CN101111496B - 长波长位移苯并三唑uv-吸收剂和它们的用途 - Google Patents
长波长位移苯并三唑uv-吸收剂和它们的用途 Download PDFInfo
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- CN101111496B CN101111496B CN2006800037870A CN200680003787A CN101111496B CN 101111496 B CN101111496 B CN 101111496B CN 2006800037870 A CN2006800037870 A CN 2006800037870A CN 200680003787 A CN200680003787 A CN 200680003787A CN 101111496 B CN101111496 B CN 101111496B
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- Prior art keywords
- phenyl
- compound
- butyl
- general formula
- acid
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- 239000012964 benzotriazole Substances 0.000 title claims abstract description 22
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000006096 absorbing agent Substances 0.000 title claims abstract description 11
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- 238000000034 method Methods 0.000 claims abstract description 27
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- 239000011368 organic material Substances 0.000 claims abstract description 16
- -1 azide chemical compound Chemical class 0.000 claims description 156
- 229910052757 nitrogen Inorganic materials 0.000 claims description 59
- 239000003795 chemical substances by application Substances 0.000 claims description 50
- 238000010521 absorption reaction Methods 0.000 claims description 44
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 43
- 238000000576 coating method Methods 0.000 claims description 41
- 239000011248 coating agent Substances 0.000 claims description 40
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 36
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 32
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- 239000000126 substance Substances 0.000 claims description 26
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- 125000003884 phenylalkyl group Chemical group 0.000 claims description 20
- 150000002431 hydrogen Chemical class 0.000 claims description 19
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
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- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical class C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 5
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- FLPKSBDJMLUTEX-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)(CCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLPKSBDJMLUTEX-UHFFFAOYSA-N 0.000 description 14
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- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 10
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- ZPNJBTBYIHBSIG-UHFFFAOYSA-N phenyl-(2,2,6,6-tetramethylpiperidin-4-yl)methanone Chemical compound C1C(C)(C)NC(C)(C)CC1C(=O)C1=CC=CC=C1 ZPNJBTBYIHBSIG-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001627 poly(4-methyl styrene) Polymers 0.000 description 1
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- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
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- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- MQOCIYICOGDBSG-UHFFFAOYSA-M potassium;hexadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCC([O-])=O MQOCIYICOGDBSG-UHFFFAOYSA-M 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
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- 239000001294 propane Substances 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
- 239000011241 protective layer Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
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- 230000000630 rising effect Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 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
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-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
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000012747 synergistic agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 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
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 229960004418 trolamine Drugs 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 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
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- 239000002076 α-tocopherol Substances 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
- Cosmetics (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明涉及一直到410-420nm有显著吸收的具有长波长位移吸收光谱的新型苯并三唑UV-吸收剂。本发明的其它方面是它们的制备方法,含有新UV-吸收剂的UV稳定化组合物和该新化合物作为有机材料的UV光稳定剂的用途。
Description
本发明涉及一直到410-420nm有显著吸收的具有长波长位移吸收光谱的新型苯并三唑UV-吸收剂。本发明的其它方面是它们的制备方法,含有新UV-吸收剂的UV稳定化组合物和该新化合物作为有机材料的UV光稳定剂的用途。
含有芳族结构部分的聚合物基材,如以芳族环氧化物,芳族聚酯或芳族(多)异氰酸酯为基础的粘合剂或涂料对于高达约410到420nm的波长的UV/VIS辐射是高度敏感的。
在表面上有UV吸收层的此类粘合剂或涂料层的保护是及其困难的,因为穿透该UV吸收外涂层的已经非常少量的辐射-甚至在410nm左右的范围内-足以引起保护涂层的层离和剥落。
其中长波长位移UV吸收剂极其有用的典型应用是汽车涂料,典型地双道涂层型金属汽车涂料。
当今的汽车涂料将防腐阴极电镀涂料直接施涂于钢板上。由于阴极电镀树脂的显著红移光敏性(一直到约400-410nm),不可能利用在外涂层中的普通的现有技术UV吸收剂来充分地保护阴极电镀涂层。
为了更好地保护此类光敏层,尝试将苯并三唑的UV吸收向着更长波长位移。例如,US5436349公开了苯并三唑UV-吸收剂,它在苯并环的5位上被烷基磺酰基取代。然而,该吸收位移对于保护如此高敏感性的材料显得不是足够大。
US6,166,218公开了,例如,苯并三唑UV吸收剂,它在苯并环的5位上被CF3基团取代,也导致稍长波长位移的吸收和导致增强的光化稳定性。然而,这一吸收位移远远不足以一直到410nm保护具有光化学敏感性的材料。
