CN1681470A - 用于染色角质纤维的试剂 - Google Patents
用于染色角质纤维的试剂 Download PDFInfo
- Publication number
- CN1681470A CN1681470A CN03821158.0A CN03821158A CN1681470A CN 1681470 A CN1681470 A CN 1681470A CN 03821158 A CN03821158 A CN 03821158A CN 1681470 A CN1681470 A CN 1681470A
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- CN
- China
- Prior art keywords
- amino
- hydroxy
- dihydro
- methyl
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000835 fiber Substances 0.000 title claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 33
- 238000004043 dyeing Methods 0.000 title claims abstract description 20
- 210000004209 hair Anatomy 0.000 claims abstract description 34
- WCFAPJDPAPDDAQ-UHFFFAOYSA-N 1,2-dihydropyrimidine Chemical class C1NC=CC=N1 WCFAPJDPAPDDAQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 14
- -1 C2-C6Alkenyl radicals Chemical class 0.000 claims description 370
- 150000003254 radicals Chemical class 0.000 claims description 101
- 150000001875 compounds Chemical class 0.000 claims description 86
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 61
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 56
- 150000003839 salts Chemical class 0.000 claims description 52
- 125000000217 alkyl group Chemical group 0.000 claims description 44
- 239000003153 chemical reaction reagent Substances 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 41
- 239000003086 colorant Substances 0.000 claims description 39
- 102000011782 Keratins Human genes 0.000 claims description 33
- 108010076876 Keratins Proteins 0.000 claims description 33
- 239000007795 chemical reaction product Substances 0.000 claims description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 29
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 27
- 239000000975 dye Substances 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 26
- 125000003118 aryl group Chemical group 0.000 claims description 26
- 125000005843 halogen group Chemical group 0.000 claims description 25
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 22
- 239000007800 oxidant agent Substances 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 16
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 15
- 239000000982 direct dye Substances 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 229940124530 sulfonamide Drugs 0.000 claims description 13
- 150000003456 sulfonamides Chemical class 0.000 claims description 13
- PYVBGEUEQLAGGN-UHFFFAOYSA-N 2,3,6-trihydroxybenzaldehyde Chemical compound OC1=CC=C(O)C(C=O)=C1O PYVBGEUEQLAGGN-UHFFFAOYSA-N 0.000 claims description 12
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 12
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 12
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 claims description 12
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000002081 enamines Chemical group 0.000 claims description 11
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 11
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 10
- PKZJLOCLABXVMC-UHFFFAOYSA-N 2-Methoxybenzaldehyde Chemical compound COC1=CC=CC=C1C=O PKZJLOCLABXVMC-UHFFFAOYSA-N 0.000 claims description 10
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 claims description 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 10
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 claims description 10
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- IXWOUPGDGMCKGT-UHFFFAOYSA-N 2,3-dihydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1O IXWOUPGDGMCKGT-UHFFFAOYSA-N 0.000 claims description 9
- 125000006577 C1-C6 hydroxyalkyl group Chemical group 0.000 claims description 9
- LUSZGTFNYDARNI-UHFFFAOYSA-N Sesamol Chemical compound OC1=CC=C2OCOC2=C1 LUSZGTFNYDARNI-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- 150000002476 indolines Chemical class 0.000 claims description 9
- APHLYZNGFCQHCT-UHFFFAOYSA-N 2,3,6-trimethoxybenzaldehyde Chemical compound COC1=CC=C(OC)C(C=O)=C1OC APHLYZNGFCQHCT-UHFFFAOYSA-N 0.000 claims description 8
- JIVGSHFYXPRRSZ-UHFFFAOYSA-N 2,3-dimethoxybenzaldehyde Chemical compound COC1=CC=CC(C=O)=C1OC JIVGSHFYXPRRSZ-UHFFFAOYSA-N 0.000 claims description 8
- WNCNWLVQSHZVKV-UHFFFAOYSA-N 2,4,5-trihydroxybenzaldehyde Chemical compound OC1=CC(O)=C(C=O)C=C1O WNCNWLVQSHZVKV-UHFFFAOYSA-N 0.000 claims description 8
- IUNJCFABHJZSKB-UHFFFAOYSA-N 2,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C(O)=C1 IUNJCFABHJZSKB-UHFFFAOYSA-N 0.000 claims description 8
