个颜料在水平珠磨机上分别进行分散。将该分散过的研磨料一起进行共混,并加入到底涂层配料中。颜料与固体粘合剂的比例调整为1/3.6。
着色的和未着色透明涂层配料
表4:2KPU透明涂层配料
初始重量 | |
Macrynal SM510n(60%供料形式)1) | 75.0g |
醋酸丁二醇酯 | 15.0g |
Solvesso1002) | 6.1g |
甲基异丁基酮 | 3.6g |
辛酸锌催化剂(8%金属) | 0.1g |
BYK 3003) | 0.2g |
总多元醇成分 | 100.0g |
用于着色透明涂层的研磨料配料的颜料制剂具有下面的P/B比:
颜料 | 研磨料配料的颜料% | 研磨料配料的固体粘合剂% |
P-1 | 15.00 | 19.77 |
将光稳定剂(见下表5;HALS和HPT)加入到上面的多元醇组份中,在其中它们很容易溶解。
对于着色透明涂层来说,将颜料(P)和固体粘合剂在水平珠磨机上进行分散,并且通过在搅拌下将上述的研磨料混入来加入到上面的多元醇组份中。
在使用之前,将40g Desmodur N 754)(异氰酸酯组份)加入到上面的多元醇组份中。随后将所形成的透明涂层配料(固含量:50%)喷涂到上面的固化(130℃,30′)后形成的干燥膜厚是35-40μm的底涂层上。
原材料:
1)Macrynal SM 510n:丙烯酸多元醇树脂(基于固体树脂是大约4.5%羟基含量);供应商:Solutia(以前的Vianova Resins)
2)Solvesso 100:芳香族烃;供应商:Exxon
3)BYK 300:流平剂;供应商:BYK-Chemie
4)Desmodur N 75:异氰酸酯组份;供应商:Bayer AG
评价所述板的色彩,随后根据SAE-J1960(Xe-WOM曝光)曝露4000h。在X-Rite SP68分光光度计上进行色彩测量,所包括的光谱和参数计算(根据DIN6174)是用CGREC软件来进行的。
表5:着色的和未着色透明涂层面板的色度和耐久性对比
添加剂(%,基于固体粘接剂) | 透明涂层的种类 | 色调C*(初始) | DE(4000h曝光之后) |
HPT-1 2.4%HALS-1 1.0% | 未着色 | 32.50 | 1.1 |
P-1 1.0%HPT-1 2.4%HALS-1 1.0% | 着色 | 39.00 | 0.6 |
与未着色透明涂层面板相比,着色透明涂层面板表现出一种明显增加的色度以及更佳的耐久性,即较少的变色。
实施例2
着色的和未着色透明涂层面板是如实施例1那样来生产的,除了着色的和未着色透明涂层的稳定剂是改变的(详见表6)。
表6:着色的和未着色透明涂层面板的色度和耐久性对比
添加剂(%,基于固体粘接剂) | 透明涂层的种类 | 色调C*(初始) | DE(4000h曝光之后) |
HPT-1 1.8%HPT-2 0.9%HALS-1 1.0% | 未着色 | 32.50 | 0.9 |
P-1 1.0%HPT-1 1.8%HPT-2 0.9%HALS-1 1.0% | 着色 | 39.00 | 0.6 |
与未着色透明涂层面板相比,着色透明涂层面板表现出一种明显增加的色度以及更佳的耐久性,即较少的变色。
Claims (18)
1.一种着色透明涂料组合物,其包含:
(a)至少一种2-羟基苯基三嗪UV吸收剂,
(b)至少一种颜料,其选自喹吖啶酮、二酮基-吡咯并吡咯、喹吖啶酮/二酮基-吡咯并吡咯、异吲哚啉酮、酞菁、BiV、苝、蒽醌红、阴丹酮蓝、偶氮甲碱Cu络合物、单偶氮Ni络合物、喹诺酞酮、异吲哚啉和萘酚AS以及其混合物和固溶体,和
(c)至少一种粘合剂。
2.根据权利要求1的着色透明涂料组合物,其中该2-羟基苯基三嗪UV吸收剂是式(I)、(II)、(III)、(IV)、(V)或者(VI):
其中
X和Y独立地是苯基、萘基、芘基、菲基或者荧蒽基,或者是被下面的基团取代的所述的苯基、所述的萘基、所述的芘基、所述的菲基或者所述的荧蒽基:被1-3个1-6个碳原子的烷基、卤素、羟基或者1-6个碳原子的烷氧基或者其混合物;或者独立地是Z1或者Z2;