现在吃惊发现,当苯并三唑UV-吸收剂的苯并环属于邻苯二甲酸酐或酰亚胺体系的一部分时,观察到最大吸收的约20-30nm的大位移,一直延伸到420nm。该化合物出乎意料地保持光化学稳定并且在典型的涂料应用中实际上没有显示出位移。
本发明的一个方面是通式(I)或(II)的化合物:
其中
R1是氢,或具有1到24个碳原子的直链或支链烷基,具有2到18个碳原子的直链或支链链烯基,具有5到12个碳原子的环烷基,具有7到15个碳原子的苯基烷基,苯基,或在苯基环上被1-4个具有1到4个碳原子的烷基取代的苯基或苯基烷基;或
L是1到12个碳原子的亚烷基,2到12个碳原子的烷叉基(alkylidene),苄叉基(benzylidene),对-亚二甲苯基或具有5到7个碳原子的亚环烷基;
R2是具有1到24个碳原子的直链或支链烷基,具有2到18个碳原子的直链或支链链烯基,具有5到12个碳原子的环烷基,具有7到15个碳原子的苯基烷基,苯基,或在苯基环上被1-3个具有1到4个碳原子的烷基取代的该苯基或该苯基烷基;或
该烷基被一个或多个-OH,-OCO-R11,-OR14,-NCO或-NH2基团或它们的混合物所取代,或该烷基或该链烯基被一个或多个-O-,-NH-或-NR14-基团或它们的混合物插入并且它们能够是未被取代的或被一个或多个-OH,-OR14或-NH2基团或它们的混合物所取代;其中
R11是氢,直链或支链C1-C18烷基,C5-C12环烷基,直链或支链C3-C8链烯基,苯基,萘基或C7-C15苯基烷基;和
R14是氢,具有1到24个碳原子的直链或支链烷基;或
R2是-OR14,基团-C(O)-O-R14,-C(O)-NHR14或-C(O)-NR14R′14,其中R′14具有与R14相同的意义;或
R2是,-NHR13或-N(R13)2;或
R2是-(CH2)m-CO-X1-(Z)p-Y-R15,其中
X1是-O-或-N(R16)-,
Y是-O-或-N(R17)-或直接的键,
Z是C2-C12-亚烷基,被1-3个氮原子、氧原子或它们的混合物所插入的C4-C12亚烷基,或是C3-C12亚烷基,亚丁烯基,亚丁炔基,亚环已基或亚苯基,它们中的每一种可以另外被羟基取代;
或基团
m是零,1或2,
p是1,或当X和Y分别是-N(R16)-和-N(R17)-时p也是零,
R15是氢,C1-C12烷基,基团
或基团-CO-C(R18)=C(H)R19或,当Y是-N(R17)-时,与R17一起形成基团-CO-CH=CH-CO-,其中
R18是氢或甲基,和R19是氢,甲基或-CO-X1-R20,其中
R20是氢,C1-C12烷基或以下通式的基团
或
R5,R6,R7和R8独立地是氢,卤素,CN,NO2或NH2;
R13是具有1到20个碳原子的烷基,具有2到20个碳原子的羟烷基,具有3到18个碳原子的链烯基,具有5到12个碳原子的环烷基,具有7到15个碳原子的苯基烷基,苯基或萘基,它们两者可以被一个或两个具有1-4个碳原子的烷基所取代;
R16和R17彼此独立地是氢,C1-C12-烷基,被1到3个氧原子插入的C3-C12-烷基,或是环己基或C7-C15苯基烷基,并且当Z是亚乙基时R16与R17一起也形成亚乙基;
X是O或NE1,其中
E1是氢,直链或支链C1-C24烷基,直链或支链C2-C18链烯基,C2-C6炔基,C5-C12环烷基,苯基,萘基或C7-C15苯基烷基;或能够被一个或多个
-F,-OH,-OR22,-NH2,-NHR22,-N(R22)2,-NHCOR23,-NR22COR23,-OCOR24,-COR25,-SO2R26,-PO(R27)n(R28)2-n,-Si(R29)n(R30)3-n,-Si(R22)3,-N+(R22)3A-,-S+(R22)2A-,
-环氧乙烷基(oxiranyl)基团或它们的混合物插入的该直链或支链C1-C24烷基,直链或支链C2-C24链烯基,C5-C12环烷基,C2-C6炔基;该直链或支链C1-C24烷基,直链或支链未被取代的或取代的C2-C24链烯基,C5-C12环烷基或C2-C6炔基也能够被一个或多个-O-,-S-,-NH-或-NR22-基团或它们的结合物所插入;
该苯基,萘基或C7-C15苯基烷基也能够被一个或多个-卤素,-CN,-CF3,-NO2,-NHR22,-N(R22)2,-SO2R26,-PO(R27)n(R28)2-n,OH,-OR22,-COR25,-R25 取代;其中
n是O,1或2;
R22是直链或支链C1-C18烷基,或直链或支链C2-C18链烯基,C5-C10环烷基,苯基或萘基,C7-C15苯基烷基,或两个R22当连接于N或Si原子上时能够与它们所连接到的原子一起形成吡咯烷,哌啶或吗啉环;
R23是氢,OR22,NHR22,N(R22)2或具有与R22相同的意义,
R24是OR22,NHR22,N(R22)2或具有与R22相同的意义,
R25是氢,OH,OR22,NHR22或N(R22)2,O-缩水甘油基或具有与R22相同的意义,
R26是OH,OR22,NHR22或N(R22)2,
R27是NH2,NHR22或N(R22)2,
R28是OH或OR22,
R29是C1或OR22,
R30是直链或支链C1-C18烷基;或
R1到R8具有以上定义的意义和
Q是直链或支链的C2-C12亚烷基,C2-C12亚烷基,后者被一个或多个-O-、NH或NR14原子插入,C5-C10亚环烷基,对-亚苯基或基团
其中*表示键。
卤素是,例如,氟,氯,溴或碘。氯是优选的。
当这些取代基中的任何一个是具有1到24个碳原子的直链或支链烷基时,此类基团是,例如,甲基,乙基,异丙基,正丁基,异丁基,仲丁基,叔丁基,叔戊基,2-乙基己基,叔辛基,月桂基,叔-十二烷基,十三烷基,正十六烷基,正十八基或二十烷基。
当该取代基中的任何一个是具有2到18个碳原子的直链或支链链烯基时,此类基团是,例如,烯丙基,戊烯基,己烯基,癸烯基(doceneyl)或油基。
优选的是具有3-16个,尤其3-12个,例如2-6个碳原子的链烯基。
当这些取代基中的任何一个是具有5到12个碳原子的环烷基时,此类基团是,例如,环戊基,环己基,环庚基,环辛基和环十二烷基。
C1-C4烷基-取代C5-C8环烷基是,例如,甲基环戊基,二甲基环戊基,甲基环己基,二甲基环己基,三甲基环己基或叔丁基环己基。
当这些基团中的任何一个是具有7到15个碳原子的苯基烷基时,此类基团是,例如,苄基,苯乙基,α-甲基苄基或α,α-二甲基苄基。
当苯基被烷基取代时,这例如是甲苯基和二甲基苯基。
被一个或多个-O-基团取代和/或被一个或多个-OH取代的烷基能够是,例如,-(OCH2CH2)wOH或-(OCH2CH2)wO(C1-C24烷基),其中w是1到12。
被一个或多个-O-插入的烷基能够是从亚乙基氧基单元或从亚丙基氧基单元或从两者的混合物衍生的。
当烷基被-NH-或-NR14-插入时,这些基团与以上-O-插入的基团类似地衍生化。优选的是乙二胺的重复单元。
例子是
CH3-O-CH2CH2-,CH3-NH-CH2CH2-,CH3-N(CH3)-CH2-,CH3-O-CH2CH2-O-CH2CH2-,CH3-(O-CH2CH2-)2O-CH2CH2-,CH3-(O-CH2CH2-)3O-CH2CH2-或CH3-(O-CH2CH2-)4O-CH2CH2-。
亚烷基是,例如,亚乙基,四亚甲基,六亚甲基,2-甲基-1,4-四亚甲基,六亚甲基,八亚甲基,十亚甲基和十二亚甲基。
亚环烷基是,例如,亚环戊基,亚环已基,亚环庚基,亚环辛基和亚环十二烷基。优选的是亚环已基。
被氧,NH或-NR14-插入的亚烷基是,例如,-CH2CH2-O-CH2CH2-, -CH2CH2-NH-CH2CH2-,-CH2CH2-N(CH3)-CH2CH2-,-CH2CH2-O-CH2CH2-O-CH2CH2-,-CH2CH2-(O-CH2CH2-)2O-CH2CH2-,-CH2CH2-(O-CH2CH2-)3O-CH2CH2-,-CH2CH2-(O-CH2CH2-)4O-CH2CH2-或-CH2CH2-NH-CH2CH2-。
该基团Q是直链或支链C1-C12亚烷基,C5-C10亚环烷基,对-亚苯基或基团
该基团能够从容易获取的二胺,例如所谓的杰夫胺类(Jeffamines),衍生。二胺的例子是乙二胺,亚丙基二胺,2-甲基-1,5-五亚甲基二胺,异佛尔酮二胺或1,2-二氨基环己烷。
类似地,该基团Z也能够从相同的可获取的二胺或从相应二醇衍生。
优选的是结构式(I)或(II)的化合物,其中
R1是氢,或具有1到24个碳原子的直链或支链烷基,具有2到18个碳原子的直链或支链链烯基,具有5到12个碳原子的环烷基,具有7到15个碳原子的苯基烷基,苯基,或在苯基环上被1-4个具有1到4个碳原子的烷基取代的苯基或苯基烷基;或
R1是基团或基团其中L 是1到12个碳原子的亚烷基,2到12个碳原子的烷叉基,苄叉基,对-亚二甲苯基或具有5到7个碳原子的亚环烷基;
R2是具有1到24个碳原子的直链或支链烷基,具有2到18个碳原子的直链或支链链烯基,具有5到12个碳原子的环烷基,具有7到15个碳原子的苯基烷基,苯基,或在苯基环上被1-3个具有1到4个碳原子的烷基取代的该苯基或该苯基烷基;或
R2是-(CH2)m-CO-X1-(Z)p-Y-R15,其中
X1是-O-,
Y是-O-或直接的键,
Z是C2-C12-亚烷基,被1-3个氮原子、氧原子或它们的混合物插入的C4-C12亚烷基,或当Y是直接的键时,Z能够另外也是直接的键;
m是2,
p是1,
R15是氢或C1-C12烷基或基团
R5,R6,R7和R8独立地是氢,Cl或Br;
X是O或NE1,其中
E1是氢,直链或支链C1-C24烷基,直链或支链C2-C18链烯基,C2-C6炔基,C5-C12环烷基,苯基,萘基或C7-C15苯基烷基;或能够被一个或多个
-F,-OH,-OR22,-NH2,-NHR22,-N(R22)2,-NHCOR23,-NR22COR23,-OCOR24,-COR25,-SO2R26,-PO(R27)n(R28)2-n,-Si(R29)n(R30)3-n,-Si(R22)3,-N+(R22)3A-,-S+(R22)2A-,
-环氧乙烷基基团或它们的混合物取代的该直链或支链C1-C24烷基,直链或支链C2-C24链烯基,C5-C12环烷基,C2-C6炔基;该直链或支链C1-C24烷基,直链或支链未被取代的或取代的C2-C24链烯基,C5-C12环烷基 或C2-C6炔基也能够被一个或多个-O-,-S-,-NH-或-NR22-基团或它们的结合物所插入;
该苯基,萘基或C7-C15苯基烷基也能够被一个或多个-卤素,-CN,-CF3,-NO2,-NHR22,-N(R22)2,-SO2R26,-PO(R27)n(R28)2-n,-OH,-OR22,-COR25,-R25取代;其中
n是O,1或2;
R22是直链或支链C1-C18烷基,或直链或支链C2-C18链烯基,C5-C10环烷基,苯基或萘基,C7-C15苯基烷基,或两个R22当连接于N或Si原子上时能够与它们所连接到的原子一起形成吡咯烷,哌啶或吗啉环;
R23是氢,OR22,NHR22,N(R22)2或具有与R22相同的意义,
R24是OR22,NHR22,N(R22)2或具有与R22相同的意义,
R25是氢,OH,OR22,NHR22或N(R22)2,O-缩水甘油基或具有与R22相同的意义,
R26是OH,OR22,NHR22或N(R22)2,
R27是NH2,NHR22或N(R22)2,
R28是OH或OR22,
R29是C1或OR22,
R30是直链或支链C1-C18烷基;或
R1到R8具有以上定义的意义和
Q是直链或支链C2-C12亚烷基,C5-C10亚环烷基或对-亚苯基或以下基团:
例如,在通式(I)或(II)的化合物中
R1是氢,或具有1到24个碳原子的直链或支链烷基,具有2到18个碳原子的直链或支链链烯基,具有5到12个碳原子的环烷基,具有7到15个碳原子的苯基烷基,苯基,或在苯基环上被1-4个具有1到4个碳原子的烷基取代的苯基或苯基烷基;