- LWRSYTXEQUUTKW-UHFFFAOYSA-N 2,4-dimethoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C(OC)=C1 LWRSYTXEQUUTKW-UHFFFAOYSA-N 0.000 claims description 8
- CLFRCXCBWIQVRN-UHFFFAOYSA-N 2,5-dihydroxybenzaldehyde Chemical compound OC1=CC=C(O)C(C=O)=C1 CLFRCXCBWIQVRN-UHFFFAOYSA-N 0.000 claims description 8
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims description 8
- VFZRZRDOXPRTSC-UHFFFAOYSA-N 3,5-Dimethoxybenzaldehyde Chemical compound COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 claims description 8
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 claims description 8
- WMPDAIZRQDCGFH-UHFFFAOYSA-N 3-methoxybenzaldehyde Chemical compound COC1=CC=CC(C=O)=C1 WMPDAIZRQDCGFH-UHFFFAOYSA-N 0.000 claims description 8
- YMWYSWXWDNMUIX-UHFFFAOYSA-N 4-hydroxy-2,3-dimethoxybenzaldehyde Chemical compound COC1=C(O)C=CC(C=O)=C1OC YMWYSWXWDNMUIX-UHFFFAOYSA-N 0.000 claims description 8
- WBIZZNFQJPOKDK-UHFFFAOYSA-N 4-hydroxy-2-methoxybenzaldehyde Chemical compound COC1=CC(O)=CC=C1C=O WBIZZNFQJPOKDK-UHFFFAOYSA-N 0.000 claims description 8
- UYGBSRJODQHNLQ-UHFFFAOYSA-N 4-hydroxy-3,5-dimethylbenzaldehyde Chemical compound CC1=CC(C=O)=CC(C)=C1O UYGBSRJODQHNLQ-UHFFFAOYSA-N 0.000 claims description 8
- GHVHDYYKJYXFGU-UHFFFAOYSA-N Beta-Orcinol Chemical compound CC1=CC(O)=C(C)C(O)=C1 GHVHDYYKJYXFGU-UHFFFAOYSA-N 0.000 claims description 8
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 8
- 238000004040 coloring Methods 0.000 claims description 8
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical compound CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 claims description 8
- 239000000118 hair dye Substances 0.000 claims description 8
- JVTZFYYHCGSXJV-UHFFFAOYSA-N isovanillin Chemical compound COC1=CC=C(C=O)C=C1O JVTZFYYHCGSXJV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Chemical class 0.000 claims description 8
- 239000002184 metal Chemical class 0.000 claims description 8
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 8
- COBXDAOIDYGHGK-UHFFFAOYSA-N syringaldehyde Natural products COC1=CC=C(C=O)C(OC)=C1O COBXDAOIDYGHGK-UHFFFAOYSA-N 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- WJUFSDZVCOTFON-UHFFFAOYSA-N veratraldehyde Chemical compound COC1=CC=C(C=O)C=C1OC WJUFSDZVCOTFON-UHFFFAOYSA-N 0.000 claims description 8
- KWSVXCAQFTWTEF-UHFFFAOYSA-N 2-(2,5-diaminophenyl)ethanol Chemical compound NC1=CC=C(N)C(CCO)=C1 KWSVXCAQFTWTEF-UHFFFAOYSA-N 0.000 claims description 7
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 claims description 7
- QGNGOGOOPUYKMC-UHFFFAOYSA-N 4-hydroxy-6-methylaniline Chemical compound CC1=CC(O)=CC=C1N QGNGOGOOPUYKMC-UHFFFAOYSA-N 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 7
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 7
- GCMNJUJAKQGROZ-UHFFFAOYSA-N 1,2-Dihydroquinolin-2-imine Chemical compound C1=CC=CC2=NC(N)=CC=C21 GCMNJUJAKQGROZ-UHFFFAOYSA-N 0.000 claims description 6
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 claims description 6
- JMFBVEWGVFCOKD-UHFFFAOYSA-N 2-n,4-n-bis(3-bromophenyl)-5-fluoropyrimidine-2,4-diamine Chemical compound N1=C(NC=2C=C(Br)C=CC=2)C(F)=CN=C1NC1=CC=CC(Br)=C1 JMFBVEWGVFCOKD-UHFFFAOYSA-N 0.000 claims description 6
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 6
- 229940018563 3-aminophenol Drugs 0.000 claims description 6
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 claims description 6
- WSEFOZIMAJPJHW-UHFFFAOYSA-N 4-amino-2-(hydroxymethyl)phenol Chemical compound NC1=CC=C(O)C(CO)=C1 WSEFOZIMAJPJHW-UHFFFAOYSA-N 0.000 claims description 6
- DCICUQFMCRPKHZ-UHFFFAOYSA-N 4-imidazol-1-ylbenzaldehyde Chemical compound C1=CC(C=O)=CC=C1N1C=NC=C1 DCICUQFMCRPKHZ-UHFFFAOYSA-N 0.000 claims description 6
- DBFYESDCPWWCHN-UHFFFAOYSA-N 5-amino-2-methylphenol Chemical compound CC1=CC=C(N)C=C1O DBFYESDCPWWCHN-UHFFFAOYSA-N 0.000 claims description 6
- KZQYIMCESJLPQH-UHFFFAOYSA-N Demethylated antipyrine Chemical compound N1C(C)=CC(=O)N1C1=CC=CC=C1 KZQYIMCESJLPQH-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 6
- 150000003857 carboxamides Chemical class 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 claims description 6
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 6
- 229940081310 piperonal Drugs 0.000 claims description 6
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- UCTUXUGXIFRVGX-UHFFFAOYSA-N 2,3,4-trimethoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C(OC)=C1OC UCTUXUGXIFRVGX-UHFFFAOYSA-N 0.000 claims description 5