X、X′、Y和Y′相同或者不同,并且其定义同X和Y;
R1是氢、1-24个碳原子的直链或者支链烷基、5-12个碳原子的环烷基、7-15个碳原子的苯基烷基、卤素、-SR3、-SOR3或者-SO2R3;或者是被下面的基团取代的所述的烷基、所述的环烷基或者所述的苯基烷基:被1-3个卤素、-R4、-OR5、-N(R5)2、-COR5、-COOR5、-OCOR5、-CN、-NO2、-SR5、-SOR5、-SO2R5或者-P(O)(OR5)2、吗啉基、哌啶基、2,2,6,6-四甲基哌啶基、哌嗪基或者N-甲基哌啶基基团或者其组合;或者是被下面的基团间断的所述的烷基或者所述的环烷基:1-4个亚苯基、-O-、-NR5-、-CONR5-、-COO-、-OCO-或者-CO基团或者其组合;或者是被上述基团的组合取代和间断取代和间断的所述的烷基或者所述的环烷基;
R1、R1′和R1″相同或者不同,并且定义同R1;
R2是氢、1-24个碳原子的直链或者支链烷基或者5-12个碳原子的环烷基;或者是被下述基团取代的所述的烷基或者所述的环烷基:1-4个卤素、环氧基、缩水甘油氧基、呋喃氧基、-R4、-OR5、-N(R5)2、-CON(R5)2、-COR5、-COOR5、-OCOR5、-OCOC(R5)=C(R5)2、-C(R5)=CCOOR5、-CN、-NCO、或者
或者其组合;或者是被下面的基团间断的所述的烷基或者所述的环烷基:1-4个环氧基、-O-、-NR5-、-CONR5-、-COO-、-OCO-、-CO-、-C(R5)=C(R5)COO-、-OCOC(R5)=C(R5)-、-C(R5)=C(R5)-、亚苯基或者亚苯基-G-亚苯基,其中G是-O-、-S-、-SO2-、-CH2-或者-C(CH3)2-或者其组合,或者是被上述基团的组合取代和间断取代和间断的所述的烷基或者所述的环烷基;或者R2是-SO2R3或者-COR6;
R2、R2′和R2″相同或者不同,并且定义同R2;
R3是1-20个碳原子的烷基、3-18个碳原子的链烯基、5-12个碳原子的环烷基、7-15个碳原子的苯基烷基、6-10个碳原子的芳基或者是被1或2个1-4个碳原子的烷基取代的所述的芳基;
R4是6-10个碳原子的芳基或者是被1-3个卤素、1-8个碳原子的烷基、1-8个碳原子的烷氧基或者其组合取代的所述的芳基;5-12个碳原子的环烷基;7-15个碳原子的苯基烷基或者在该苯环上被1-3个卤素、1-8个碳原子的烷基、1-8个碳原子的烷氧基或者其组合取代的所述的苯基烷基;或者2-18个碳原子的直链或者支链链烯基;
R5的定义同R4;或者R5还是氢或者1-24个碳原子的直链或者支链烷基、2-24个碳原子的链烯基;或者R5是下式的基团:
T是氢、氧基、羟基、-OT1、1-24个碳原子的烷基、被1-3个羟基取代的所述的烷基;苄基或者2-18个碳原子的烷酰基;
T1是1-24个碳原子的烷基、5-12个碳原子的环烷基、2-24个碳原子的链烯基、5-12个碳原子的环烯基、7-15个碳原子的苯基烷基、7-12个碳原子的饱和的或者不饱和的双环或者三环烃基团或者6-10个碳原子的芳基或者被1-3个1-4个碳原子烷基取代的所述的芳基;
R6是1-18个碳原子的直链或者支链烷基、2-12个碳原子的直链或者支链链烯基、苯氧基、1-12个碳原子的烷基氨基、6-12个碳原子的芳基氨基、-R7COOH或者-NH-R8-NCO;
R7是2-14个碳原子的亚烷基、或者亚苯基;
R8是2-24个碳原子的亚烷基、亚苯基、甲代亚苯基、二苯基甲烷或者基团
t是0-9;
L是1-12个碳原子的直链或者支链亚烷基、5-12个碳原子的亚环烷基或者被亚环己基或者亚苯基取代的或者间断的亚烷基;或者L是亚苄基;或者L是-S-、-S-S-、-S-E-S-、-SO-、-SO2-、-SO-E-SO-、-SO2-E-SO2-、-CH2-NH-E-NH-CH2-或者