R2是具有1到24个碳原子的直链或支链烷基,具有2到18个碳原子的直链或支链链烯基,具有5到12个碳原子的环烷基,具有7到15个碳原子的苯基烷基,苯基,或在苯基环上被1-3个具有1到4个碳原子的烷基取代的该苯基或该苯基烷基;或
R2是-(CH2)2-CO-O-(Z)-O-R15,其中
Z是C2-C12-亚烷基,被1-3个氧原子插入的C4-C12亚烷基;
R15是氢或C1-C12烷基或基团
R5,R6,R7和R8独立地是氢,Cl或Br;
X是O或NE1,其中
E1是氢,直链或支链C1-C24烷基,C5-C12环烷基,苯基或C7-C15苯基烷基;或该直链或支链C1-C24烷基或C5-C12环烷基能够被一个或多个-F,-OH,-OR22,-NH2,-NHR22,-N(R22)2取代;
该苯基或C7-C15苯基烷基也能够被一个或多个-卤素,-CN,-CF3,-OH,-OR22,-COR22,-R22取代;其中
R22是直链或支链C1-C18烷基,直链或支链C2-C18链烯基,C5-C10环烷基,C6-C16苯基或萘基,C7-C15苯基烷基;或
R1到R8具有以上定义的意义和
Q是C2-C12亚烷基,C5-C7亚环烷基,对-亚苯基或基团
特别优选的是结构式(I)或(II)的化合物,其中
R1是氢,具有1到12个碳原子的直链或支链烷基或具有7到15个碳原子的苯基烷基;
R2是具有1到12个碳原子的直链或支链烷基或具有7到15个碳原子的苯基烷基,苯基,或在苯基环上被1-3个具有1-4个碳原子的烷基取代的该苯基或该苯基烷基;
R5和R6是氢或两者中的一个是Cl或Br;
R7和R8独立地是氢,Cl或Br;
X是O或NE1,其中
E1是氢,未被取代的或被1-4个OH取代的直链或支链C1-C6烷基,未被取代的或被F,CF3,CN或Cl取代的苯基,或C7-C9苯基烷基。
结构式(I)的化合物一般是优选的。
各有用的化合物例如是化合物1b和2c
本发明的附加方面是结构式(I)或(II)的化合物的制备方法:
其中该取代基R1到R8与权利要求1中定义相同,该方法包括让通式(III),(IV)或(V)的化合物
与通式(X)的叠氮化合物进行反应
Mn+(N3 -)r(X)
式中
R101,R102,R103和R104各自独立地是是氢或C1-C18烷基,
R105是C1-C18烷基,和
r是1,2或3。
根据本发明的方法的优选的反应条件是如下:
反应能够在熔体中或在溶剂中进行。特别理想的是其中反应在溶剂中进行的通式I或II的化合物的制备方法。
合适溶剂是,例如,偶极非质子传递溶剂,质子溶剂,脂肪族或芳族羧酸的酯,醚类,卤代烃类,芳族溶剂,胺和烷氧基苯类。
偶极非质子传递溶剂的例子是二烷基亚砜,例如二甲基亚砜;羧酰胺类,例如甲酰胺,二甲基甲酰胺或N,N-二甲基乙酰胺;内酰胺,例如N-甲基吡咯烷酮;磷酰胺,例如六甲基磷酰三胺;烷基化脲类,例如N,N’-二甲基亚乙基脲,N,N’-二甲基亚丙基脲或N,N,N′,N’-四甲基脲;和腈类,例如乙腈或苄腈。
质子溶剂的例子是聚(亚烷基)二醇,例如聚乙二醇;聚(亚烷基)二醇单醚,例如二乙二醇一甲基醚,和水,后者本身或在有所提及的一种或多种溶剂的单相或二相混合物中,也有可能添加相转移催化剂,例如,四烷基铵盐,四烷基鏻盐或冠醚。相同的相转移催化剂也能够以固体/液体形式用于两相体系中。
脂肪族或芳族羧酸的优选酯是,例如,乙酸丁酯,乙酸环已基酯和苯甲酸甲酯。
优选的乙醚是,例如,二烷基醚,特别二丁基醚,四氢呋喃,二噁烷和(聚)亚烷基二醇二烷基醚。
卤代烃例如是二氯甲烷和氯仿。
芳族溶剂是,例如,甲苯,氯苯和硝基苯。
合适的胺溶剂是,例如,三乙基胺,三丁基胺和苄基-二甲基胺。
优选的烷氧基苯类例如是苯甲醚和苯乙醚。
通式I的化合物的制备方法也能够在离子或超临界流体例如挥发性二氧化碳中进行。
特别理想的是其中反应在偶极非质子溶剂中进行的通式I或II的化合物的制备方法。
反应温度能够在宽范围内变化但要求在选择时有令人满意的转化率,该温度优选是10℃-200℃,特别20℃-150℃。
其它苯并三唑化合物的类似方法早已公开在WO02/24668中。
优选的是通式I或II的化合物的制备方法,其中通式III、IV或V的化合物的量与通式X的叠氮化合物的量的摩尔比率是1:1至1:3,尤其1:1至1:2,例如1:1至1:1.3。当存在了也能够与叠氮化物反应的官能化侧基时,通式IX的叠氮化合物的过量因此增大。
在特定的实施方案中,该反应是在催化剂存在下进行。
此类催化剂包括,例如,铜(I)或铜(II)盐或其它过渡金属盐,例如基于铁,钴,镍,钯,铂,金或锌。代替过渡金属盐,它的阴离子能够在宽范围内变化,还有可能使用相同金属的金属配合物和金属配合物盐作为催化剂。优选的是铜(I)和铜(II)氯化物、溴化物和碘化物的使用,特别优选的是铜(I)溴化物的使用。
催化剂有利地以0.01-10wt%,尤其0.1-5wt%,例如0.1-5wt%的量使用,基于所使用的通式III、IV或V的化合物的重量。
反应也能够在附加的碱存在下或在碱性pH缓冲体系存在下进行。合适的pH缓冲体系包括,例如,碱金属或碱土金属氢氧化物;碱金属或碱土金属醇化物;碱金属或碱土金属羧酸盐,例如乙酸盐或碳酸盐;碱金属或碱土金属磷酸盐;叔胺,例如三乙胺或三丁基胺;以及未取代的或取代的吡啶。
通式III、IV或V的起始化合物中的一些可以从文献中已知或能够与在实施例1和2中所述的程序类似地制备。
然而,还有可能由制备此类化合物的普通方法制备该苯并三唑。通常的程序包括取代的邻硝基苯胺(W则是NO2)的重氮化,接着所形成的重氮盐与取代酚的偶联,和偶氮苯中间体还原成相应的所需苯并三唑。该方法例如已描述在美国专利5276161和美国专利5977219 中。这些苯并三唑的起始原料部分地是商品或能够由正常的有机合成方法来制备。
苯并三唑的其它制备方法例如已在Science of Synthesis13.13,575-576中给出。
该还原过程不仅能够通过水合来进行,而且可通过其它方法,例如在EP O751134中所述的方法来进行。当发生H-转移时,试剂如甲酸或它的盐,次膦酸或它的盐或连二磷酸的碱金属或铵盐与催化剂一起是有用的。该催化剂例如是贵金属。
本发明的苯并三唑一般可用作各种基材中的UV吸收剂。因此,本发明的附加方面是被稳定化以抵抗光诱导降解的一种组合物,该组合物包括,
(a)易于光诱导降解(subject to light-induced degradation)的有机材料,和
(b)如上所述的通式I或II的化合物。
通常,通式I或II的化合物是以0.1%-30%,优选0.5%-15%和更优选1%-10%(按重量)的量存在,基于有机材料的重量。
在一个方面该有机材料是记录材料。
根据本发明的记录材料适合于压敏复制系统,使用微囊剂的复印系统,热敏复制系统,照相材料和喷墨打印。
根据本发明的记录材料突出表现在质量上的出乎意料的改进,尤其相对于耐光牢度。
根据本发明的记录材料具有为特殊应用所已知的构造。它们由通常的载体例如纸或塑料膜组成,它们已经涂有一个或多个层。取决于材料的类型,这些层含有合适的必要的组分,对于照相材料而言,例如卤化银乳胶,染料成色剂,染料和类似物。特别适合于喷墨打印的材料具有对于常规载体上的油墨有特殊吸收性的层。无涂层纸也能够用于喷墨打印。在这种情况下,该纸同时用作载体材料和用作油墨吸收层。喷墨打印的合适材料例如已描述在美国专利No.5,073,448(引入在这里供参考)中。
该记录材料也可以是透明的,例如,对于投射膜的情况。
通式I或II的化合物能够早在梳理材料(carder material)的生产时被引入到在造纸过程的梳理材料(carder material)中,例如,通过添加到纸浆中。第二种施涂方法是用通式I或II的化合物的水溶液喷雾该 梳理材料或将该化合物添加到涂料组合物中。
为适合于投射的透明记录材料所用的涂料组合物不能含有任何散射光的颗粒物,如颜料和填料。
染料结合涂料组合物含有大量的其它添加剂,例如抗氧化剂,光稳定剂(也包括不属于根据本发明的UV吸收剂的其它UV吸收剂),粘度改进剂,荧光增白剂,生物杀伤剂和/或抗静电剂。
涂料组合物通常制备如下:
将水溶性的组分,例如粘结剂,溶于水中并搅拌在一起。固体组分,例如早已描述过的填料和其它添加剂,被分散在这一含水介质中。理想地利用设备,例如超声处理机,叶轮搅拌机,均化器,胶体磨,珠粒磨机,砂磨机,高速搅拌器等等来进行分散。通式I或II的化合物能够容易地引入到涂料组合物中。
根据本发明的记录材料优选含有1-5000mg/m2,尤其50-1200mg/m2,的通式I化合物。
正如早已提到,根据本发明的记录材料包括宽的领域。通式I或II的化合物能够,例如,用于压敏复制系统中。它们能够被引入纸中以保护微囊密封的染料前体免受光的影响,或被引入到显影剂层的粘结剂中以保护在其中形成的染料。
采用借助于压力来显影的光敏微囊剂的复印系统已描述在美国专利No 4,416,966;4,483,912;4,352,200;4,535,050;4,536,463;4,551,407;4,562,137和4,608,330中,以及描述在EP-A 139,479;EP-A 162,664;EP-A 164,931;EP-A 237,024;EP-A 237,025或EP-A 260,129中。在所有这些系统中,该化合物能够引入到染料接收层中。然而,该化合物也能够引入到给体层中,以便保护成色剂免受光的影响。
能够被稳定化的照相材料是照相用染料和含有该染料或它的前体的层,例如照相纸和膜。合适材料,例如,已描述在美国专利No.5,364,749(引入在这里供参考)中。通式I或II的化合物在这里用作UV过滤剂以抵抗静电骤增。在彩色照相材料中成色剂和染料也被保护防止光化分解。
本化合物能够用于全部类型的彩色照相材料中。例如,它们能够是用于彩色相纸,彩色反转照相纸,直接正性彩色材料,彩色照相胶卷,彩色正片,彩色反转片,等等。优选的是它们尤其可用于含有反 转底物或形成正像的照相用彩色材料。
彩色照相记录材料通常在载体上含有感蓝和/或感绿和/或感红的卤化银乳胶层和如果需要的话保护层,该化合物优选是位于感绿或感红层中或位于在感绿和感红层之间的层中或位于在该卤化银乳胶层之上的层中。
以光聚合,光增塑或微囊剂破裂的原理为基础,或当使用具有热敏的和光敏的重氮盐,具有氧化剂的无色染料或具有路易斯酸的染料内酯类时,通式I或II的化合物也能够用于记录材料中。
此外,它们能够用于一些记录材料中,后者用于染料扩散转移印刷,热蜡转移印刷和非矩阵印刷并且可以为静电印刷机,电照相印刷机,电泳印刷机,磁强记录印刷机和激光-电子照相印刷机和笔式绘图机。在以上这些之中,染料扩散转移印刷的记录材料是优选的,它例如描述在EP-A-507,734中。
它们也能够用于油墨,优选用于喷墨打印,按照例如另外在美国专利No.5,098,477(引入在这里供参考)中所述。
在本发明的另一个特定的实施方案中,有机材料是天然的,半合成或合成的聚合物。
以下给出此类聚合物的实例。
1、单烯烃和二烯烃的聚合物,例如聚丙烯,聚异丁烯,聚丁烯-1,聚-4-甲基戊烯-1,聚异戊二烯或聚丁二烯,以及环状烯烃如环戊烯或降冰片烯的聚合物,聚乙烯(任选地加以交联),例如高密度聚乙烯(HDPE),高密度和高分子量聚乙烯(HDPE-HMW),高密度和超高分子量聚乙烯(HDPE-UHMW),中等密度聚乙烯(MDPE),低密度聚乙烯(LDPE),线性低密度聚乙烯(LLDPE),(VLDPE)和(ULDPE)。
聚烯烃,即在前面的段落中例举的单烯烃的聚合物,优选聚乙烯和聚丙烯,能够通过不同的方法,和优选通过下面的方法来制备:
a)自由基聚合反应(一般在高压和升高的温度下)。