- YESOPQNVGIQNEV-UHFFFAOYSA-N 2-(4-amino-2-nitroanilino)benzoic acid Chemical compound [O-][N+](=O)C1=CC(N)=CC=C1NC1=CC=CC=C1C(O)=O YESOPQNVGIQNEV-UHFFFAOYSA-N 0.000 claims description 5
- RBUQOUQQUQCSAU-UHFFFAOYSA-N 2-(4-aminoanilino)ethanol Chemical compound NC1=CC=C(NCCO)C=C1 RBUQOUQQUQCSAU-UHFFFAOYSA-N 0.000 claims description 5
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 5
- GQENNFHUCSKOPN-UHFFFAOYSA-N 2-ethoxy-4-hydroxybenzaldehyde Chemical compound CCOC1=CC(O)=CC=C1C=O GQENNFHUCSKOPN-UHFFFAOYSA-N 0.000 claims description 5
- JYMORVWTSQQBRD-UHFFFAOYSA-N 2-ethyl-3-methylnaphthalene-1-carbaldehyde Chemical compound C1=CC=CC2=C(C=O)C(CC)=C(C)C=C21 JYMORVWTSQQBRD-UHFFFAOYSA-N 0.000 claims description 5
- PCYGLFXKCBFGPC-UHFFFAOYSA-N 3,4-Dihydroxy hydroxymethyl benzene Natural products OCC1=CC=C(O)C(O)=C1 PCYGLFXKCBFGPC-UHFFFAOYSA-N 0.000 claims description 5
- HEMGYNNCNNODNX-UHFFFAOYSA-N 3,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1N HEMGYNNCNNODNX-UHFFFAOYSA-N 0.000 claims description 5
- XYRDGCCCBJITBH-UHFFFAOYSA-N 3-amino-2-chloro-6-methylphenol Chemical compound CC1=CC=C(N)C(Cl)=C1O XYRDGCCCBJITBH-UHFFFAOYSA-N 0.000 claims description 5
- PZKNKZNLQYKXFV-UHFFFAOYSA-N 4-amino-2-(aminomethyl)phenol Chemical compound NCC1=CC(N)=CC=C1O PZKNKZNLQYKXFV-UHFFFAOYSA-N 0.000 claims description 5
- JQVAPEJNIZULEK-UHFFFAOYSA-N 4-chlorobenzene-1,3-diol Chemical compound OC1=CC=C(Cl)C(O)=C1 JQVAPEJNIZULEK-UHFFFAOYSA-N 0.000 claims description 5
- FOAQOAXQMISINY-UHFFFAOYSA-N 4-morpholin-4-ylbenzaldehyde Chemical compound C1=CC(C=O)=CC=C1N1CCOCC1 FOAQOAXQMISINY-UHFFFAOYSA-N 0.000 claims description 5
- SGNZYJXNUURYCH-UHFFFAOYSA-N 5,6-dihydroxyindole Chemical compound C1=C(O)C(O)=CC2=C1NC=C2 SGNZYJXNUURYCH-UHFFFAOYSA-N 0.000 claims description 5
- WEPOCTWSRWLQLL-UHFFFAOYSA-N 6-methoxypyridine-2,3-diamine Chemical compound COC1=CC=C(N)C(N)=N1 WEPOCTWSRWLQLL-UHFFFAOYSA-N 0.000 claims description 5
- GZGZVOLBULPDFD-UHFFFAOYSA-N HC Red No. 3 Chemical compound NC1=CC=C(NCCO)C([N+]([O-])=O)=C1 GZGZVOLBULPDFD-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 5
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 5
- DKZBBWMURDFHNE-NSCUHMNNSA-N coniferyl aldehyde Chemical compound COC1=CC(\C=C\C=O)=CC=C1O DKZBBWMURDFHNE-NSCUHMNNSA-N 0.000 claims description 5
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- VGSVNUGKHOVSPK-UHFFFAOYSA-N leukoaminochrome Chemical compound C1=C(O)C(O)=CC2=C1NCC2 VGSVNUGKHOVSPK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 150000003142 primary aromatic amines Chemical class 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- DKZBBWMURDFHNE-UHFFFAOYSA-N trans-coniferylaldehyde Natural products COC1=CC(C=CC=O)=CC=C1O DKZBBWMURDFHNE-UHFFFAOYSA-N 0.000 claims description 5
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 5
- 235000012141 vanillin Nutrition 0.000 claims description 5
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 5
- VUIMBZIZZFSQEE-UHFFFAOYSA-N 1-(1h-indol-3-yl)ethanone Chemical compound C1=CC=C2C(C(=O)C)=CNC2=C1 VUIMBZIZZFSQEE-UHFFFAOYSA-N 0.000 claims description 4
- OQWWMUWGSBRNMA-UHFFFAOYSA-N 1-(2,4-diaminophenoxy)ethanol Chemical compound CC(O)OC1=CC=C(N)C=C1N OQWWMUWGSBRNMA-UHFFFAOYSA-N 0.000 claims description 4
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- FAGMGMRSURYROS-UHFFFAOYSA-M trihexadecyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(CCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCC FAGMGMRSURYROS-UHFFFAOYSA-M 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/10—Preparations for permanently dyeing the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/35—Ketones, e.g. benzophenone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
- A61K8/4953—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom containing pyrimidine ring derivatives, e.g. minoxidil
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Emergency Medicine (AREA)
- Cosmetics (AREA)
Abstract
本发明涉及一种用于染色角蛋白纤维特别是头发的试剂,包括1,2-二氢嘧啶鎓衍生物和反应性羰基化合物,及所述试剂的组合物在用于染色角蛋白纤维、润色或者发色调整以前着色的角蛋白纤维中的用途,以及染色角蛋白纤维特别是头发的方法。
Description
本发明涉及一种用于染色(着色)含角蛋白纤维特别是头发的试剂,包括结合有反应性羰基化合物的1,2-二氢嘧啶鎓衍生物,及该化合物在用于染色含角蛋白纤维、润色或者发色调整已经着色的含角蛋白纤维中的用途,以及染色含角蛋白纤维特别是头发的方法。
为染色含角蛋白纤维,通常使用大量的染料或者氧化染料,后者得自于一种或多种显影液成份彼此或者与一种或多种偶合剂组份的氧化偶合。偶合剂和显影液成份也称为氧化染料前体。
通常,在对或者邻位含有另外的自由或者取代的羟基或者氨基的一级芳香胺、二氨基吡啶衍生物、杂环腙、4-氨基吡唑啉酮以及吡啶2,4,5,6-四氨基嘧啶和其衍生物用作显影液成份。