E是2-12个碳原子的亚烷基、5-12个碳原子的亚环烷基或者被5-12个碳原子的亚环烷基间断或者端接的亚烷基;
n是2、3或者4;
当n是2时;Q是2-16个碳原子的直链或者支链亚烷基;或者是被1-3个羟基基团取代的所述的亚烷基;或者是被1-3个-CH=CH-或者-O-间断的所述的亚烷基;或者是被上述基团的组合取代和间断取代和间断的所述的亚烷基;或者Q 是亚二甲苯基或者是基团-CONH-R8-NHCO-、-CH2CH(OH)CH2O-R9-OCH2CH(OH)CH2-、-CO-R10-CO-、或者-(CH2)m-COO-R11-OOC-(CH2)m-,其中m是1-3;或者Q是
R9是2-50个碳原子的亚烷基;或者是被1-10个-O-、亚苯基或者基团-亚苯基-G-亚苯基间断的所述的亚烷基,其中G是-O-、-S-、-SO2-、-CH2-或者-C(CH3)2-;
R10是2-10个碳原子的亚烷基,或者是被1-4个-O-、-S-或者-CH=CH-间断的所述的亚烷基;或者R10是6-12个碳原子的亚芳基;
R11是2-20个碳原子的亚烷基或者是被1-8个-O-间断的所述的亚烷基;
当n是3时,Q是基团-[(CH2)mCOO]3-R12,其中m是1-3,R12是3-12个碳原子的烷三基;
当n是4时,Q是基团-[(CH2)mCOO]4-R13,其中m是1-3,R13是4-12个碳原子的烷四基;
Z1是下式的基团:
Z2是下式的基团:
其中
r1和r2彼此独立地是0或者1;
R14、R15、R16、R17、R18、R19、R20、R21、R22和R23彼此独立地是氢、羟基、氰基、1-20个碳原子的烷基、1-20个碳原子的烷氧基、7-15个碳原子的苯基烷基、5-12个碳原子的环烷基、5-12个碳原子的环烷氧基、卤素、1-5个碳原子的卤代烷基、磺基、羧基、2-12个碳原子的酰基氨基、2-12个碳原子的酰氧基、2-12个碳原子的烷氧基羰基、或者氨基羰基;或者R17和R18或者R22和R23与它们连接到其上的苯基一起是被1-3个-O-或者-NR5-间断的环状基团。
3.根据权利要求2的着色透明涂料组合物,其中组份(a)是式(I)、(II)或者(III)的2-羟基苯基三嗪UV吸收剂,其中
X和Y独立地是苯基,或者是被下面的基团取代的所述的苯基:1-3个1-6个碳原子的烷基、羟基或者1-6个碳原子的烷氧基或者其混合物;或者独立地是Z1或者Z2;
R1是氢;
R1′和R1″定义同R1;
R2是氢、1-24个碳原子的直链或者支链烷基;或者是被下面的基团取代的所述的烷基:1-4个-R4、-OR5、-N(R5)2、-CON(R5)2、-COR5、-COOR5、-OCOR5、-OCOC(R5)=C(R5)2、-C(R5)=CCOOR5、或者其组合;或者是被下面的基团间断的所述的烷基:1-4个-O-、-NR5-、-CONR5-、-COO-、-OCO-、-CO-、-C(R5)=C(R5)COO-、-OCOC(R5)=C(R5)-、-C(R5)=C(R5)-、或者其组合,或者是被上述基团的组合取代和间断的所述的烷基;或者R2是-COR6;
R2、R2′和R2″相同或者不同,并且定义同R2;
R4是2-18个碳原子的直链或者支链链烯基;
R5的定义同R4;或者R5还是氢或者1-24个碳原子的直链或者支链烷基、2-24个碳原子的链烯基;
R6是1-18个碳原子的直链或者支链烷基、2-12个碳原子的直链或者支链链烯基、1-12个碳原子的烷基氨基;
Z1是下式的基团:
Z2是下式的基团:
其中
r1和r2彼此独立地是0或者1;
R14、R15、R16、R17、R18、R19、R20、R21、R22和R23彼此独立地是氢、羟基、1-20个碳原子的烷基、1-20个碳原子的烷氧基、羧基、2-12个碳原子的酰基氨基、2-12个碳原子的酰氧基、2-12个碳原子的烷氧基羰基、或者氨基羰基。