b)使用一般含有一种或一种以上的元素周期表的IVb,Vb,VIb或VIII族的金属的催化剂的催化聚合反应。这些金属通常具有一个或一个以上的配位体,典型的是π键或σ键配位的氧化物,卤化物,醇化物,酯类,醚类,胺类,烷基类,链烯基类和/或芳基类。这些金属配合物可以是游离形式或被固定在基底上,典型地在活化氯化镁、氯 化钛(III)、氧化铝或氧化硅上。这些催化剂可以溶于或不溶于聚合反应介质中。该催化剂本身可用于聚合反应或另外使用活化剂,典型的是金属烷基化物,金属氢化物,金属烷基卤化物,金属烷基氧化物或金属烷基噁烷(alkyloxanes),该金属是元素周期表的Ia,IIa和/或IIIa族的元素。活化剂可以方便地另外用酯,醚,胺或甲硅烷基醚基团改性。这些催化剂体系通常被命名为Phillips,Standard Oil Indiana,Ziegler(-Natta),TNZ(Dupont),金属茂或单中心(single site)催化剂(SSC)。
2、在以上1)项提到的聚合物的混合物,例如聚丙烯与聚异丁烯的混合物,聚丙烯与聚乙烯的混合物(例如PP/HDPE,PP/LDPE)和不同类型的聚乙烯的混合物(例如LDPE/HDPE)。
3、单烯烃和二烯烃的共聚物,或单烯烃和二烯烃与其它乙烯基单体的共聚物,例如乙烯/丙烯共聚物,线性低密度聚乙烯(LLDPE)和它与低密度聚乙烯(LDPE)的混合物,丙烯/丁烯-1共聚物,丙烯/异丁烯共聚物,乙烯/丁烯-1共聚物,乙烯/己烯共聚物,乙烯/甲基戊烯共聚物,乙烯/庚烯共聚物,乙烯/辛烯共聚物,乙烯/乙烯基环己烷共聚物,乙烯/环烯烃共聚物(例如乙烯/降冰片烯如COC),乙烯/1-烯烃共聚物,其中1-烯烃就地产生;丙烯/丁二烯共聚物,异丁烯/异戊二烯共聚物,乙烯/乙烯基环己烷共聚物,乙烯/丙烯酸烷基酯共聚物,乙烯/甲基丙烯酸烷基酯共聚物,乙烯/乙酸乙烯酯共聚物或乙烯/丙烯酸共聚物和它们的盐类(离聚物类)以及乙烯与丙烯和二烯烃如己二烯、二聚环戊二烯或乙叉基一降冰片烯的三元共聚物;和此类共聚物相互之间的混合物和与以上1)项中提到的聚合物的混合物,例如聚丙烯/乙烯-丙烯共聚物,LDPE/乙烯-乙酸乙烯酯共聚物(EVA),LDPE/乙烯-丙烯酸共聚物(EAA),LLDPE/EVA,LLDPE/EAA和交替或无规聚亚烷基/一氧化碳共聚物和它们与其它聚合物如聚酰胺的混合物。
4、烃类树脂(例如C5-C9),包括它们的氢化改性物(例如增粘剂)和聚亚烷基和淀粉的混合物。
以上1.)至4.)的均聚物和共聚物可具有任何立体结构,其中包括间同立构,全同立构,半全同立构,或无规立构;其中无规立构聚合物是优选的。立构规正嵌段聚合物也包括在内。
5、聚苯乙烯,聚(对-甲基苯乙烯),聚(α-甲基苯乙烯)。
6、从乙烯基芳族单体,包括苯乙烯,α-甲基苯乙烯,乙烯基甲苯的所有异构体,尤其对乙烯基甲苯,乙基苯乙烯、丙基苯乙烯、乙烯基联苯、乙烯基萘和乙烯基蒽的所有异构体,以及它们的混合物所形成的均聚物和共聚物。均聚物和共聚物可以具有任何立体结构,其中包括间同立构,全同立构,半全同立构或无规立构;其中无规立构聚合物是优选的。还包括立构规正嵌段聚合物。
6a.包括上述乙烯基芳族单体和选自乙烯,丙烯,二烯,腈类,酸类,马来酸酐类,马来酰亚胺类,乙酸乙烯酯和氯乙烯或丙烯酸衍生物和它们的混合物中的共聚单体的共聚物,例如苯乙烯/丁二烯,苯乙烯/丙烯腈,苯乙烯/乙烯(互聚物),苯乙烯/甲基丙烯酸烷基酯,苯乙烯/丁二烯/丙烯酸烷基酯,苯乙烯/丁二烯/甲基丙烯酸烷基酯,苯乙烯/马来酸酐,苯乙烯/丙烯腈/丙烯酸甲酯,高抗冲击强度的苯乙烯共聚物和另一种聚合物如聚丙烯酸酯、二烯烃聚合物或乙烯/丙烯/二烯烃三元共聚物的混合物;以及苯乙烯的嵌段共聚物,如苯乙烯/丁二烯/苯乙烯,苯乙烯/异戊二烯/苯乙烯,苯乙烯/乙烯/丁烯/苯乙烯或苯乙烯/乙烯/丙烯/苯乙烯。
6b.由在以上项6)中提及的聚合物的氢化获得的氢化芳族聚合物,尤其包括通过氢化无规立构聚苯乙烯制备的聚环己基乙烯(PCHE),常常称之为聚乙烯基环己烷(PVCH)。
6c.由在以上项6a)中提及的聚合物的氢化获得的氢化芳族聚合物。
均聚物和共聚物可以具有任何立体结构,包括包括间同立构,全同立构,半全同立构或无规立构;其中无规立构聚合物是优选的。还包括立构规正嵌段聚合物。
7、乙烯基芳族单体如苯乙烯或α-甲基苯乙烯的接枝共聚物,例如聚丁二烯上接枝苯乙烯,聚丁二烯-苯乙烯或聚丁二烯-丙烯腈共聚物上接枝苯乙烯;聚丁二烯上接枝苯乙烯和丙烯腈(或甲基丙烯腈);聚丁二烯上接枝苯乙烯、丙烯腈和甲基丙烯酸甲酯;聚丁二烯上接枝苯乙烯和马来酸酐;聚丁二烯上接枝苯乙烯、丙烯腈和马来酸酐或马来酰亚胺;聚丁二烯上接枝苯乙烯和马来酰亚胺;聚丁二烯上接枝苯乙烯和丙烯酸烷基酯或甲基丙烯酸烷基酯;乙烯/丙烯/二烯烃三元共聚物上接枝苯乙烯和丙烯腈;聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯 上接枝苯乙烯和丙烯腈;丙烯酸酯/丁二烯共聚物上接枝苯乙烯和丙烯腈,以及它们与项6)所列举的共聚物的混合物,例如已知为ABS、MBS、ASA或AES聚合物的共聚物混合物。
8、含卤素的聚合物类,如聚氯丁二烯,氯化橡胶,异丁烯-异戊二烯的氯化和溴化共聚物(卤代丁基橡胶),氯化或氯磺化聚乙烯,乙烯和氯化乙烯的共聚物,表氯醇均-或共聚物,尤其含卤素的乙烯基化合物的聚合物,例如聚氯乙烯,聚偏氯乙烯,聚氟乙烯,聚偏氟乙烯,以及它们的共聚物,如氯乙烯/偏氯乙烯,氯乙烯/乙酸乙烯酯或偏氯乙烯/乙酸乙烯酯共聚物。
9、由α,β-不饱和羧酸和其衍生物得到的聚合物,如聚丙烯酸酯和聚甲基丙烯酸酯;用丙烯酸丁酯进行冲击改性的聚甲基丙烯酸甲酯,聚丙烯酰胺和聚丙烯腈。
10、在项9)中提到的单体相互之间的或与其它不饱和单体的共聚物例如丙烯腈/丁二烯共聚物,丙烯腈/丙烯酸烷基酯共聚物,丙烯腈/丙烯酸烷氧基烷基酯或丙烯腈/卤代乙烯共聚物或丙烯腈/甲基丙烯酸烷基酯/丁二烯三元共聚物。
11、由不饱和醇类和胺类或酰基衍生物或其缩醛类得到的聚合物,例如聚乙烯醇,聚乙酸乙烯酯,聚硬脂酸乙烯酯,聚苯甲酸乙烯酯,聚马来酸乙烯酯,聚乙烯醇缩丁醛,聚邻苯二甲酸烯丙酯或聚烯丙基蜜胺;以及它们与以上1)项中提到的烯烃的共聚物。
12、环醚的均聚物和共聚物,如聚亚烷基二醇,聚环氧乙烷,聚环氧丙烷或它们与双缩水甘油基醚的共聚物。
13、聚缩醛类,如聚甲醛和含有环氧乙烷作为共聚单体的那些聚甲醛;用热塑性聚氨酯、丙烯酸酯或MBS改性的聚缩醛类。
14、聚苯醚和聚苯硫醚,以及聚苯醚与苯乙烯聚合物或聚酰胺的混合物。
15、由羟基封端的聚醚、聚酯或聚丁二烯与脂族或芳族多异氰酸酯衍生而来的聚氨酯,以及它的前体。
16、由二胺和二羧酸和/或氨基羧酸或相应的内酰胺衍生而来的聚酰胺和共聚酰胺,例如聚酰胺4,聚酰胺6,聚酰胺6/6,6/10,6/9,6/12,4/6,12/12,聚酰胺11,聚酰胺12,以间-二甲苯二胺和己二酸为原料的芳族聚酰胺;从六亚甲基二胺和间苯二甲酸或/和对苯二甲酸 制备的和有或没有高弹体作为改性剂的聚酰胺,例如聚-2,4,4-三甲基亚己基对苯二甲酰二胺或聚间亚苯基间苯二甲酰二胺;还有上述聚酰胺与聚烯烃,烯烃共聚物,离聚物或化学键连接的或接枝的弹性体,或与聚醚类,如聚乙二醇、聚丙二醇或聚亚丁基二醇的嵌段共聚物;以及用EPDM或ABS改性的聚酰胺或共聚酰胺;和在加工过程中缩合的聚酰胺(RIM聚酰胺体系)。
17、聚脲,聚酰亚胺,聚酰胺-酰亚胺,聚醚酰亚胺,聚酰亚胺酯,聚乙内酰脲和聚苯并咪唑。
18、由二羧酸和二醇和/或羟基羧酸或相应的内酯衍生而来的聚酯,例如聚对苯二甲酸乙二醇酯,聚对苯二甲酸丁二醇酯,聚1,4-二羟甲基环己烷对苯二甲酸酯,聚萘二甲酸亚烷基二醇酯(PAN)和聚羟基苯甲酸酯,以及由羟基封端的聚醚衍生而来的嵌段共聚酯;还有用聚碳酸酯或MBS改性的聚酯类。
19、聚碳酸酯和聚酯-碳酸酯。
20、聚酮。
21、聚砜,聚醚-砜和聚醚-酮。
22、从醛与酚类、脲和三聚氰胺衍生而来的交联聚合物,例如酚醛树脂,脲醛树脂和三聚氰胺/甲醛树脂。
23、干燥和非干燥性醇酸树脂。
24、从饱和的和不饱和的二羧酸与多羟基醇的共聚酯和作为交联剂的乙烯基化合物衍生而来的不饱和聚酯树脂,以及它们的具有低可燃性的含卤素的改性产物。
25、从取代的丙烯酸酯衍生而来的可交联丙烯酸树脂,例如环氧丙烯酸酯,聚氨酯丙烯酸酯或聚酯丙烯酸酯。
26、用蜜胺树脂,尿素树脂,异氰酸酯,异氰脲酸酯,聚异氰酸酯或环氧树脂加以交联的醇酸树脂,聚酯树脂和丙烯酸酯树脂。
27、从脂族、环脂族、杂环族或芳族缩水甘油基化合物衍生而来的交联环氧树脂,例如双酚A和双酚F的二缩水甘油醚的产物,它们用常规的硬化剂如酸酐或胺类加以交联,有或没有促进剂。
28、天然聚合物,如纤维素、橡胶、明胶和它们的化学改性的同源(homologous)衍生物,例如乙酸纤维素,丙酸纤维素和丁酸纤维素,或纤维素醚类,如甲基纤维素;以及松香和它的衍生物。
29、上述聚合物的共混物(多元共混物),例如PP/EPDM,聚酰胺/EPDM或ABS,PVC/EVA,PVC/ABS,PVC/MBS,PC/ABS,PBTP/ABS,PC/ASA,PC/PBT,PVC/CPE,PVC/丙烯酸酯,POM/热塑性PUR,PC/热塑性PUR,POM/丙烯酸酯,POM/MBS,PPO/HIPS,PPO/PA6.6和共聚物,PA/HDPE,PA/PP,PA/PPO,PBT/PC/ABS或PBT/PET/PC。
例如聚合物是热塑性聚合物。
在另一个实施方案中该有机材料是涂料,尤其汽车涂料。
用于涂料中的树脂典型地是交联聚合物,例如,从醛与苯酚,脲和蜜胺形成的,如苯酚/甲醛树脂,脲/甲醛树脂和蜜胺/甲醛树脂。
也有用的是从饱和的和不饱和的二羧酸与多元醇和作为交联剂的乙烯基化合物的共聚酯形成的不饱和聚酯树脂,以及它们的具有不易燃性的含卤素的改进产物。
优选使用的是从取代丙烯酸酯,例如环氧树脂丙烯酸酯,聚氨酯丙烯酸酯或聚酯丙烯酸酯所形成的可交联的丙烯酸树脂。
也可能的是用三聚氰胺树脂,尿素树脂,异氰酸酯,异氰脲酸酯,多异氰酸酯或环氧树脂交联的醇酸树脂、聚酯树脂和丙烯酸酯树脂。
交联的环氧树脂是从脂肪族,环脂族,杂环族或芳族缩水甘油基化合物形成,例如双酚A和双酚F的二缩水甘油醚的产物,它们用普通的硬化剂如酸酐或胺类进行交联,有或没有促进剂。
涂料也能够是含有烯属不饱和单体或低聚物和多不饱和的脂肪族低聚物的辐射可固化组合物。
根据本发明能够被稳定化以抵抗光的作用的醇酸树脂漆是普通的耐热漆,后者尤其用于涂覆汽车(汽车罩面漆),例如以醇酸/三聚氰胺树脂和醇酸/丙烯酸/三聚氰胺树脂为基础的漆(参见H.Wagner和H.F.Sarx,“Lackkunstharze”(1977),第99-123页)。其它交联剂包括甘脲(glycouril)树脂,封闭的异氰酸酯或环氧树脂。
需要指出的是,本发明的化合物适合用于非酸催化的热固性树脂如环氧树脂,环氧-聚酯树脂,乙烯基树脂,醇酸树脂,丙烯酸树脂和聚酯树脂,任选用硅、异氰酸酯或异氰脲酸酯改性。环氧树脂和环氧-聚酯树脂用普通的交联剂如酸,酸酐,胺等等进行交联。因此,环氧化物可以用作已经通过在骨架结构上存在反应活性基团而得以改性的 各种丙烯酸或聚酯树脂体系的交联剂。
当水溶性、水混溶性的或水可分散性的涂料是所需要的时,形成了在树脂中存在的酸基的铵盐。粉末涂料组合物能够通过甲基丙烯酸缩水甘油酯与所选择的醇组分进行反应来制备。
在特定的实施方案中,上述的涂料被施涂于基材上,后者对于波长大于380nm的电磁辐射是敏感的。
典型的敏感基材是,例如,附着于金属基材上的阴极沉积的层。此类涂料典型地用于汽车工业。
由于对波长大于380nm的电磁辐射敏感,可以理解例如在至多440nm,优选至多420nm和尤其至多410nm的波长范围内的UV或可见光。
在其中通式(I)或(II)的化合物可用作稳定剂抵抗UV和/或可见光的有害影响的各种有机材料中,其它稳定剂和添加剂也可以存在。
随后给出例子。
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;侧链呈线性或支化的壬基苯酚类,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-双十二烷基硫代甲基-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.羟基化硫代二苯基醚类,例如,2,2′-硫代双(6-叔丁基-4-甲基苯酚),2,2′-硫代双(4-辛基苯酚),4,4′-硫代双(6-叔丁基-3-甲基苯酚),4,4′-硫代双(6-叔丁基-2-甲基苯酚),4,4′-硫代双(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)二环戊二烯,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,二硫代对苯二甲酸双(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基酯。