特定典型的例子是对苯二胺、对间甲苯二胺、2,4,5,6-四氨基嘧啶、对氨基苯酚、N,N-双(2-羟乙基)-对苯二胺、2-(2,5-二氨基苯基)乙醇、2-(2,5-二氨基苯氧基)乙醇、1-苯基-3-羧氨基-4-氨基吡唑啉-5-酮、4-氨基-3-甲基苯酚、2-氨甲基-4-氨基苯酚、2-羟甲基-4-氨基苯酚、2-羟基-4,5,6-三氨基嘧啶、2,4-二羟基-5,6-二氨基嘧啶和2,5,6-三氨基-4-羟基嘧啶。
通常,间苯二胺衍生物、萘酚、间苯二酚和间苯二酚衍生物、吡唑啉酮、间氨基苯酚和取代的吡啶衍生物。适当的偶合剂物质特别是α-萘酚、1,5-,2,7-和1,7-二羟基萘、5-氨基-2-甲基苯酚、间氨基苯酚、间苯二酚、间苯二酚单甲醚、间苯二胺、2,4-二氨基苯氧基乙醇、2-氨基-4-(2-羟乙基氨基)茴香醚(莱曼蓝色)、1-苯基-3-甲基吡唑啉-5-酮、2,4-二氯-3-氨基苯酚、1,3-二(2,4-二氨基苯氧基)丙烷、2-氯代间苯二酚、4-氯代间苯二酚、2-氯代-6-甲基-3-氨基苯酚、2-甲基间苯二酚、5-甲基间苯二酚、3-氨基-6-甲氧基-2-甲氨基吡啶和3,5-二氨基-2,6-二甲氧基吡啶可用作偶合剂组份。
关于其它通常的染料组份,明确地参考如下系列文献:“皮肤病学”,Ch.Culnan,H.Maibach所编,Marcel Dekker Inc.出版,New York,Basel,1986,vol.7,Ch.Zviak,The Science of Hair Care,Ch.7,248-250页(大量的染料),和Ch.8,264-267页(氧化染料)和“European Inventoryof Cosmetic Raw MateRIals”,1996,由the European Commission出版,可从Bundesverband der deutschen IndustRIe-und Handelsunternehmenfür Arzneimittel以软盘获得,Reformwaren und Krperpflegemittele.V.,Mannheim。
尽管利用氧化染料可得到具有良好坚牢度性质的充分着色,但受氧化剂比如H2O2的影响通常发生颜色的显色,所述的氧化剂有时可导致对纤维的损害。制备带红色范围具有令人满意坚牢度性质的氧化毛发着色证明仍然是有问题的,特别对于具有良好的耐洗牢度和耐摩擦程度。而且,一些氧化染料前体或者特定的氧化染料前体混合物有时对于敏感皮肤的人可产生敏化效应。大量的染料可以在温和的条件下使用,但是有这样的缺点,即通常着色的坚牢度性质不充分。
包括1,2-二氢嘧啶鎓衍生物的着色剂,以及它们用于染色含角蛋白纤维或者用于润色或者发色调整已经着色的含角蛋白纤维迄今为止没有报道过。
嘧啶酮用作亚甲基碱的反应描述在H.Baumann及其他的出版物,Liebigs Ann.Chem.中,1968,717,124-136。包括1,2-二氢嘧啶鎓衍生物的毛发着色剂或者公开的半花青用于染色含角蛋白纤维没有提出过。
在德国专利申请DE-A1-2047431中,描述了用于着色阴离子改性纤维比如酸改性的聚酯或者丙烯腈聚合物的阳离子次甲基染料。对于阳离子次甲基染料的合成,尤其使用3,4-二氢-3-甲基-4-亚甲基喹唑啉-2-酮和1,3,6-三甲基-4-亚甲基嘧啶-2-酮以及必要的对苯二醛。
在该德国专利申请DE-A1-2165913中,提出了一种利用光敏感染料制作漂白影像的方法。要求的光敏感染料属于嘧啶酮或者硫代嘧啶酮类染料。
本发明的目的是提供用于含角蛋白纤维特别是头发的着色剂,其颜色深度、灰色覆盖度和坚牢度性质例如光-、摩擦-和耐洗牢度以及耐汗坚牢度和冷烫坚牢度与通常的氧化毛发着色剂性质上至少相当,特别在带红色的范围,但不必取决于氧化剂例如实施例H2O2。况且,该染料不具有任何或者仅极低的敏化度。
令人惊奇的是,现在已经发现在通式1中举例说明的1,2-二氢嘧啶鎓衍生物,特别是结合包括至少一个反应性羰基的化合物,非常适于染色含角蛋白纤维,甚至在没有氧化剂的情况下。它们提供具有优异亮度和颜色深度的着色,得到许多色相。特别是,在从黄色到黄褐色、橙色、褐橙色、褐色、红、红紫罗兰到蓝紫罗兰和黑色色调范围得到具有改进坚牢度性质的着色。然而,不必要排除加入氧化剂。
本发明的主题是用于染色含角蛋白纤维特别是头发的试剂,包括根据通式1和、或其烯胺形式的至少一种1,2-二氢嘧啶鎓衍生物,
其中,
■R1和R2彼此独立地代表直链的或者环状的C1-C6烷基、C2-C6链烯基团、任选取代的芳基、任选取代的杂芳基、芳基C1-C6烷基、C1-C6羟烷基、C2-C6多羟烷基、C1-C6烷氧基-C1-C6烷基、基团RIRIIN-(CH2)m-,其中RI和RII彼此独立地代表氢原子、C1-C4烷基、C1-C4羟烷基或者芳基C1-C6烷基,其中RI和RII与氮原子可形成5-,6-或者7-元环,和m代表2,3,4,5或者6。
■R3和R4彼此独立地代表氢原子或者C1-C6烷基,其中至少一种基团R3和R4是指C1-C6烷基,
■R5代表氢原子、C1-C6烷基、C1-C6羟烷基、C2-C6多羟烷基团、C1-C6烷氧基、C1-C6羟基烷氧基、基团RIIIIRIVN-(CH2)q-,其中RIII和RIV彼此独立地代表氢原子、C1-C6烷基、C1-C6羟烷基或者芳基C1-C6烷基,及q代表1、2、3、4、5或者6,其中基团R5与R3或者R4基团之一可形成5-或者6-元芳烃或者脂肪族的环,而且所述的环可以任选被如下的基团取代,卤素原子、C1-C6烷基、C1-C6羟烷基、C2-C6多羟烷基团、C1-C6烷氧基、C1-C6羟基烷氧基、硝基、羟基、基团RVRVIN-(CH2)s-,其中RV和RVI彼此独立地代表氢原子、C1-C6烷基、C1-C6羟烷基或者芳基C1-C6烷基,s代表0、1、2、3、4、5或者6,
■Y代表氧原子、硫原子或者基团NRVII,其中RVII代表氢原子、芳基、杂芳基、C1-C6烷基或者C1-C6芳烷基,
■X-代表卤化物、苯磺酸盐、对甲苯磺酸盐、C1-C4链烷磺酸盐、三氟甲烷磺酸盐、高氯酸盐、0.5硫酸盐、硫酸氢盐、四氟硼酸盐、六氟磷酸盐或者四氯锌酸盐,
和至少一种含有反应性羰基(组分B)的化合物。
在优选实施方式中,Y代表氧或者硫原子,特别优选代表氧原子。
优选,X-代表卤化物、特别是氯化物、溴化物或者碘化物,对甲苯磺酸盐、四氟硼酸盐、三氟甲烷磺酸盐、六氟磷酸盐、0.5硫酸盐或者硫酸氢盐。该阴离子氯化物、溴化物、碘化物、硫酸氢盐或者对甲苯磺酸盐特别优选用作X-。
R5优选代表氢原子。
根据通式I的至少一种R3或者R4基团代表C1-C6烷基。所述的烷基在其α-碳原子上载带有至少两个氢原子。特别优选的烷基是甲基、乙基、丙基、正丁基、异丁基、正戊基、异戊基、正己基。相当特别优选的是当R3和R4彼此独立地代表氢或者甲基,其中至少一种基团R3或者R4是指甲基。
优选,根据通式I的化合物选自1,2-二氢-1,3,4,6-四甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3-二乙基-4,6-二甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3-二丙基-4,6-二甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3-二(2-羟乙基)-4,6-二甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3-联苯-4,6-二甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3,4,6-四甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-二乙基-4,6-二甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-二丙基-4,6-二甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-二(2-羟乙基)-4,6-二甲基-2-硫代-硫酸氢嘧啶、1,2-二氢-1,3-联苯-4,6-二甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3,4-三甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3,4-三甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3,4-甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3-二乙基-4-甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-二丙基-4-甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3-二丙基-4-甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-二(2-羟乙基)-4-甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3-二(2-羟乙基)-4-甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-联苯-4-甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3-联苯-4-甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3,4,5,6-五甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3,4,6-四甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3-二乙基-4,6-二甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3-二丙基-4,6-二甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3-二(2-羟乙基)-4,6-二甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