4.根据权利要求1-3任一项的着色透明涂料组合物,其中组份(a)是两种或多种不同的2-羟基苯基三嗪UV吸收剂的混合物。
5.根据权利要求1-4的着色透明涂料组合物,其中组份(b)是C.I.颜料红170、177、179、202、254、264、C.I.颜料紫19、23、C.I.颜料蓝15、15:1、15:2、15:3、15:4、15:6、16、60、C.I.颜料黄109、110、129、138、139、150、184、C.I.颜料绿7、36、C.I.颜料橙48、73、二酮基-吡咯并吡咯颜料、喹吖啶酮颜料、喹吖啶酮/二酮基-吡咯并吡咯颜料;以及其混合物或者其固溶体。
6.根据权利要求1-5任一项的着色透明涂料组合物,其中组份(c)是醇酸树脂、聚酯树脂、丙烯酸树脂、环氧树脂、聚氨酯树脂、蜜胺/甲醛树脂、脲/甲醛树脂、封闭的异氰酸酯树脂或者其组合。
7.根据权利要求1-6任一项的着色透明涂料组合物,其中该涂料组合物是一种汽车涂料组合物。
8.根据权利要求1-7任一项的着色透明涂料组合物,其中组份(a)的存在量是固体粘合剂(c)的0.2-20重量%。
9.根据权利要求1-8任一项的着色透明涂料组合物,其中组份(b)的存在量是固体粘合剂(c)的0.2-10重量%。
10.根据权利要求1-9任一项的着色透明涂料组合物,其中组份(a)与组份(b)的重量比是10∶1-1∶1。
11.根据权利要求1-10任一项的着色透明涂料组合物,其包含另外的添加剂。
12.根据权利要求11的着色透明涂料组合物,其包含作为另外的添加剂的酚和/或胺抗氧化剂、空间位阻胺稳定剂、不同于权利要求1所定义的UV-吸收剂的UV-吸收剂、亚磷酸酯、亚膦酸酯、苯并呋喃酮、金属硬脂酸盐、金属氧化物、有机磷化合物、羟基胺和/或阻燃剂。
13.根据权利要求12的着色透明涂料组合物,其包含作为另外的添加剂的空间位阻胺稳定剂和/或UV吸收剂,其选自草酰胺、2-羟基苯甲酮、苯甲酸酯、丙烯酸酯和2-(2′-羟基苯基)苯并***。
14.一种着色透明涂层,其是通过将权利要求1-13任一项的着色透明涂料组合物施涂到基底而获得的。
15.根据权利要求14的着色透明涂层,其是一种汽车涂层。
16.根据权利要求15的着色透明涂层,其中该汽车涂层包含下面的层:
(d)阴极沉积的涂层,其粘附到金属基底上;
(e)至少一个随后的涂层,其粘附到所述的阴极沉积涂层上;
(f)至少一个含有颜料或者颜料混合物的底涂层;
(g)权利要求14所定义的着色透明涂层。
17.一种制备着色透明涂层的方法,所述方法包括将权利要求1-13任一项的着色透明涂料组合物施涂到基底上。
18.根据权利要求17的方法,其中该基底包含下面的层:
(d)阴极沉积的涂层,其粘附到金属基底上;
(e)至少一个随后的涂层,其粘附到所述的阴极沉积涂层上;和
(f)至少一个含有颜料或者颜料混合物的底涂层。
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CN104955910A (zh) * | 2013-02-01 | 2015-09-30 | 拜耳材料科技股份有限公司 | 可uv固化的涂料组合物 |
CN105408433A (zh) * | 2013-08-30 | 2016-03-16 | Sdc科技有限公司 | 可成型的基于氨基塑料树脂的涂料组合物 |
CN105838230A (zh) * | 2016-04-29 | 2016-08-10 | *** | 一种木器用水性聚氨酯涂料及其制备方法 |
CN106537255A (zh) * | 2014-04-18 | 2017-03-22 | 陶氏环球技术有限责任公司 | 用于lcd的彩色滤光片的蒽醌化合物 |
CN107109085A (zh) * | 2014-12-19 | 2017-08-29 | 巴斯夫欧洲公司 | 用于保护基材以防UV/Vis辐射的UV吸收剂和颜料的组合 |