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,硫代二甘醇,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,硫代二甘醇,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,硫代二甘醇,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,硫代二甘醇,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。
1.17.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)六亚甲基二胺,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)三亚甲基二胺,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-亚苯基二胺,N,N′-二仲丁基-对-亚苯基二胺,N,N′-双(1,4-二甲基戊基)-对-亚苯基二胺,N,N′-双(1-乙基-3-甲基戊基)-对-亚苯基二胺,N,N’-双(1-甲基庚基)-对亚苯基二胺,N,N’-二环己基-对亚苯基二胺,N,N′-二苯基-对-亚苯基二胺,N,N′-双(2-萘基)-对-亚苯基二胺,N-异丙基-N′-苯基-对-亚苯基二胺,N-(1,3-二甲基丁基)-N′-苯基-对-亚苯基二胺,N-(1-甲基庚基)-N′-苯基-对-亚苯基二胺,N-环己基-N′-苯基-对-亚苯基二胺,4-(对甲苯氨磺酰基)二苯胺,N,N′-二甲基-N,N′-二仲丁基-对亚苯基二胺,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,辛基化二苯胺(例如p,p′-二叔辛基二苯胺),4-正丁基氨基苯酚,4-丁酰氨基苯酚,4-壬酰氨基苯酚,4-十二酰氨基苯酚,4-十八酰氨基苯酚,双(4-甲氧基苯基)胺,2,6-二叔丁基-4-二甲氨基甲基苯酚,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-双[(2-甲基苯基)氨基]乙烷,1,2-双(苯基氨基)丙烷,(邻甲苯基)双胍,双[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/叔辛基二苯基胺类的混合物,单和二烷基化壬基二苯基胺类的混合物,单和二烷基化十二烷基二苯基胺类的混合物,单和二烷基化异丙基/异己基二苯基胺类的混合物,单和二烷基化叔丁基二苯基胺类的混合物,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,N,N-双(2,2,6,6-四甲基-哌啶-4-基)-六亚甲基二胺,双(2,2,6,6-四甲基-哌啶-4-基)癸二酸酯,2,2,6,6-四甲基哌啶-4-酮,2,2,6,6-四甲基哌啶-4-醇。
2.UV吸收剂和光稳定剂
2.1.2-(2′-羟基苯基)苯并三唑类,例如2-(2′-羟基-5′-甲基苯基)苯并三唑,2-(3′,5′-二叔丁基-2′-羟基苯基)苯并三唑,2-(5′-叔丁基-2′-羟基苯基)苯并三唑,2-(2′-羟基-5′-(1,1,3,3-四甲基丁基)苯基)苯并三唑,2-(3′,5′-二叔丁基-2′-羟基苯基)-5-氯-苯并三唑,2-(3′-叔丁基-2′-羟基-5′-甲基苯基)-5-氯-苯并三唑,2-(3′-仲丁基-5′-叔丁基-2′-羟基苯基)苯并三唑,2-(2′-羟基-4′-辛氧基苯基)苯并三唑,2-(3′,5′-二叔戊基-2′-羟基苯基)苯并三唑,2-(3′,5′-双-(α,α-二甲基苄基)-2′-羟基苯基)苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰基乙基)苯基)-5-氯-苯并三唑,2-(3′-叔丁基-5′-[2-(2-乙基己氧基)-羰基乙基]-2′-羟基苯基)-5-氯-苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰基乙基)苯基)-5-氯-苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰基乙基)苯基)苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰基乙基)苯基)苯并三唑,2-(3′-叔丁基-5′-[2-(2-乙基己氧基)羰基乙基]-2′-羟基苯基)苯并三唑,2-(3′-十二烷基-2′-羟基-5′-甲基苯基)苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-异辛氧基羰基乙基)苯基苯并三唑,2,2′-亚甲基-双[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基苯酚];2-[3′-叔丁基-5′-(2-甲氧基羰基乙基)-2′-羟基苯基]-2H-苯并三唑与聚乙二醇300的酯基转移产物;[R-CH2CH2-COO-CH2CH2-]2-其中R=3′-叔丁基-4′-羟基-5′-2H-苯并三唑-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]苯并三唑;2-[2’-羟基-3’-(1,1,3,3-四甲基丁基)-5’-(α,α-二甲基苄基)苯基]苯并三唑。
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.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-甲酯基肉桂酸甲酯,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-甲酯基-对甲氧基肉桂酸甲酯和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;例如癸二酸双(2,2,6,6-四甲基-4-哌啶基)酯,琥珀酸双(2,2,6,6-四甲基-4-哌啶基)酯,癸二酸双(1,2,2,6,6-五甲基-4-哌啶基)酯,癸二酸双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)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-羟基哌啶和琥珀酸的缩合物,N,N′-双(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,次氮基三乙酸三(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-亚乙基)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-硬脂酰氧基-2,2,6,6-四甲基哌啶,2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸双(1,2,2,6,6-五甲基哌啶基)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,癸二酸双(1-辛氧基-2,2,6,6-四甲基哌啶基)酯,丁二酸双(1-辛氧基-2,2,6,6-四甲基哌啶基)酯,N,N′-双-(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,4-十六烷氧基-2,2,6,6-四甲基哌啶和4-硬脂氧基-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)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-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-二丁基胺和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,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-甲氧基苯基)乙烯,N,N’-双甲酰基-N,N’-双(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,2,4-双[N-(1-环己氧基-2,2,6,6-四甲基哌啶-4-基)-N-丁基氨基]-6-(2-羟乙基)氨基-1,3,5-三嗪,1-(2-羟基-2-甲基丙氧基)-4-十八烷酰基氧基-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 Reg.No.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-环己氧基-2,2,6,6-哌啶-4-基)丁基氨基]-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、草酰胺类,例如4,4′-二辛氧基-N,N′-草酰二苯胺,2,2′-二乙氧基-N,N’-草酰二苯胺,2,2′-二辛氧基-5,5’-二叔丁基-N,N’-草酰二苯胺(2,2’-dioctyloxy-5,5’-di-tert-butoxanilide),2,2’-二(十二烷氧基)- 5,5’-二叔丁基-N,N’-草酰二苯胺,2-乙氧基-2′-乙基-N,N’-草酰二苯胺,N,N′-双(3-二甲氨基丙基)草酰胺,2-乙氧基-5-叔丁基-2′-乙氧基-N,N’-草酰二苯胺和它与2-乙氧基-2′-乙基-5,4′-二叔丁氧基N,N’-草酰二苯胺的混合物以及邻-和对-甲氧基双取代的N,N’-草酰二苯胺类的混合物和邻-和对-乙氧基-二取代的N,N’草酰二苯胺类的混合物。
2.8.2-(2-羟基苯基)-1,3,5-三嗪类,例如2,4,6-三(2-羟基-4-辛氧基苯基)-1,3,5-三嗪,2-(2-羟基-4-辛氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,2-(2,4-二羟基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,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,2-(2-羟基-4-辛氧基苯基)-4,6-双(4-甲基苯基)-1,3,5-三嗪,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,2-(2-羟基-4-十三烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,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,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,2-[4-(十二烷氧基/十三烷氧基-2-羟基丙氧基)-2-羟基-苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,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,2-(2-羟基-4-己氧基)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-羟基丙氧基]苯基}-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪,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。