3-联苯-4,6-二甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3,4,6-四甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-二丙基-4,6-二甲基-2-硫代-硫酸氢嘧啶、1,2-二氢-1,3-二(2-羟乙基)-4,6-二甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-联苯-4,6-二甲基-2-硫代-硫酸氢嘧啶、1,2-二氢-1,3,4-三甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3,4-三甲基-2-硫代-硫酸氢嘧啶、1,2-二氢-1,3-二乙基-4-甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3-二乙基-4-甲基-2-硫代-硫酸氢嘧啶、1,2-二氢-1,3-二丙基-4-甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3-二丙基-4-甲基-2-硫代-硫酸氢嘧啶、1,2-二氢-1,3-二(2-羟乙基)-4-甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3-二(2-羟乙基)-4-甲基-2-硫代-硫酸氢嘧啶、1,2-二氢-1,3-联苯-4-甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3-联苯-4-甲基-2-硫代-硫酸氢嘧啶、1,2-二氢-3,4-二甲基-2-氧代-氯化喹唑啉、1,2-二氢-3,4-二甲基-2-氧代-对甲苯磺酸喹唑啉、1,2-二氢-3,4-二甲基-2-硫代-氯化喹唑啉、1,2-二氢-3,4-二甲基-2-硫代-对甲苯磺酸喹唑啉、1,2-二氢-1,3,4-三甲基-2-硫代-硫酸氢喹唑啉、1,3,4-三甲基-2-氧代-2,3,5,6,7,8-硫酸氢六氢喹啉、1,3,4-三甲基-2-硫代-2,3,5,6,7,8-硫酸氢六氢喹啉、1,3,4-三甲基-2-氧代-3,5,6,7-四氢-2H-环戊二烯并硫酸氢嘧啶和1,3,4-三甲基-2-硫代-3,5,6,7-四氢-2H-环戊二烯并硫酸氢嘧啶。
根据通式I组分A相当特别优选发明的化合物选自1,2-二氢-1,3,4,6-四甲基-2-氯化氧嘧啶、1,2-二氢-1,3,4,6-四甲基-2-硫酸氢氧嘧啶、1,2-二氢-1,3,4-三甲基-2-氯化氧嘧啶、1,2-二氢-4,6-二甲基-1,3-二丙基-2-氯化氧嘧啶、1,2-二氢-1,3,4,6-四甲基-2-硫酸氢硫代氧嘧啶和1,2-二氢-1,3,4,5,6-五甲基-2-氯化氧嘧啶。
在本发明的上下文中以下应提到引用当作取代基的基团的例子。C1-C6烷基的例子是基团甲基、乙基、丙基、异丙基、正丁基、仲丁基、特丁基、正戊基和正己基。优选的烷基是丙基、甲基和乙基。适当的环状烷基的例子是环戊基和环己基。C2-C6链烯基团的例子是乙烯基和烯丙基。根据本发明,优选的示范性C1-C6烷氧基团是甲氧基或者乙氧基。甲氧基羰基-、乙氧基羰基-、正丙氧基羰基-、异丙氧基羰基-、正丁氧基羰基-、仲丁氧基羰基-和特丁氧基羰基是C1-C4烷氧羰基的例子;甲氧基羰基和乙氧基羰基在本发明中是特别优选的。另外,C1-C6羟烷基团的优选的例子是引用当作羟甲基-、2-羟乙基-、2-羟丙基-、3-羟丙基-、4-羟丁基-、5-羟戊基-和6-羟己基。2-羟乙基团是特别优选的。甲氧基乙基-、乙氧基乙基-、甲氧基丙基-、甲氧基丁基-、乙氧基丁基-和甲氧基己基是C1-C6烷氧基C1-C6烷基的例子。C2-C6多羟烷基的例子是2,3-二羟基丙基、3,4-二羟基丁基和2,4-二羟基丁基。优选的羟基C1-C6烷氧基是2-羟基乙氧基。优选的芳基是苯基、萘基和联苯基。
卤素原子的例子是氟、氯、溴或碘原子,其中氯原子是相当特别优选的。优选的芳基C1-C6氨基烷基是苯甲基和2-苯乙基。氨甲基、2-氨乙基、3-氨丙基、2-二甲基氨乙基、二乙基氨甲基、二甲基氨甲基、2-甲基氨乙基、二甲基氨基、哌啶基甲基、吡咯烷基甲基、吗啉基甲基和氨基是基团RIRIIN-(CH2)m-的例子,其中二乙基氨甲基、哌啶基甲基、2-二甲基氨乙基、二甲基氨基和氨基是特别优选的。 杂芳基的例子是哟咯烷基、2-呋喃基、2-噻吩基、4-吡啶基、3-吡啶基、2-吡啶基、三唑基和1-咪唑啉基。杂环(C1-4)烷基的例子是吡咯烷基-(C1-4)烷基、哌啶基-(C1-4)烷基、吗啉代-(C1-4)烷基、2-呋喃基-(C1-4)烷基、2-噻吩基-(C1-4)烷基、4-吡啶基-(C1-4)烷基、3-吡啶基-(C1-4)烷基、2-吡啶基-(C1-4)烷基、三唑基-(C1-4)烷基和1-咪唑啉基-(C1-4)烷基。优选的(C1-4)羧烷基是3-羧丙基。特别优选的C2-C6链烯基是亚乙烯基和丙烯基。特别优选的C4-C6链二烯基团是1,3-丁二烯-1,4-二基。基团1-羧亚丙基和1-羧亚乙基是优选的羧基C1-C4亚烷基团。根据本发明,随后的使用术语源自于这里给出的定义。
根据通式I本发明的1,2-二氢嘧啶鎓衍生物是CH-酸化合物。根据通式I它们与烯胺形式的1,2-二氢嘧啶鎓衍生物化学平衡存在。相应的烯胺特别地可以从通式I的化合物通过利用可在C1-C6烷基R3或者R4的α-碳原子去质子化的碱进行合成。下面举例说明去质子化的例子,其中为清楚起见,基团R-CH2-选用作R3。根据通式Ia的化合物是一种本发明烯胺形式的1,2-二氢嘧啶鎓衍生物。
含角蛋白纤维应该被理解为羊毛、毛皮、羽毛和特别是头发。 然而原则上,本发明的着色剂还可以用于染色其它的天然纤维比如棉、黄麻、剑麻、亚麻布或者丝、改性的天然纤维比如再生纤维素、硝基-、烷基-或羟烷基-或乙酰纤维素。
根据通式I大多数的1,2-二氢嘧啶鎓衍生物公开于文献中,可在市场上买到,或者根据如下的已知合成过程:D.Lloyd et al.,J.Chem.Soc.Perkin Trans I,1977,16,1862-1869;S.T.Oswald et al.,J.Heterocycl.Chem.,1974,11(3),441-443;H.Baumann et al.,Liebigs Ann.Chem.,1968,717,124-136 and V.A.Chuiguk,Ukr.Khim.Zh.(RussEd.),1982,48(11),1220-1223。
如果根据本发明通式I的化合物,和至少一种具有反应性羰基的物质(以后称为组分B或者反应性羰基化合物)包括在本发明的试剂中,可得到在宽的色调范围内具有增强亮度和改进坚牢度性质(耐光度、耐洗性、耐磨度)的着色。本发明的反应性羰基化合物含至少一个羰基作为活性基团,所述的活性基团与通式I的CH-酸化合物反应形成碳-碳键。况且,根据本发明也可使用那些化合物,其中反应性羰基用这样的方式得到,要使得到的羰基对通式ICH-酸化合物的碳原子的反应性仍然存在。这些衍生物优选是如下的加成化合物:
a)胺和它们的衍生物形成亚胺或者肟作为加成化合物;
b)在反应性羰基化合物的羰基碳原子上醇形成乙缩醛或者酮缩醇作为加成化合物。
组分B优选选自根据通式II的化合物,
其中
■AR代表苯、萘、吡啶、嘧啶、吡嗪、哒嗪、咔唑、吡咯、吡唑、呋喃、噻吩、1,2,3-三嗪、1,3,5-三嗪、喹啉、异喹啉、吲哚、二氢吲哚、中氮茚、二氢化茚、咪唑、1,2,4-三唑、1,2,3-三唑、四唑、苯并咪唑、1,3-噻唑、苯并噻唑、吲唑、苯并恶唑、喹喔啉、喹唑啉、喹嗪、噌啉、吖啶、久洛尼定、苊、芴、联苯基、二苯基甲烷、二苯甲酮、二苯醚、偶氮苯、色酮、香豆素、二苯胺、芪,其中N-杂原子的还可以被季铵化,
■R6代表氢原子、C1-C6烷基、C2-C6酰基、C2-C4链烯基、C1-C4全氟烷基、任选取代的芳基或者杂芳基,
■R7、R8和R9互相独立地代表氢原子、卤素原子、C1-C6烷基、C1-C6烷氧基、C1-C6氨基烷基、C1-C6羟烷基、C1-C6烷氧基C1-C6烷基氧基、C2-C6酰基,乙酰基、羧基、羧酸根合、氨甲酰基、磺基、硫酸根合、磺酰胺、磺酰氨基、C2-C6链烯基、芳基、芳基C1-C6烷基、羟基、硝基、吡咯烷基、吗啉代、哌啶基、氨基、胺基或者1-咪唑啉基,其中后三个基团可以被一种或多种C1-C6烷基、C1-C6羧烷基C1-C6羟烷基、C2-C6链烯基、C1-C6烷氧基C1-C6烷基取代,用任选取代的苄基、磺基(C1-C4)烷基或者杂环(C1-C4)烷基取代,
其中基团R7、R8、R9和-Z-Y-R6的两个也和该分子的残基一起形成缩合的任选取代的5-、6-或者7-元环,所述的环上同样可有缩合的芳环,其中体系AR取决于环尺寸可以有另外的取代基,所述的取代基彼此独立地代表相同的基团如R7、R8和R9,
■Z代表直接键合、羰基、羧基(C1-C4)亚烷基、任选取代的C2-C6链烯基、C4-C6链二烯、亚呋喃基、亚噻吩基、亚芳基、亚乙烯基亚芳基、亚乙烯基亚呋喃基、亚乙烯基亚噻吩基,其中Z与-Y-R6基团还可以一起形成任选取代的5-6-或者7-元环。
■Y代表选自羰基、根据通式III的基团和根据通式IV的基团,
■其中R10代表氢原子、羟基、C1-C4烷氧基、C1-C6烷基、C1-C6羟烷基、C2-C6多羟烷基、C1-C6烷氧基C1-C6烷基,
■R11和R12彼此独立地代表C1-C6烷基、芳基或者与通式IV的结构元素O-C-O一起形成5-或者6-元环。