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JP5669584B2 (ja) * | 2008-03-12 | 2015-02-12 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | フラットパネルディスプレイ用光学フィルム |
CN105358528B (zh) | 2013-07-08 | 2021-07-20 | 巴斯夫欧洲公司 | 新型光稳定剂 |
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CN107746389B (zh) * | 2017-09-14 | 2019-10-22 | 江苏丹霞新材料有限公司 | 将傅克法制备芳基均三嗪类紫外光吸收剂中的催化剂再循环利用的方法 |
KR20220037804A (ko) | 2020-09-18 | 2022-03-25 | 주식회사 엘지화학 | 화합물 및 이를 포함하는 유기 발광 소자 |
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- 2007-12-17 EP EP07857654.3A patent/EP2104716B1/en not_active Not-in-force
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Cited By (6)
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CN104955910A (zh) * | 2013-02-01 | 2015-09-30 | 拜耳材料科技股份有限公司 | 可uv固化的涂料组合物 |
CN105408433A (zh) * | 2013-08-30 | 2016-03-16 | Sdc科技有限公司 | 可成型的基于氨基塑料树脂的涂料组合物 |
CN105408433B (zh) * | 2013-08-30 | 2017-09-15 | Sdc 科技有限公司 | 可成型的基于氨基塑料树脂的涂料组合物 |
CN106537255A (zh) * | 2014-04-18 | 2017-03-22 | 陶氏环球技术有限责任公司 | 用于lcd的彩色滤光片的蒽醌化合物 |
CN107109085A (zh) * | 2014-12-19 | 2017-08-29 | 巴斯夫欧洲公司 | 用于保护基材以防UV/Vis辐射的UV吸收剂和颜料的组合 |
CN105838230A (zh) * | 2016-04-29 | 2016-08-10 | *** | 一种木器用水性聚氨酯涂料及其制备方法 |
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ES2670436T3 (es) | 2018-05-30 |
KR101541431B1 (ko) | 2015-08-03 |
CN103819960A (zh) | 2014-05-28 |
EP2104716B1 (en) | 2018-02-21 |
US20100062270A1 (en) | 2010-03-11 |
EP2104716A1 (en) | 2009-09-30 |
WO2008086929A1 (en) | 2008-07-24 |
KR20090110828A (ko) | 2009-10-22 |
JP5580599B2 (ja) | 2014-08-27 |
PL2104716T3 (pl) | 2018-07-31 |
US20150079412A1 (en) | 2015-03-19 |
JP2010515791A (ja) | 2010-05-13 |
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