3.金属减活剂类,例如N,N′,N′-二苯基草酰胺,N-水杨醛-N′-水杨酰基肼,N,N′-双(水杨酰基)肼,N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)肼,3-水杨酰基氨基-1,2,4-三唑,双(苄叉基)草酰二肼,N,N’-草酰二苯胺,间苯二甲酰二肼,癸二酰双(苯基肼),N,N′-二乙酰基己二酰二肼,N,N′-双(水杨酰基)草酰二肼,N,N′-双(水杨酰基)硫代丙酰基二肼。
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,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,二亚磷酸二硬脂基季戊四醇酯,亚磷酸三(2,4-二叔丁基苯基)酯,二亚磷酸二异癸基季戊四醇酯,二亚 磷酸双(2,4-二叔丁基苯基)季戊四醇酯,二亚磷酸双(2,6-二叔丁基-4-甲基苯基)-季戊四醇酯,二亚磷酸二异癸基氧基季戊四醇酯,二亚磷酸双(2,4-二叔丁基-6-甲基苯基)季戊四醇酯,二亚磷酸双(2,4,6-三叔丁基苯基)季戊四醇酯,三亚磷酸三硬脂基山梨糖醇酯,二亚膦酸四(2,4-二叔丁基苯基)4,4′-亚联苯基酯,6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并[d,g]-1,3,2-dioxaphosphocin,亚磷酸双(2,4-二叔丁基-6-甲基苯基)甲基酯,亚磷酸双(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[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-次氮基[三乙基三(3,3’,5,5’-四叔丁基-1,1’-二苯基-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’-联苯基-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-dioxaphophirane。
具体实例是以下亚磷酸酯:
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-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-十八烷基羟基胺,N-十七烷基-N-十八烷基羟基胺,由氢化牛油脂肪胺得到的N,N-二烷基羟基胺。
6.硝酮类,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-十八烷基-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,由氢化牛油脂肪胺衍生而来的N,N-二烷基羟基胺获得的硝酮。
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,二丁基二硫代氨基甲酸锌,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,聚乙烯基吡咯烷酮,双氰胺,三烯丙基氰脲酸酯,脲衍生物,肼衍生物,胺类,聚酰胺类,聚氨酯类,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,蓖麻酸钠和棕榈酸钾,邻苯二酚锑或邻苯二酚锌。
11.成核剂类,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,玻璃泡,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。
13.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。
14.苯并呋喃酮类和二氢吲哚酮类,例如在US-A-4,325,863,US-A-4,338,244,US-A-5,175,312,US-A-5,216,052,US-A-5,252,643,DE-A-4,316,611,DE-A-4,316,622,DE-A-4,316,876;EP-A-0589839,EP-A-0591102,EP-A-1291384中公开的那些,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-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-乙酰基-异辛基苯基)-5-异辛基苯并呋喃-2-酮。
优选地,以上组合物另外含有位阻胺稳定剂和/或UV吸收剂,该试剂选自s-三嗪类,N,N’-草酰二苯胺类,羟基二苯甲酮类,苯甲酸酯类,α-氰基丙烯酸酯和与如上所述的通式(I)或(II)的那些不同的苯并三唑类。
当添加另外的UV-吸收剂时,它们优选以0.1%-30%,更优选0.5%-15%和最优选1%-10%(按重量)的量添加,基于有机材料的重量。
当另外添加受阻胺光稳定剂时它优选以0.1%-10%,更优选0.5%-5%和最优选1%-3%(按重量)的量添加,基于有机材料的重量。
通式I或II的UV吸收剂和其它UV吸收剂和/或位阻胺稳定剂的总量例如是0.5%-15%(按重量),基于有机材料的重量。
以上给出了不同类型的受阻胺光稳定剂和UV吸收剂的例子。
特别地优选的UV吸收剂是下列s-三嗪类和苯并三唑类:
=以下的混合物:
a)R1=R2=CH(CH3)-COO-C8H17,R3=R4=H;
b)R1=R2=R3=CH(CH3)-COO-C8H17,R4=H;
c)R1=R2=R3=R4=CH(CH3)-COO-C8H17
羟苯基三嗪UV吸收剂是已知的并且部分地是商品。
最合适的苯并三唑UV吸收剂能够以商品名
TINUVIN384(RTM),TINUVIN928(RTM),TINUVIN900(RTM),TINUVIN328(RTM)和TINUVIN1130(RTM)。
商购。
优选地,组分(c)的位阻胺化合物选自下列商购产品:
DASTIB845(RTM),TINUVIN770(RTM),TINUVIN765(RTM),TINUVIN144(RTM),TINUVIN123(RTM),TINUVIN111(RTM),TINUVIN783(RTM),TINUVIN791(RTM),TINUVIN123(RTM),TINUVIN292(RTM),TINUVIN152(RTM),TINUVIN144(RTM),MARK LA52(RTM),MARK LA57(RTM),MARK LA62(RTM),MARK LA67(RTM),HOSTAVIN N20(RTM),HOSTAVIN N24(RTM),SANDUVOR3050(RTM),SANDUVOR3058(RTM),DIACETAM5(RTM),SUMISORB TM61(RTM),UVINUL4049(RTM),SANDUVOR PR31(RTM),GOODRITE UV3034(RTM),GOODRITE UV3150(RTM),GOODRITE UV3159(RTM),GOODRITE3110×128(RTM),UVINUL4050H(RTM),CHIMASSORB944(RTM),CHIMASSORB2020(RTM),CYASORB UV3346(RTM),CYASORB
UV3529(RTM),DASTIB1082(RTM),CHIMASSORB119(RTM),UVASIL299(RTM),UVASIL125(RTM),UVASIL2000(RTM),UVINUL5050H(RTM),LICHTSCHUTZSTOFF UV31(RTM),LUCHEM HA B18(RTM),MARK LA63(RTM),MARK LA68(RTM),UVASORB HA88(RTM),TINUVIN622(RTM),HOSTAVIN N30(RTM)和FERRO AM806(RTM)。
特别优选的是
TINUVIN770(RTM),TINUVIN292(RTM),TINUVIN123(RTM),TINUVIN144(RTM)和TINUVIN152(RTM)。
本发明的又一个方面是通式I或II的化合物作为有机材料中的紫外线(UV)和可见(VIS)光吸收剂的用途。
以上对于化合物给出的定义和优选项同样适用于本发明的另一个方面。
下列实施例举例说明了本发明。
A)制备实施例
实施例A1.羟苯基苯并三唑1b的制备
a)将亚硝基硫酸(在硫酸中40%;14.0g,44.1mmol)在15℃下慢慢地添加到4-氨基-5-溴邻苯二甲酰亚胺(95%;10.7g,39.9mmol)在乙酸(200ml)中的搅拌悬浮液中。在添加过程中,反应混合物的温度利用冰浴保持在15℃和17℃之间。在加料完成(四分之三小时)之后,搅拌继续进行两个小时。反应混合物然后被转移到滴液漏斗中和慢慢地在-15℃下添加到2-枯基-4-叔辛基苯酚(95%;13.7g,40.1mmol)在甲醇/间二甲苯(85/15(按体积);200ml)中形成的、含有氢氧化钠微粒(1.8g,45.0mmol)和乙酸钠(13.1g,159.7mmol)的搅拌溶液中。在添加过程中,反应混合物的温度借助于异丙醇-干冰浴保持在-15℃和-9℃之间;该pH由电极来测量并且通过氢氧化钠(在水中30%浓度;总250ml)的伴随添加来保持高于5。在加料结束(两个小时;初始pH13.7,最终pH5.6)之后,移走冷却浴,红色悬浮液搅拌一夜。添加水(150ml)和甲苯(250ml),分离出水相并用甲苯(1×250ml)洗涤。合并的有机相用水洗涤(2×250ml),干燥(MgSO4),过滤和蒸发溶剂,获得30g的红色油。 添加甲醇(60g),该悬浮液被加热到回流。在冷却(冰浴)之后,化合物1a结晶成红色固体,它被滤出,用甲醇洗涤并干燥。产量16.2g(27.4mmol,68.8%)。
熔点:178-179℃。
1H-NMR(300MHz,CD2Cl2),δ(ppm):13.14(s,1H),8.34(s,1H),8.18(s,1H),7.92(d-like,1H),7.76(d-like,1H),7.28-7.24(m,4H),7.20-7.15(m,1H),3.20(s,3H),1.87(s,2H),1.82(s,6H),1.51(s,6H),0.86(s,9H).
b)将化合物1a(17.2g,29.1mmol),叠氮化钠(99%;2.5g,38.1mmol)和1-甲基-2-吡咯烷酮(60ml)的搅拌混合物加热至120℃。保持温度,直至氮气散发停止为止(1.5小时)。深颜色溶液通过添加水(100ml)和甲苯(150ml)被冷却至25℃。水相被分出并用甲苯(1×50ml)洗涤。合并的有机相用水洗涤(3×50ml),干燥(MgSO4),过滤和蒸发溶剂,获得17g的粘性的红色油,它在静置时固化。将粗物质溶于热的甲苯中。添加己烷和溶液冷却下来,因此化合物1b结晶为黄色固体,固体物被滤出并加以干燥(8g)。滤液被蒸干和残留物从己烷中结晶而获得另外3.5g。产量11.5g(21.9mmol,75.3%)。
熔点:198-199℃。
1H-NMR(300MHz,CD2Cl2),δ(ppm):10.97(s,1H),8.40-8.39(m,3H),7.76(d-like,1H),7.31-7.24(m,4H),7.20-7.15(m,1H),3.25(s,3H),1.91(s,2H),1.83(s,6H),1.54(s,6H),0.86(s,9H).