组分B特别优选选自苯乙酮、苯丙酮、2-羟苯乙酮、3-羟苯乙酮、4-羟苯乙酮、2-羟苯丙酮、3-羟苯丙酮、4-羟苯丙酮、2-羟苯丁酮、3-羟苯丁酮、4-羟苯丁酮、2,4-二羟基苯乙酮、2,5-二羟基苯乙酮、2,6-二羟基苯乙酮、2,3,4-三羟基苯乙酮、3,4,5-三羟基苯乙酮、2,4,6-三羟基苯乙酮、2,4,6-三甲氧基苯乙酮、3,4,5-三甲氧基苯乙酮、3,4,5-三甲氧基苯乙酮-二乙基缩酮、4-羟基-3-甲氧基-苯乙酮、3,5-二甲氧基-4-羟苯乙酮、4-氨基苯乙酮、4-二甲基氨基苯乙酮、4-吗啉基苯乙酮、4-哌啶基苯乙酮、4-咪唑基苯乙酮、2-羟基-5-溴代-苯乙酮、4-羟基-3-硝基苯乙酮、苯乙酮-2-羧酸、苯乙酮-4-羧酸、二苯甲酮、4-羟基二苯甲酮、2-氨基二苯甲酮、4,4′-二羟基二苯甲酮、2,4-二羟基-二苯甲酮、2,4,4′-三羟基二苯甲酮、2,3,4-三羟基二苯甲酮、2-羟基-1-萘乙酮、1-羟基-2-萘乙酮、色酮、色酮-2-羧酸、黄酮、3-羟基黄酮、3,5,7-三羟基黄酮、4′,5,7-三羟基黄酮、5,6,7-三羟基黄酮、五羟黄酮、1-2,3-二氢-1-茚酮、9-芴酮、3-羟基芴酮、蒽酮、1,8-二羟基蒽酮、香草醛、松柏醛、2-甲氧基苯甲醛、3-甲氧基苯甲醛、4-甲氧基苯甲醛、2-乙氧基苯甲醛、3-乙氧基苯甲醛、4-乙氧基苯甲醛、4-羟基-2,3-二甲氧基-苯甲醛、4-羟基-2,5-二甲氧基-苯甲醛、4-羟基-2,6-二甲氧基-苯甲醛、4-羟基-2-甲基苯甲醛、4-羟基-3-甲基-苯甲醛、4-羟基-2,3-二甲基苯甲醛、4-羟基-2,5-二甲基-苯甲醛、4-羟基-2,6-二甲基苯甲醛、4-羟基-3,5-二甲氧基-苯甲醛、4-羟基-3,5-二甲基苯甲醛、3,5-二乙氧基-4-羟基-苯甲醛、2,6-二乙氧基-4-羟基苯甲醛、3-羟基-4-甲氧基-苯甲醛、2-羟基-2-甲氧基苯甲醛、2-乙氧基-4-羟基-苯甲醛、3-乙氧基-4-羟基-苯甲醛、4-乙氧基-2-羟基-苯甲醛、4-乙氧基-3-羟基-苯甲醛、2,3-二甲氧基苯甲醛、2,4-二甲氧基苯甲醛、2,5-二甲氧基苯甲醛、2,6-二甲氧基苯甲醛、3,4-二甲氧基苯甲醛、3,5-二甲氧基苯甲醛、2,3,4-三甲氧基苯甲醛、2,3,5-三甲氧基苯甲醛、2,3,6-三甲氧基苯甲醛、2,4,6-三甲氧基苯甲醛、2,4,5-三甲氧基苯甲醛、2,5,6-三甲氧基苯甲醛、2-羟基苯甲醛、3-羟基苯甲醛、4-羟基苯甲醛、2,3-二羟基苯甲醛、2,4-二羟基苯甲醛、2,5-二羟基苯甲醛、2,6-二羟基苯甲醛、3,4-二羟基苯甲醛、3,5-二羟基苯甲醛、2,3,4-三羟基苯甲醛、2,3,5-三羟基苯甲醛、2,3,6-三羟基苯甲醛、2,4,6-三羟基苯甲醛、2,4,5-三羟基苯甲醛、2,5,6-三羟基苯甲醛、4-羟基-2-甲氧基苯甲醛、4-二甲氨基苯甲醛、4-二乙基氨基苯甲醛、4-二甲基氨基-2-羟基苯甲醛、4-二乙基氨基-2-羟基苯甲醛、4-吡咯烷基苯甲醛、4-吗啉基苯甲醛、2-吗啉基苯甲醛、4-哌啶基苯甲醛、2-甲氧基-1-萘甲醛、4-甲氧基-1-萘甲醛、2-羟基-1-萘甲醛、2,4-二羟基-1-萘甲醛、4-羟基-3-甲氧基-1-萘甲醛、2-羟基-4-甲氧基-1-萘甲醛、3-羟基-4-甲氧基-1-萘甲醛、2,4-二甲氧基-1-萘甲醛、3,4-二甲氧基-1-萘甲醛、4-羟基-1-萘甲醛、4-二甲基氨基-1-萘甲醛、4-二甲基氨基亚肉桂醛、2-二甲氨基苯甲醛、2-氯代-4-二甲氨基苯甲醛、4-二甲基氨基-2-甲基苯甲醛、4-二乙基氨基亚肉桂醛、4-二丁基氨基苯甲醛、4-二苯基氨基-苯甲醛、4-二甲基氨基-2-甲氧基苯甲醛、4-(1-咪唑基)-苯甲醛、胡椒醛、2,3,6,7-四氢化-1H,5H-苯并[ij]喹嗪-9-甲醛、2,3,6,7-四氢化-8-羟基-1H,5H-苯并[ij]喹嗪-9-甲醛、N-乙基咔唑-3-醛、2-甲酰基亚甲基-1,3,3-三甲基二氢吲哚(Fischer醛或者tribasen醛)、2-吲哚醛、3-吲哚醛、1-甲基吲哚-3-醛、2-甲基吲哚-3-醛、1-乙酰基吲哚-3-醛、3-乙酰基吲哚、1-甲基-3-乙酰基吲哚、2-(1′,3′,3′-三甲基-2-二氢亚吲哚基)乙醛、1-甲基吡咯-2-醛、1-甲基-2-乙酰基吡咯、4-嘧啶醛、2-嘧啶醛、3-嘧啶醛、4-乙酰基吡啶、2-乙酰基吡啶、3-乙酰基吡啶、吡哆醛、喹啉-3-醛、喹啉-4-醛、安替比林-4-醛、糠醛、5-硝基糠醛、2-噻吩甲酰-三氟丙酮、色酮-3-醛、3-(5′-硝基-2′-呋喃基)-丙烯醛、3-(2′-呋喃基)-丙烯醛和咪唑-2-醛、1,3-二乙酰基苯、1,4-二乙酰基苯、1,3,5-三乙酰基苯、2-苯甲酰基-苯乙酮、2-(4′-甲氧苯甲酰)苯乙酮、2-(2′-糠酰)苯乙酮、2-(2′-吡啶酰基)苯乙酮和2-(3′-吡啶酰基)苯乙酮、亚苄基丙酮、4-羟基苯亚甲基丙酮、2-羟基苯亚甲基丙酮、4-甲氧亚苄基丙酮、4-羟基-3-甲氧亚苄基丙酮、4-二甲基氨基亚苄基丙酮、3,4-亚甲二氧基亚苄基丙酮、4-吡咯烷基亚苄基丙酮、4-哌啶基亚苄基丙酮、4-吗啉基苯亚甲基丙酮、4-二乙基氨基苯亚甲基丙酮、3-亚苄基-2,4-戊二酮、3-(4′-羟基苯亚甲基)-2,4-戊二酮、3-(4′-二甲基氨基亚苄基丙酮)-2,4-戊二酮、2-苯亚甲基环己酮、2-(4′-羟基苯亚甲基)环己酮、2-(4’-二甲基氨基亚苄基)环己酮、2-亚苄基-1,3-环己二酮、2-(4′-羟基苯亚甲基)-1,3-环己二酮、3-(4’-二甲基氨基亚苄基)-1,3-环己二酮、2-亚苄基-5,5-二甲基-1,3-环己二酮、2-(4′-羟基苯亚甲基)-5,5-二甲基-1,3-环己二酮、2-(4′-羟基-3-甲氧亚苄基)-5,5-二甲基-1,3-环己二酮、2-(4’-二甲基氨基亚苄基)-5,5-二甲基-1,3-环己二酮、2-苯亚甲基环戊酮、2′-(4-羟基苯亚甲基)-环戊酮、2-(4’-二甲基氨基亚苄基)环戊酮、5-(4-甲基氨基苯基)戊-2,4-二烯醛、5-(4-乙基氨基苯基)戊-2,4-二烯醛、5-(4-甲基苯基)戊-2,4-二烯醛、5-(3,4-二甲氧基苯基)戊-2,4-二烯醛、5-(2,4-二甲氧基苯基)戊-2,4-二烯醛、5-(4-哌啶基苯基)戊-2,4-二烯醛、5-(4-吗啉基苯基)戊-2,4-二烯醛、5-(4-吡咯烷基苯基)戊-2,4-二烯醛、6-(4-二甲基氨基苯基)六-3,5-二烯-2-酮、6-(4-二乙基氨基苯基)六-3,5-二烯-2-酮、6-(4-甲氧基苯基)六-3,5-二烯-2-酮、6-(3,4-二甲氧基苯基)六-3,5-二烯-2-酮、6-(2,4-二甲氧基苯基)六-3,5-二烯-2-酮、6-(4-哌啶基苯基)六-3,5-二烯-2-酮、6-(4-吗啉基苯基)六-3,5-二烯-2-酮、6-(4-吡咯烷基苯基)六-3,5-二烯-2-酮、5-(4-二甲基氨基-1-萘基)戊-3,5-二烯醛、2-硝基苯甲醛、3-硝基苯甲醛、4-硝基苯甲醛、4-甲基-3-硝基苯甲醛、3-羟基-4-硝基苯甲醛、4-羟基-3-硝基苯甲醛、5-羟基-2-硝基苯甲醛、2-羟基-5-硝基苯甲醛、2-羟基-3-硝基苯甲醛、2-氟代-3-硝基苯甲醛、3-甲氧基-2-硝基苯甲醛、4-氯代-3-硝基苯甲醛、2-氯代-6-硝基苯甲醛、5-氯代-2-硝基苯甲醛、4-氯代-2-硝基苯甲醛、2,4-二硝基苯甲醛、2,6-二硝基苯甲醛、2-羟基-3-甲氧基-5-硝基苯甲醛、4,5-二甲氧基-2-硝基苯甲醛、6-硝基胡椒醛、2-硝基胡椒醛、5-硝基香草醛、2,5-二硝基水杨醛、5-溴代-3-硝基水杨醛、3-硝基-4-甲酰基苯磺酸、4-硝基-1-萘甲醛、2-硝基肉桂醛、3-硝基肉桂醛、4-硝基肉桂醛、9-乙基-3-咔唑醛、3-乙酰基咔唑、3,6-二乙酰基-9-乙基咔唑、3-乙酰基-9-甲基咔唑、1,4-二甲基-3-咔唑醛、1,4,9-三甲基-3-咔唑醛、4-甲酰基-1-甲基吡啶鎓、2-甲酰基-1-甲基吡啶鎓-、4-甲酰基-1-乙基吡啶鎓-、2-甲酰基-1-乙基吡啶鎓-、4-甲酰基-1-苯基吡啶鎓-、2-甲酰基-1-苯基吡啶鎓-、4-甲酰基-1,2-二甲基吡啶鎓-、4-甲酰基-1,3-二甲基吡啶鎓-、4-甲酰基-1-甲基喹啉鎓-、2-甲酰基-1-甲基喹啉鎓-、4-乙酰基-1-甲基吡啶鎓-、2-乙酰基-1-甲基吡啶鎓-、4-乙酰基-1-甲基喹啉鎓-、5-甲酰基-1-甲基喹啉鎓-、6-甲酰基-1-甲基喹啉鎓-、7-甲酰基-1-甲基喹啉鎓-、8-甲酰基-1-甲基喹啉鎓-、5-甲酰基-1-乙基喹啉鎓-、6-甲酰基-1-乙基喹啉鎓-、7-甲酰基-1-乙基喹啉鎓-、8-甲酰基-1-乙基喹啉鎓-、5-甲酰基-1-苯基喹啉鎓-、6-甲酰基-1-苯基喹啉鎓-、7-甲酰基-1-苯基喹啉鎓-、8-甲酰基-1-苯基喹啉鎓、5-甲酰基-1-烯丙基喹啉鎓-、6-甲酰基-1-烯丙基喹啉鎓-、7-甲酰基-1-烯丙基喹啉鎓-和8-甲酰基-1-烯丙基喹啉鎓-、5-乙酰基-1-甲基喹啉鎓-、6-乙酰基-1-甲基喹啉鎓-、7-乙酰基-1-甲基喹啉鎓-、8-乙酰基-1-甲基喹啉鎓、5-乙酰基-1-乙基喹啉鎓-、6-乙酰基-1-乙基喹啉鎓-、7-乙酰基-1-乙基喹啉鎓-、8-乙酰基-1-乙基喹啉鎓、5-乙酰基-1-苯基喹啉鎓-、6-乙酰基-1-苯基喹啉鎓-、7-乙酰基-1-苯基喹啉鎓-8-乙酰基-1-苯基喹啉鎓-、5-乙酰基-1-烯丙基喹啉鎓-、6-乙酰基-1-烯丙基喹啉鎓-、7-乙酰基-1-烯丙基喹啉鎓-和8-乙酰基-1-烯丙基喹啉鎓-、9-甲酰基-10-甲基吖啶鎓-、4-(2′-甲酰基乙烯基)-1-甲基吡啶鎓-、1,3-二甲基-2-(4′-甲酰基苯基)苯并咪唑鎓-、1,3-二甲基-2-(4′-甲酰基苯基)咪唑鎓-、2-(4′-甲酰基苯基)-3-甲基苯并噻唑鎓-、2-(4′-乙酰基苯基)-3-甲基苯并噻唑鎓-、2-(4′-甲酰基苯基)-3-甲基苯并恶唑鎓-、2-(5′-甲酰基-2′-呋喃基)-3-甲基苯并噻唑鎓-、2-(5′-甲酰基-2′-呋喃基)-3-甲基苯并噻唑鎓-、2-(5′-甲酰基-2′-噻吩基)-3-甲基苯并噻唑鎓-、2-(3′-甲酰基苯基)-3-甲基苯并噻唑鎓-、2-(4′-甲酰基-1-萘基)-3-甲基苯并噻唑鎓-、5-氯代-2-(4′-甲酰基苯基)-3-甲基苯并噻唑鎓-、2-(4′-甲酰基苯基)-3,5-二甲基苯并噻唑鎓苯磺酸盐、-对-甲苯磺酸盐、-甲烷磺酸盐、-高氯酸盐、-硫酸盐、-氯化物、-溴化物、-碘化物、-四氯锌酸盐、-甲基磺酸盐、-三氟甲烷磺酸盐、-四氟硼酸盐、靛红、1-甲基-靛红、1-烯丙基-靛红、1-羟甲基-靛红、5-氯代-靛红、5-甲氧基-靛红、5-硝基靛红、6-硝基靛红、5-磺基靛红、5-羧基靛红、奎靛红、1-甲基奎靛红和上述化合物的任何混合物。
在特定的实施方式中,有利的是用这样的方式选择组分B以使通式II的基团Y不是羰基。在这种情况下,有利的是组分B选自:2-{[(2-羟乙基)亚氨基]甲基}酚、3-{[(2-羟乙基)亚氨基]甲基}酚、4-{[(2-羟乙基)亚氨基]甲基}酚、3-{[2-羟乙基)亚氨基]甲基}苯-1,2-二醇,4-{[(2-羟乙基)亚氨基]甲基}苯-1-1,3-二醇、2-{[(2-羟乙基)亚氨基]甲基}苯-1,4-二醇、2-{[(2-羟乙基)亚氨基]甲基}苯-1,3-二醇、4-{[(2-羟乙基)亚氨基]甲基}苯-1,2-二醇、5-{[(2-羟乙基)亚氨基]甲基}苯-1,3-二醇、4-{[2-羟乙基)亚氨基]甲基}苯-1,2,3-三醇、6-{[(2-羟乙基)亚氨基]甲基}苯-1,2,4-三醇、3-{[(2-羟乙基)亚氨基]甲基}苯-1,2,4-三醇、2-{[(2-羟乙基)亚氨基]甲基}苯-1,3,5-三醇、5-{[(2-羟乙基)亚氨基]甲基}苯-1,2,4-三醇、3-{[(2-羟乙基)亚氨基]甲基}苯-1,2,4-三醇、2-{[(2-甲基苯基)亚甲基]氨基}乙醇、2-{[(3-甲基苯基)亚甲基]氨基}乙醇、2-{[(4-甲基苯基)亚甲基]氨基}乙醇、2-{[(2-乙氧基苯基)亚甲基]氨基}乙醇、2-{[(3-乙氧基苯基)亚甲基]氨基}乙醇、2-{[(4-乙氧基苯基)-亚甲基]氨基}乙醇、2-{[(2,3-二甲氧基苯基)亚甲基]氨基}乙醇、2-{[(2,4-二甲氧基苯基)亚甲基]氨基}乙醇、2-[[(2,5-二甲氧基苯基)亚甲基]氨基}乙醇、2-{[(2,6-二甲氧基苯基)亚甲基]氨基}乙醇、2-{[(2,4-二甲氧基苯基)亚甲基]氨基}乙醇、2-{[(3,5-二甲氧基苯基)亚甲基]氨基}乙醇、2-{[(2,3,4-三甲氧基苯基)亚甲基]氨基}乙醇、2-{[(2,3,5-三甲氧基苯基)亚甲基]氨基}乙醇、2-{[(2,3,6-三甲氧基苯基)亚甲基]氨基}乙醇、2-{[(2,4,6-三甲氧基苯基)亚甲基]氨基}乙醇、2-{[(2,4,5-三甲氧基苯基)亚甲基]氨基}乙醇、2-{[(2,3,6-三甲氧基苯基)亚甲基]氨基}乙醇、4-{[(2-羟乙基)亚氨基]甲基}-3-甲氧基苯酚、4-{[(2-羟乙基)亚氨基]甲基}-2-甲氧基苯酚、5-{[(2-羟乙基)亚氨基]甲基}-2-甲氧基苯酚、2-{[(2-羟乙基)亚氨基]甲基}-5-甲氧基苯酚、3-乙氧基-4-{[(2-羟乙基)亚氨基]甲基}酚、2-乙氧基-4-{[(2-羟乙基)亚氨基]甲基}酚、5-乙氧基-2-{[(2-羟乙基)亚氨基]甲基}酚、2-乙氧基-5-{[(2-羟乙基)亚氨基]甲基}酚、4-{[(2-羟乙基)亚氨基]甲基}-2,3-二甲氧基酚、4-{[(2-羟乙基)亚氨基]甲基}-2,5-二甲氧基酚、4-{[(2-羟乙基)亚氨基]甲基}-3,5-二甲氧基酚、4-{[(2-羟乙基)亚氨基]甲基}-2,6-二甲氧基酚、2,6-二乙氧基-4-{[(2-羟乙基)亚氨基]甲基}酚、3,5-二乙氧基-4-{[(2-羟乙基)亚氨基]甲基}酚、4-{[(2-羟乙基)亚氨基]甲基}-3-甲基苯酚、4-{[(2-羟乙基)亚氨基]甲基}-2-甲基苯酚、4-{[(2-羟乙基)亚氨基]甲基}-2,3-二甲苯酚、二甲苯酚、4-{[(2-羟乙基)亚氨基]甲基}-2,5-二甲苯酚、4-{[(2-羟乙基)亚氨基]甲基}-3,5-二甲苯酚、4-{[(2-羟乙基)亚氨基]甲基}-2,6-二甲苯酚、2-({[4-(二丁基氨基)苯基]亚甲基}氨基)乙醇、2-({[2-氯代-4-(二甲基氨基)苯基]亚甲基}氨基)乙醇、2-({[4-(二甲基氨基)-2-甲基苯基]亚甲基}氨基)乙醇、2-({[4-(二甲基氨基)-2-甲基苯基]亚甲基}氨基)乙醇、2-({[2-(二甲基氨基)苯基]亚甲基}氨基)乙醇、2-({[4-(二甲基氨基)苯基]亚甲基}氨基)乙醇、2-({[4-(二乙基氨基)苯基]亚甲基}氨基)乙醇、5-(二甲基氨基)-2-{[(2-羟乙基)亚氨基]甲基}酚、5-(二乙基氨基)-2-{[(2-羟乙基)亚氨基]甲基}酚、2-{[(4-吡咯烷-1-基苯基)亚甲基]氨基}乙醇、2-{[(4-哌啶-1-基苯基)亚甲基]氨基}乙醇、2-{[(4-吗啉-4-基苯基)亚甲基]氨基}乙醇、2-{[(2-吗啉-4-基苯基)亚甲基]氨基}乙醇、2-{[(2-甲氧基-1-萘基)亚甲基]氨基}乙醇、2-{[(4-甲氧基-1-萘基)亚甲基]氨基}乙醇、1-{[(2-羟乙基)亚氨基]甲基}-2-萘酚、4-{[(2-羟乙基)亚氨基]甲基}-1-萘酚、4-{[(2-羟乙基)亚氨基]甲基}萘-1,3-二醇、4-{[(2-羟乙基)亚氨基]甲基}-2-甲氧基-1-萘酚、1-{[(2-羟乙基)亚氨基]甲基}-4-甲氧基-2-萘酚、4-{[(2-羟乙基)亚氨基]甲基}-1-甲氧基-2-萘酚、2-{[(2,4-二甲氧基-1-萘基)亚甲基]氨基}乙醇、2-{[(3,4-二甲氧基-1-萘基)亚甲基]氨基}乙醇、2-({[4-(二甲基氨基)-1-萘基]亚甲基}氨基)乙醇、2-({3-[4-(二甲基氨基)苯基]-2-亚丙烯基}氨基)乙醇、2-({3-[4-(二乙基氨基)苯基)-2-亚丙烯基)氨基)乙醇、4-{3-[(2-羟乙基)-亚氨基]-1-丙烯基}-2-甲氧基苯酚、2-(二乙氧基甲基)酚、3-(二乙氧基甲基)酚、4-(二乙氧基甲基)酚、3-(二乙氧基甲基)苯-1,2-二醇、4-(二乙氧基甲基)苯-1,3-二醇、2-(二乙氧基甲基)苯-1,4-二醇、2-(二乙氧基甲基)-苯-1,3-二醇、4-(二乙氧基甲基)苯-1,2-二醇、5-(二乙氧基甲基)苯-1,3-二醇、4-(二乙氧基甲基)苯-1,2,3-三醇、6-(二乙氧基甲基苯-1,2,4-三醇、3-(二乙氧基甲基)苯-1,2,4-三醇、2-(二乙氧基甲基)苯-1,3,5-三醇、5-(二乙氧基甲基)苯-1,2,4-三醇、3-(二乙氧基甲基)苯-1,2,4-三醇、1-(二乙氧基甲基)-2-甲氧基苯、1-(二乙氧基甲基)-3-甲氧基苯、1-(二乙氧基甲基)-4-甲氧基苯、1-(二乙氧基甲基)-2-乙氧基苯、1-(二乙氧基甲基)-3-乙氧基苯、1-(二乙氧基甲基)-4-乙氧基苯、1-(二乙氧基甲基)-2,3-二甲氧基苯、1-(二乙氧基甲基)-2,4-二甲氧基苯、2-(二乙氧基甲基)-1,4-二甲氧基苯、2-(二乙氧基甲基)-1,3-二甲氧基苯、4-(二乙氧基甲基)-1,2-二甲氧基苯、1-(二乙氧基甲基)-3,5-二甲氧基苯、1-(二乙氧基甲基)-2,3,4-三甲氧基苯、1-(二乙氧基甲基)-2,3,5-三甲氧基苯、2-(二乙氧基甲基)-1,3,4-三甲氧基苯、2-(二乙氧基甲基)-1,3,5-三甲氧基苯、1-(二乙氧基甲基)-2,4,5-三甲氧基苯、2-(二乙氧基甲基)-1,3,4-三甲氧基苯、4-(二乙氧基甲基)-3-甲氧基苯酚、4-(二乙氧基甲基)-2-甲氧基苯酚、5-(二乙氧基甲基)-2-甲氧基苯酚、2-(二乙氧基甲基)-5-甲氧基苯酚、4-(二乙氧基甲基)-3-乙氧基酚、4-(二乙氧基甲基)-2-乙氧基酚、2-(二乙氧基甲基)-5-乙氧基酚、5-(二乙氧基甲基)-2-乙氧基酚、4-(二乙氧基甲基)-2,3-二甲氧基酚、4-(二乙氧基甲基)-2,5-二甲氧基酚、4-(二乙氧基甲基)-3,5-二甲氧基酚、4-(二乙氧基甲基)-2,6-二甲氧基酚、4-(二乙氧基甲基)-2,6-二乙氧基酚、4-(二乙氧基甲基)-3,5-二乙氧基酚、4-(二乙氧基甲基)-3-甲基苯酚、4-(二乙氧基甲基)-2-甲基苯酚、4-(二乙氧基甲基)-2,3-二甲苯酚、4-(二乙氧基甲基)-2,5-二甲苯酚、4-(二乙氧基甲基)-3,5-二甲苯酚、4-(二乙氧基甲基)-2,6-二甲苯酚、N-[4-(二乙氧基甲基)苯基]-N,N-二丁胺、N-[3-氯代-4-(二乙氧基甲基)苯基]-N,N-二甲胺、N-[4-(二乙氧基甲基)-3-甲基苯基]-N,N-二甲胺、N-[4-(二乙氧基甲基)-3-甲基苯基]-N,N-二甲胺、N-[2-(二乙氧基甲基)苯基]-N,N-二甲胺、N-[4-(二乙氧基甲基)苯基]-N,N-二甲胺、N-[4-(二乙氧基甲基)苯基]-N,N-二乙胺、2-(二乙氧基甲基)-5-(二甲基氨基)酚、2-(二乙氧基甲基)-5-(二乙基氨基)酚、1-[4-(二乙氧基甲基)苯基]吡咯烷、1-[4-(二乙氧基甲基)苯基]哌啶、4-[4-(二乙氧基甲基)苯基]吗啉、4-[2-(二乙氧基甲基)苯基]吗啉、1-(二乙氧基甲基)-2-甲氧基萘、1-(二乙氧基甲基)-4-甲氧基萘、1-(二乙氧基甲基)-2-萘酚、4-(二乙氧基甲基)-1-萘酚、4-(二乙氧基甲基)-萘-1,3-二醇、4-(二乙氧基甲基)-2-甲氧基-1-萘酚、1-(二乙氧基甲基)-4-甲氧基-2-萘酚、4-(二乙氧基甲基)-1-甲氧基-2-萘酚、1-(二乙氧基甲基)-2,4-二甲氧基萘、4-(二乙氧基甲基)-1,2-二甲氧基萘、N-[4-(二乙氧基甲基)-1-萘基]-N,N-二甲胺、N-{4-[3,3-二乙氧基丙-1-烯基]苯基}-N,N-二甲胺、N-{4-[3,3-二乙氧基丙-1-烯基]苯基}-N,N-二乙胺和4-(3,3-二乙氧基丙-1-烯基)-2-甲氧基苯酚。
苯甲醛、肉桂醛和萘甲醛及它们的衍生物,特别是具有一个或多个羟基、烷氧基和氨基取代基的是相当特别优选的用作组分B。本发明中根据通式V的化合物是优选的,
■其中R13、R14和R15独立地彼此代表氢原子、卤素原子、C1-C6烷基、羟基、C1-C6烷氧基、氨基C1-C6烷基氨基、二(C2-C6羟烷基)氨基、二(C1-C6烷氧基-C1-C6烷基)氨基、C1-C6羟基烷氧基、磺酰基团、羧基、磺酸基、磺酰胺基团、磺酰胺基团、氨甲酰基团、C2-C6酰基团、乙酰基或者硝基,
■Z’代表直接键合或者亚乙烯基团,
■R13a和R14a代表氢,与该分子的残基一起可以形成5-或者6-元芳烃或者脂肪族的环。