实施例A2.羟苯基苯并三唑2c的制备
a)4-氨基-N-甲基邻苯二甲酰亚胺(17.8g,10.0mmol),乙酸钠(1.64 g,20mmol)和乙酸(30g)的混合物在室温下一起搅拌。在充分搅拌的情况下,将在乙酸(10ml)中的溴(3.22g,20mmol)滴加进去。在添加约一半的溴之后形成沉淀物。在溴的添加结束之后搅拌继续进行16小时。然后添加水添加(40ml),产物通过过滤收集,用水洗涤(10ml)并干燥。
产量:3.18g(95%)。
熔点:216℃-218℃。
1H-NMR(300MHz,DMSO-d6),δ(ppm):7.92(s,1H),6.46(s,broad,2H),2.96(s,3H)。
b)将亚硝基硫酸(在硫酸中40%;14.0g,44.1mmol)在15℃下慢慢地添加到3-氨基-4,6-二溴邻苯二甲酰亚胺(13.4g,40.0mmol)在乙酸(200ml)中的搅拌悬浮液中。在添加过程中,反应混合物的温度利用冰浴保持在15℃和17℃之间。在加料完成(四分之三小时)之后,搅拌继续进行一个小时。反应混合物然后被转移到滴液漏斗中和慢慢地在-15℃下添加到2-枯基-4-叔辛基苯酚(95%;13.7g,40.1mmol)在甲醇/间二甲苯(85/15(按体积);200ml)中形成的、含有氢氧化钠微粒(1.8g,45.0mmol)和乙酸钠(13.1g,159.7mmol)的搅拌溶液中。在添加过程中,反应混合物的温度借助于异丙醇-干冰浴保持在-15℃和-9℃之间;该pH由电极来测量并且通过氢氧化钠(在水中30%浓度;总250ml)的伴随添加来保持高于5。在加料结束(两个小时;初始pH13.7,最终pH5.6)之后,移走冷却浴,红色悬浮液搅拌一夜。化合物2b,它结晶为红色固体,被滤出,用异丙醇洗涤并干燥。
产量16.6g(62.0%)。
熔点:180℃(度)
1H-NMR(300MHz,CDCl3),δ(ppm):11.70(s,1H),8.14(s,1H),7.78(d-like,1H),7.70(d-like,1H),7.30-7.28(m,4H),7.21-7.17(m,1H),3.16(s,3H),1.82(s,6H),1.81(s,2H),1.46(s,6H),0.83(s,9H).
c)将化合物2b(6.70g,10mmol),叠氮化钠(99%;0.85g,13mmol)和1-甲基-2-吡咯烷酮(25ml)的搅拌混合物加热至50℃。保持温度,直至氮气散发停止为止(2小时)。深颜色溶液通过添加水(250ml)和甲苯(150ml)被冷却至25℃。水相被分出,沉淀在乙酸乙酯中的产物通过 过滤来收集。粗物质从热的甲苯(20ml)中重结晶,滤出并干燥。产量1.05g(17.4%)。
熔点:221℃-225℃(度)。
1H-NMR(300MHz,CDCl3),δ(ppm):10.89(s,1H),8.41(s,1H)8.39(d-like,1H),7.74(d-like,1H),7.29-7.26(m,4H),7.22-7.17(m,1H),3.26(s,3H),1.87(s,2H),1.84(s,6H),1.53(s,6H),0.84(s,9H).
实施例A3.羟苯基苯并三唑3d(I)-3d(V)经由二羧酸3a和酸酐3b从酰亚胺1b的制备,没有中间体酰胺酸3c(I)-3c(V)的分离。
通式3a的中间化合物和它们的类似化合物也可用作UV吸收剂。
a)将KOH(53.3g,950mmol)在25℃下慢慢地添加到1b(49.8g,94.9mmol)和乙醇/水(1/1(按体积);200g加上40ml的总量)的搅拌混合物中。在用乙醇(50ml)进一步稀释之后,混合物升至80℃,它在该温度下保持19.75小时。添加另外的KOH(2.65g,47.2mmol)并在80℃下连续搅拌另外29小时。在旋转蒸发器上蒸馏出乙醇,所得桔黄色悬浮液用水稀释(500ml)。混合物通过HCl(水溶液,32%w/w)的缓慢添加被酸化(pH2),黄色沉淀物被滤出。滤饼用水洗涤(3×100ml)并在真空箱中在40℃下干燥,而获得黄色固体形式的3a(53.3g)。
熔点:150-175℃(度)
HPLC-UV/APCI-MS负:529.3(M);对于C31H35N3O5计算值:529.3 1H-NMR(300MHz,DMSO-d6),δ(ppm):10.38(s,1H),8.57(br s,2H),7.98(d,J=1.9Hz,1H),7.64(d,J=1.9Hz,1H),7.26-7.18(m,4H),7.14·7.08(m,1H),1.80(s,2H),1.75(s,6H),1.43(s,6H),0.78(s,9H).
b)-d);3d(I):将3a(4.2g,7.9mmol)和甲苯(40g)的搅拌混合物升温至回流状态并在回流状态下保持到水的形成(水由迪安-斯达克榻分水器分离)停止为止(3.75小时;t1)。然后添加苯胺(98%;0.83g,8.7mmol),混合物回流另外1.25小时(t2)。在旋转蒸发器上蒸馏出甲苯,残留物由色谱法(硅胶,己烷/甲苯/乙酸乙酯9/0.5/1)提纯,获得黄色固体形式的3d(I)(2.4g,51.6%)。
熔点:220-221℃。
对于C37H38N4O3(586.74)的分析计算:C,75.74;H,6.53;N,9.55。实测值:C,75.52;H,6.53;N,9.28。
1H-NMR(400MHz,DMSO-d6),δ(ppm):10.26(br s,1H),8.68(s,2H),7.96(d,J=1.8Hz,1H),7.69(d,J=1.8Hz,1H),7.56-7.45(m,5H),7.26-7.20(m,4H),7.14-7.10(m,1H),1.82(s,2H),1.76(s,6H),1.45(s,6H),0.79(s,9H).
b)-d);3d(II):与3d(I)类似地,从3a(6.35g,12.0mmol),甲苯(70g)和4-氨基苄腈(97%;1.6g,13.1mmol)制备,回流分别持续1.1小时(t1)和2.25小时(t2)。残留物由色谱法提纯(硅胶,甲苯)获得黄色固体形式的3d(II)(4.2g,57.3%)。
熔点:252-253℃
对于C38H37N5O3(611.75)的分析计算:C,74.61;H,6.10;N,11.45。
实测值:C,74.04;H,5.83;N,11.37。
1H-NMR(400MHz,DMSO-d6),δ(ppm):10.24(br s,1H),8.72(s,2H),8.05(d,J=8.5Hz,2H),7.95(d,J=1.8Hz,1H),7.76(d,J=8.5Hz,2H),7.69(d,J=1.8Hz,1H),7.26-7.18(m,4H),7.16-7.10(m,1H),1.82(s,2H),1.76(s,6H),1.44(s,6H),0.79(s,9H).
b)-d);3d(III):与3d(I)类似地,从3a(6.35g,12.0mmol),甲苯(70g)和2-氯苯胺(98%;1.7g,13.1mmol)制备,回流分别持续1.0小时(t1)和3.25小时(t2)。残留物由色谱法提纯(硅胶,甲苯/乙酸乙酯9/1)获得黄色固体形式的3d(III)(2.2g,29.5%)。
熔点:179-180℃
对于C37H37ClN4O3(621.19)的分析计算:C,71.54;H,6.00;Cl,5.71;N,9.02。实测值:C,71.04;H,5.90;Cl,5.93;N,8.89。
1H-NMR(300MHz,DMSO-d6),δ(ppm):10.22(s,1H),8.76(s,2H),7.95(d,J=2.1Hz,1H),7.75-7.67(m,3H),7.62-7.53(m,2H),7.27-7.19(m,4H),7.15-7.09(m,1H),1.82(s,2H),1.76(s,6H),1.45(s,6H),0.79(s,9H).
b)-d);3d(IV):与3d(I)类似地,从3a(6.35g,12.0mmol),甲苯(70g)和2,6-二异丙基苯胺(90%;2.6g,13.2mmol)制备,回流分别持续1.0小时(t1)和3.0小时(t2)。残留物由色谱法提纯(硅胶,甲苯)获得黄色固体形式的3d(IV)(3.3g,41.0%)。
熔点:210-211℃
对于C43H50N4O3(670.90)的分析计算值:C,76.98;H,7.51;N,8.35。
实测值:C,76.70;H,7.47;N,8.29。
1H-NMR(300MHz,CD2Cl2),δ(ppm):11.03(s,1H),8.53(s,2H),8.45(d,J=2.4Hz,1H),7.79(d,J=2.4Hz,1H),7.58-7.53(m,1H),7.39-7.36(m,2H),7.33-7.26(m,4H),7.22-7.16(m,1H),2.78(septet,J=6.8Hz,2H),1.93(s,2H),1.85(s,6H),1.56(s,6H),1.19(d,J=6.8Hz,12H),0.88(s,9H).
b)-d);3d(V):与3d(I)类似地,从3a(6.35g,12.0mmol),甲苯(70g)和乙醇胺(99%;0.81g,13.1mmol)制备,回流分别持续1.25小时(t1)和1.5小时(t2)。残留物由色谱法提纯(硅胶,甲苯)获得黄色固体形式的3d(V)(2.8g,42.1%)。
熔点:161-162℃
对于C33H38N4O4(554.70)的分析计算值:C,71.46;H,6.90;N,10.10。实测值:C,71.07;H,6.92;N,10.03。
1H-NMR(300MHz,DMSO-d6),δ(ppm):10.23(s,1H),8.57(s,2H),7.94(d,J=2.2Hz,1H),7.67(d,J=2.2Hz,1H),7.26-7.18(m,4H),7.14-7.08(m,1H),4.88(t,J=5.9Hz,1H),3.72-3.59(m,4H),1.81(s,2H),1.75(s,6H),1.44(s,6H),0.78(s,9H).
b)N,N′-二环己基碳二亚胺(99%;2.7g,13.0mmol),3a(6.35g,12.0mmol)和二氯甲烷(40ml)的混合物在25℃下搅拌一小时。N,N′-二环己脲被滤出,在旋转蒸发器上蒸馏出二氯甲烷,获得黄色固体形式的3b(5.5g,89.6%)。
熔点:145-160℃(度)
HPLC-UV/APCI-MS.negative):511.2(M);对于C31H33N3O4的计算值:511.2
1H-NMR(300MHz,CD2Cl2),δ(ppm):10.89(s,1H),8.63(s,2H),8.44(d,J=2.3Hz,1H),7.81(d,J=2.3Hz,1H),7.31-7.24(m,4H),7.22-7.15(m,1H),1.91(s,2H),1.84(s,6H),1.55(s,6H),0.86(s,9H).
B)应用实施例
使用的材料
丙烯酰基/蜜胺清漆配方:
d)乙酸丁酯/丁醇(37:8wt./wt.) 4.33g
e)异丁醇 4.87g
g)结晶油306 8.74g
总计 100.00g
粘结剂原材料:
100:芳族烃,bp.163-180℃(Exxon Corp.)
6结晶油30:脂族烃,bp.145-200℃(Shell Corp.)
UV吸收剂和其它稳定剂
从Ciba Specialty Chemicals获得的商品UV-吸收剂。
N,N’-草酰二苯胺是Sanduvor3206
实施例A1和A3的化合物1b和3d(I)-(V)是根据本发明的UV吸收剂。
从Ciba Specialty Chemicals获得的位阻胺稳定剂。
实施例B1:UV吸收剂的光持久性
UV吸收剂的光持久性评价如下:
将本发明的UV吸收剂以基于该配制料的固体含量(固体含量:50.4%)的3%浓度引入到热固性丙烯酸/蜜胺透明涂料(基于SC303/SC370/MF650)中。该透明涂料被喷涂到玻璃板上,导致在固化(130℃/30分钟)之后形成了20μm的透明涂料的干膜厚度。
在试样的曝光前,使用UV/VIS分光光度计(Perkin Elmer,Lamda40)记录UV-吸收光谱。参比:未稳定化的丙烯酸/蜜胺透明涂料。随后该试样在Xenon-WOM老化试验机(Atlas Corp.)中根据SAE J1960进行曝光。在曝光之后保留的UV吸收剂的百分比(在λmax下测定)是通过在规则的曝光间隔之后记录UV-吸收光谱来监测的。试验结果总结在表1中。
表1:在Xe-WOM曝光过程中UV吸收剂的光持久性
实施例B2:有保护外涂层的光持久性
在第二实施例中,将两种后续的澄明涂料施涂在彼此之上。第一种透明涂料(透明涂料I)被稳定化并按照在实施例B1中详细描述的那样被施涂。第二种热固性丙烯酸/蜜胺透明涂料(基于SC303/SC370/MF650)随后被喷涂到第一种透明涂层上,在固化(130℃/30分钟)之后形成了40μm的第二种透明涂料(透明涂料II)的干膜厚度。第二种透明涂层通过使用作为共稳定剂的3%TINUVIN109/1.5%TINUVIN400和1%TINUVIN152的UV吸收剂结合物(HALS)来稳定化。参比:未稳定化的第一种透明涂料。按照在实施例B1中所述,在试样的曝光前,使用UV/VIS分光光度计(PerkinElmer,Lamda40)记录UV-透射谱。随后该试样在Xenon-WOM老化试验机(Atlas Corp.)中根据SAE J1960进行曝光。作为曝光时间的透射值(在396nm测定)是通过在规则的曝光间隔之后记录透射谱来监测的。试验结果总结在表2中:
表2:在Xe-WOM曝光过程中作为曝光间隔的函数的透射值(在396nm测定)
实施例B3:在阴极电镀涂层上的透明涂层施涂
按照在实施例B1中所述方法制备热固性丙烯酸/蜜胺透明涂料。漆被喷涂到从ACT Laboratories(ACT Laboratories,Inc.,South-field,Michigan48075,USA)商购的电镀涂覆的铝板(ED6950A,10×30cm)上,在固化(130℃/30分钟)之后形成20μm的干膜厚度。板随后在Xenon-WOM老化试验机(Atlas Corp.)中根据SAE J1960进行曝光。在透明涂层之下的电镀涂层的UV保护的程度是在规则的曝光间隔作为电镀涂层的泛黄指数(根据DIN6174的b*值)的函数来监测的。结果总结在表3中:
表3:与透明涂层稳定化有关的电镀涂层的泛黄
结果清楚地表明:
a)没有合适UV保护的电镀涂层的显著泛黄/UV光诱导降解
b)电镀涂层使用现有UV吸收剂包装料(TINUVIN109/TINUVIN400)的不充分保护,它截掉了在300-385nm之间的全部紫外光
c)电镀涂层使用UV吸收剂时的的优异保护,一直到可见光波长区域有显著的吸收。
实施例B4:施涂到电镀涂层上的透明涂层的粘合性
按照在实施例2中所详细描述的方法,两种后续的透明涂料层被施涂在从ACT Laboratories(ACT Laboratories,Inc.,Southfield,Michigan48075,USA)商购的电镀涂覆的铝板(ED6950A,10×30cm)的表面上。参比:a)未稳定化的两种透明涂层,b)用以TINUVIN109/TINUVIN400为基础的现有UV吸收剂包装料稳定化的第二种透明涂料,即截掉在300-385nm之间的全部紫外光。
随后该试样在Xenon-WOM老化试验机(Atlas Corp.)中根据SAE J1960进行曝光。在透明涂层和光敏电镀涂层之间的粘合性是每隔一定间隔通过十字划线法(ISO2409),随后通过胶带试验法来测定。试验结果总结在表4中
表4:在老化之后在电镀涂层上的透明涂层的粘合性
附注:Gt0,根据ISO2409=最佳(粘合性没有损失)
Gt5=最差(完全剥离)
实施例B5:UV吸收剂的光持久性
实验参数与实施例B1中所列出的相同,例外的是该UV-吸收剂与作为助稳定剂的HALS(即基于配制料的固体含量的1%123)相结合进行试验。
表5:在Xe-WOM曝光过程中UV吸收剂的光持久性
实施例B6:后续的透明涂料
在另一个实施例中,将两种后续的澄明涂料施涂在彼此之上。第一种透明涂料(透明涂料I)用本发明的UV吸收剂与位阻胺一起来稳定化,并按照在实施例B1中所述方法来施涂。第二种热固性丙烯酸/蜜胺透明涂料(基于SC303/SC370/MF650)随后被喷涂到第一种透明涂层上,在固化(130℃/30分钟)之后形成了40μm的第二种透明涂料(透明涂料II)的干膜厚度。第二种透明涂层通过使用作为共稳定剂的3%109/1.5%TINUVIN400和1%TINUVIN152的UV吸收剂结合物(HALS)来稳定化。参比是未稳定化的第一种透明涂料。
按照在实施例B1中所述,在试样的曝光前,使用UV/VIS分光光度计(Perkin Elmer,Lamda40)记录UV-透射谱。随后该试样在Xenon-WOM老化试验机(Atlas Corp.)中根据SAE J1960进行曝光。作为曝光时间的透射值(在396nm测定)是通过在规则的曝光间隔之后记录透射谱来监测的。试验结果总结在表6中:
表6:在Xe-WOM曝光过程中在特定的曝光间隔之后的透射值(在396nm测定)
透明涂料II配制剂:
(在二甲苯/丁醇中65%溶液,26∶9wt./wt.)
(在Solvesso1003中75%
(在异丁醇中55%)
d)乙酸丁酯/丁醇(37:8wt./wt.) 4.33g
e)异丁醇 4.87g
g)结晶油 306 8.74g
h) MA7(在Solvesso150中1%) 1.20g
总计 100.00g
Claims (17)
2.具有通式(I)的根据权利要求1的化合物。
5.根据权利要求4的方法,其中反应是在溶剂中进行的。
6.根据权利要求4的方法,其中通式III、IV或V的化合物的量与通式X的叠氮化物化合物的量的摩尔比率是1∶1到1∶3。
7.根据权利要求4的方法,其中反应是在催化剂存在下进行的。
8.稳定化以抵抗光诱导降解的组合物,它包括,
(a)易于光诱导降解的有机材料,和
(b)根据权利要求1的通式I或II的化合物。
9.根据权利要求8的组合物,它另外含有位阻胺稳定剂和/或UV吸收剂,所述位阻胺稳定剂和UV吸收剂选自s-三嗪类,N,N’-草酰二苯胺类,羟基二苯甲酮类,苯甲酸酯类,α-氰基丙烯酸酯类和与根据权利要求1的通式(I)或(II)的那些化合物不同的苯并三唑类。
10.根据权利要求8的组合物,其中有机材料是记录材料。
11.根据权利要求8的组合物,其中该有机材料是天然,半合成或合成聚合物。
12.根据权利要求11的组合物,其中聚合物是热塑性聚合物。
13.根据权利要求8的组合物,其中有机材料是涂料。
14.根据权利要求13的组合物,其中涂料是汽车涂料。
15.根据权利要求13的组合物,其中涂料施涂在基材上,其对于波长大于380nm的电磁辐射是敏感的。
16.根据权利要求8的组合物,其中通式I或II的化合物是以0.1重量%-30重量%的量存在,基于该有机材料的重量。
17.权利要求1的通式I或II的化合物作为涂料中的紫外线(UV)和可见(VIS)光吸收剂的用途。
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US6566507B2 (en) * | 2000-08-03 | 2003-05-20 | Ciba Specialty Chemicals Corporation | Processes for the preparation of benzotriazole UV absorbers |
ATE279503T1 (de) * | 2001-03-27 | 2004-10-15 | Ciba Sc Holding Ag | Wäschespülmittel enthaltend ein benztriazol als uv absorbierungsmittel |
JP2004277581A (ja) * | 2003-03-17 | 2004-10-07 | Konica Minolta Holdings Inc | セルロースエステルフィルム、偏光板、液晶表示装置、セルロースエステルフィルムの製造方法、偏光板の製造方法 |
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2006
- 2006-01-23 EP EP06707786A patent/EP1844049B1/en active Active
- 2006-01-23 DE DE602006020839T patent/DE602006020839D1/de active Active
- 2006-01-23 CN CN2006800037870A patent/CN101111496B/zh active Active
- 2006-01-23 RU RU2007132974/04A patent/RU2414471C2/ru not_active IP Right Cessation
- 2006-01-23 BR BRPI0606893-6A patent/BRPI0606893B1/pt not_active IP Right Cessation
- 2006-01-23 US US11/795,543 patent/US7695643B2/en active Active
- 2006-01-23 JP JP2007553581A patent/JP4975646B2/ja active Active
- 2006-01-23 WO PCT/EP2006/050354 patent/WO2006082145A1/en active Application Filing
- 2006-01-23 KR KR1020077020027A patent/KR101322194B1/ko active IP Right Grant
- 2006-01-23 AT AT06707786T patent/ATE502942T1/de not_active IP Right Cessation
- 2006-01-26 TW TW095103077A patent/TWI391393B/zh not_active IP Right Cessation
- 2006-01-26 MY MYPI20060366A patent/MY144674A/en unknown
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EP0717313A1 (en) * | 1994-11-30 | 1996-06-19 | Eastman Kodak Company | Benzotriazole based UV absorbing compounds and photographic elements containing them |
GB2346369A (en) * | 1999-01-21 | 2000-08-09 | Ciba Sc Holding Ag | Benzotriazole uv absorbers |
WO2002028854A1 (en) * | 2000-10-03 | 2002-04-11 | Ciba Specialty Chemicals Holding Inc. | Heteroaryl substituted hydroxyphenyltriazine uv-absorbers |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI588019B (zh) * | 2013-01-15 | 2017-06-21 | Sk化學公司 | 熱收縮性聚酯類薄膜 |
CN104744675A (zh) * | 2015-03-30 | 2015-07-01 | 华南理工大学 | 含6H–吡咯并[3,4–f]苯并三唑–5,7–二酮的共轭聚合物及其应用 |
Also Published As
Publication number | Publication date |
---|---|
EP1844049B1 (en) | 2011-03-23 |
TWI391393B (zh) | 2013-04-01 |
ATE502942T1 (de) | 2011-04-15 |
DE602006020839D1 (de) | 2011-05-05 |
US7695643B2 (en) | 2010-04-13 |
KR101322194B1 (ko) | 2013-10-30 |
BRPI0606893B1 (pt) | 2014-10-14 |
JP2008528657A (ja) | 2008-07-31 |
CN101111496A (zh) | 2008-01-23 |
BRPI0606893A2 (pt) | 2009-07-21 |
US20080157025A1 (en) | 2008-07-03 |
KR20070104640A (ko) | 2007-10-26 |
EP1844049A1 (en) | 2007-10-17 |
TW200633988A (en) | 2006-10-01 |
RU2007132974A (ru) | 2009-03-10 |
RU2414471C2 (ru) | 2011-03-20 |
MY144674A (en) | 2011-10-31 |
JP4975646B2 (ja) | 2012-07-11 |
WO2006082145A1 (en) | 2006-08-10 |
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