相当特别优选的化合物组分B选自:香草醛、松柏醛、2-甲氧基苯甲醛、3-甲氧基苯甲醛、4-甲氧基苯甲醛、2-乙氧基苯甲醛、3-乙氧基苯甲醛、4-乙氧基苯甲醛、4-羟基-2,3-二甲氧基-苯甲醛、4-羟基-2,5-二甲氧基苯甲醛、4-羟基-2,6-二甲氧基苯甲醛、4-羟基-2-甲基苯甲醛、4-羟基-3-甲基苯甲醛、4-羟基-2,3-二甲基苯甲醛、4-羟基-2,5-二甲基苯甲醛、4-羟基-2,6-二甲基苯甲醛、4-羟基-3,5-二甲氧基苯甲醛、4-羟基-3,5-二甲基苯甲醛、3,5-二乙氧基-4-羟基苯甲醛、2,6-二乙氧基-4-羟基苯甲醛、3-羟基-4-甲氧基苯甲醛、2-羟基-2-甲氧基苯甲醛、2-乙氧基-4-羟基苯甲醛、3-乙氧基-4-羟基苯甲醛、4-乙氧基-2-羟基-苯甲醛、4-乙氧基-3-羟基苯甲醛、2,3-二甲氧基苯甲醛、2,4-二甲氧基苯甲醛、2,5-二甲氧基苯甲醛、2,6-二甲氧基苯甲醛、3,4-二甲氧基苯甲醛、3,5-二甲氧基苯甲醛、2,3,4-三甲氧基苯甲醛、2,3,5-三甲氧基苯甲醛、2,3,6-三甲氧基苯甲醛、2,4,6-三甲氧基苯甲醛、2,4,5-三甲氧基苯甲醛、2,5,6-三甲氧基苯甲醛、2-羟基苯甲醛、3-羟基苯甲醛、4-羟基苯甲醛、2,3-二羟基苯甲醛、2,4-二羟基苯甲醛、2,5-二羟基苯甲醛、2,6-二羟基苯甲醛、3,4-二羟基苯甲醛、3,5-二羟基苯甲醛、2,3,4-三羟基苯甲醛、2,3,5-三羟基苯甲醛、2,3,6-三羟基苯甲醛、2,4,6-三羟基苯甲醛、2,4,5-三羟基苯甲醛、2,5,6-三羟基苯甲醛、4-羟基-2-甲氧基苯甲醛、4-二甲氨基苯甲醛、4-二乙基氨基苯甲醛、4-二甲基氨基-2-羟基苯甲醛、4-二乙基氨基-2-羟基苯甲醛、4-吡咯烷基苯甲醛、4-吗啉基苯甲醛、2-吗啉基苯甲醛、4-哌啶基苯甲醛、2-甲氧基-1-萘甲醛、4-甲氧基-1-萘甲醛、2-羟基-1-萘甲醛、2,4-二羟基-1-萘甲醛、4-羟基-3-甲氧基-1-萘甲醛、2-羟基-4-甲氧基-1-萘甲醛、3-羟基-4-甲氧基-1-萘甲醛、2,4-二甲氧基-1-萘甲醛、3,4-二甲氧基-1-萘甲醛、4-羟基-1-萘甲醛、4-二甲基氨基-1-萘甲醛、4-二甲基氨基亚肉桂醛、2-二甲氨基苯甲醛、2-氯代-4-二甲氨基苯甲醛、4-二甲基氨基-2-甲基苯甲醛、4-二乙基氨基亚肉桂醛、4-二丁基氨基苯甲醛、4-二苯基氨基苯甲醛、4-二甲基氨基-2-甲氧基苯甲醛、4-(1-咪唑基)-苯甲醛和胡椒醛。
在第二实施方式中,有利的是通过在本发明试剂中除了加入至少一种通式I的化合物和至少一种反应性羰基化合物(组分B)及至少另外的化合物用作组份C,可拓宽色谱并改善坚牢度性质,所述的组分C选自(a)CH-酸化合物和(b)含有一级或者二级氨基或者羟基的化合物,其选自芳烃羟基化合物、一级的或者二级芳香胺和含氮杂环化合物。
组份C的CH-酸化合物选自1,2,3,3-四甲基-3H-碘化吲哚、1,2,3,3-四甲基-3H-对甲苯磺酸吲哚、1,2,3,3-四甲基-3H-甲烷磺酸吲哚、1,3,3-三甲基-2-亚甲基二氢吲哚(Fischer碱)、2,3-二甲基-苯并噻唑鎓碘化物、2,3-二甲基苯并噻唑鎓吲哚对甲苯磺酸盐、2,3-二甲基-萘并[1,2-d]噻唑鎓对甲苯磺酸盐、3-乙基-2-甲基-萘并[1,2-d]对甲苯磺酸噻唑鎓盐、绕丹宁、绕丹宁-3-乙酸、1,4-碘化二甲基喹啉鎓物、1,2-碘化二甲基喹啉鎓物、巴比土酸、硫代巴比土酸、1,3-二甲基硫代巴比土酸、1,3-二乙基硫代巴比土酸、1,3-二乙基巴比妥酸、2-羟基吲哚、3-乙酸吲羟酯、2-香豆冉酮、5-羟基-2-香豆冉酮、6-羟基-2-香豆冉酮、3-甲基-1-苯基-吡唑啉-5-酮、二氢化茚-1,2-二酮、二氢化茚-1,3-二酮、茚满-1-酮、苯甲酰乙腈、3-二氰亚甲基茚满-1-酮、2-氨基-4-亚氨基-1,3-盐酸噻唑啉化物、5,5-二甲基环己烷-1,3-二酮、2H-1,4-苯并恶嗪-4H-3-酮、3-乙基-2-甲基-苯并恶唑鎓碘化物、3-乙基-2-甲基苯并噻唑鎓碘化物、1-乙基-4-甲基喹啉鎓碘化物、1-乙基-2-甲基喹啉鎓碘化物、1,2,3-三甲基喹啉鎓碘化物、3-乙基-2-苯并恶唑鎓对甲苯磺酸盐、3-乙基-2-甲基-苯并噻唑鎓对甲苯磺酸盐、1-乙基-4-甲基-喹啉鎓对甲苯磺酸盐、1-乙基-2-甲基喹啉鎓对甲苯磺酸盐和1,2,3-三甲基喹喔啉鎓对甲苯磺酸盐。
组份C的一级和二级芳香胺优选选自:N,N-二甲基-对苯二胺、N,N-二乙基-对苯二胺、N-(2-羟乙基)-N-乙基-对苯二胺、N,N-二(2-羟乙基)-对苯二胺、N-(2-甲氧基乙基)-对苯二胺、2,3-二氯-对苯二胺、2,4-二氯-对苯二胺、2,5-二氯-对苯二胺、2-氯代-对苯二胺、2,5-二羟基-4-吗啉基苯胺、2-氨基苯酚、3-氨基苯酚、4-氨基苯酚、2-氨甲基-4-氨基苯酚、2-羟甲基-4-氨基苯酚、邻苯二胺、间苯二胺、对苯二胺、2,5-二氨基甲苯、2,5-二氨基苯酚、2,5-二氨基茴香醚、2,5-二氨基苯乙醇、4-氨基-3-甲基苯酚、2-(2,5-二氨基苯基)乙醇、2,4-二氨基苯氧基乙醇、2-(2,5-二氨基苯氧基)乙醇、3-氨基-4-(2-羟乙氧基)酚、3,4-亚甲二氧基苯酚、3,4-亚甲二氧基苯胺、3-氨基-2,4-二氯苯酚、4-甲基氨基酚、2-甲基-5-氨基苯酚、3-甲基-4-氨基苯酚、2-甲基-5-(2-羟乙基氨基)酚、3-氨基-2-氯代-6-甲基苯酚、2-甲基-5-氨基-4-氯酚、5-(2-羟乙基氨基)-4-甲氧基-2-甲基苯酚、4-氨基-2-羟基甲基酚、2-(二乙基氨甲基)-4-氨基苯酚、4-氨基-1-羟基-2-(2-羟基乙基氨基甲基)苯、1-羟基-2-氨基-5-甲基-苯、1-羟基-2-氨基-6-甲基-苯、2-氨基-5-乙酰胺基苯酚、1,3-二甲基-2,5-苯二胺、5-(3-羟基丙基氨基)-2-甲基苯酚、5-氨基-4-甲氧基-2-甲基苯酚、N,N-二甲基-3-氨基苯酚、N-环戊基-3-氨基苯酚、5-氨基-4-氟代-2-甲基苯酚、2,4-二氨基-5-氟代甲苯、2,4-二氨基-5-(2-羟基乙氧基)-甲苯、2,4-二氨基-5-甲基苯乙醚、3,5-二氨基-2-甲氧基-1-甲苯、2-氨基-4-(2-羟乙基氨基)茴香醚、2,6-二(2-羟乙基氨基)-1-甲苯、1,3-二氨基-2,4-二甲氧基苯、3,5-二氨基-2-甲氧基-甲苯、2-氨基苯甲酸、3-氨基苯甲酸、4-氨基苯甲酸、2-氨基苯乙酸、3-氨基苯乙酸、4-氨基苯乙酸、2,3-二氨基苯甲酸、2,4-二氨基苯甲酸、2,5-二氨基苯甲酸、3,4-二氨基苯甲酸、3,5-二氨基苯甲酸、4-氨基水杨酸、5-氨基水杨酸、3-氨基-4-羟基苯甲酸、4-氨基-3-羟基苯甲酸、2-氨基苯磺酸、3-氨基苯磺酸、4-氨基苯磺酸、3-氨基-4-羟基苯磺酸、4-氨基-3-羟基萘-1-磺酸、6-氨基-7-羟基萘-2-磺酸、7-氨基-4-羟基萘-2-磺酸、4-氨基-5-羟基萘-2,7-二磺酸、3-氨基-2-萘甲酸、3-氨基酞酸、5-氨基间苯二甲酸、1,3,5-三氨基苯、1,2,4-三氨基苯、1,2,4,5-四氨基苯、2,4,5-三氨基酚、五氨基苯、六氨基苯、2,4,6-三氨基间苯二酚、4,5-二氨基邻苯二酚、4,6-二氨基连苯三酚、1-(2-羟基-5-氨基苯甲基)-2-咪唑啉酮、4-氨基-2((4-[(5-氨基-2-羟苯基)甲基]-哌嗪基)甲基)酚、3,5-二氨基-4-羟基邻苯二酚、1,4-二(4-氨基苯基)-1,4-二氮环庚烷、芳腈比如2-氨基-4-羟基苯腈、4-氨基-2-羟基苯腈、4-氨基苯基腈、2,4-二氨基苯基腈、含有硝基的氨基化合物比如3-氨基-6-甲基氨基-2-硝基吡啶、苦氨酸、[8-[(4-氨基-2-硝基苯基)-偶氮基]-7-羟基-萘--2-基]三甲基氯化铵、[8-[(4-氨基-3-硝基苯基)-偶氮基)-7-羟基-萘-2-基]]三甲基氯化铵(碱性棕17)、1-羟基-2-氨基-4,6-二硝基苯、1-氨基-2-硝基-4-[二(2-羟乙基)氨基]苯、1-氨基-2-[(2-羟乙基)氨基]-5-硝基苯(HCYellow Nr.5)、1-氨基-2-硝基-4-[(2-羟乙基)氨基]苯(HC Red Nr.7)、2-氯代-5-硝基-N-2-羟乙基-1,4-苯二胺、1-[(2-羟乙基)氨基]-2-硝基-4-氨基苯(HC Red Nr.3)、4-氨基-3-硝基苯酚、4-氨基-2-硝基苯酚、6-硝基-邻甲苯胺、1-氨基-3-甲基-4-[(2-羟乙基)氨基]-6-硝基苯(HC VioletNr.1)、1-氨基-2-硝基-4-[(2,3-二羟基丙基)氨基]-5-氯苯(HC RedNr.10)、2-(4-氨基-2-硝基苯胺基)苯甲酸、6-硝基-2,5-二氨基吡啶、2-氨基-6-氯代-4-硝基苯酚、1-氨基-2-(3-硝基苯基偶氮)-7-苯基偶氮-8-萘酚-3,6-二磺酸的二钠盐(acid blue Nr.29)、1-氨基-2-(2-羟基-4-硝基苯基偶氮)-8-萘酚-3,6-二磺酸的二钠盐(Palatinchrome green)、1-氨基-2-(3-氯代-2-羟基-5-硝基苯基偶氮)-8-萘酚-3,6-二磺酸的二钠盐(Gallion)、4-氨基-4′-硝基芪-2,2′-二磺酸的二钠盐、2,4-二氨基-3’,5’-二硝基-2’-羟基-5-甲基偶氮苯(Mordant brown 4)、4′-氨基-4-硝基二苯胺-2-磺酸、4′-氨基-3′-硝基苯基-2-羧酸、1-氨基-4-硝基-2-(2-硝基苯亚甲基氨基)苯、2-[2-(二乙基氨基)乙基氨基]-5-硝基苯胺、3-氨基-4-羟基-5-硝基苯磺酸、3-氨基-3′-硝基联苯基-1,3-氨基-4-硝基苊、2-氨基-1-硝基萘、5-氨基-6-硝基苯并-1,3-二羰基合成醇、苯胺、特别是含硝基的苯胺比如4-硝基苯胺、2-硝基苯胺、1,4-二氨基-2-硝基苯、1,2-二氨基-4-硝基苯、1-氨基-2-甲基-6-硝基苯、4-硝基-1,3-苯二胺、2-硝基-4-氨基-1-(2-羟乙基氨基)苯、2-硝基-1-氨基-4-[二(2-羟乙基)氨基]苯、4-氨基-2-硝基二苯胺-2′-羧酸、1-氨基-5-氯代-4-(2-羟乙基氨基)-2-硝基苯、含有另外的芳基的芳香苯胺或者酚,如在通式VI中举例说明,
■其中R16代表羟基或者氨基,可以用C1-C6烷基-、C1-C6羟烷基-、C1-C6烷氧基-或C1-C6烷氧基-C1-C6烷基取代,
■R17、R18、R19、R20和R21彼此独立地代表氢原子、羟基或者氨基,可以由C1-C6烷基-、C1~C6羟烷基、C1-C6烷氧基-、C1-C6氨基烷基或C1-C6烷氧基-C1-C6烷基取代,和
■Z”是直接键合、1~4个碳原子的饱和的或者不饱和碳链,任选用羟基、羰基-、磺酰或亚氨基、氧或硫原子或者通式VII的基团取代,
-Q’-(CH2-Q-CH2-Q”)o- (VII)
■其中Q是指直接键合、CH2-或者CHOH基团,
■Q’和Q”彼此独立地代表氧原子、NR22基团,其中R22是指氢原子、C1-C6烷基或者C1-C6羟烷基,其中两个基团也可与分子的残基一起形成5-、6-或者7-元环,及基团O--(CH2)p-NH或者NH--(CH2)p’-O,其中p和p’是2或者3,
■O是指1~4的数字,
比如4,4′-二氨基芪和它的盐酸盐、4,4′-二胺基芪-2,2′-二磺酸的单或二钠盐、4-氨基-4′-二甲基氨基芪和它的盐酸盐、4,4’-二氨基二苯基甲烷,4,4’-二氨基二苯基硫化物、4,4′二氨基二苯基亚砜、4,4′-二氨基二苯基胺、4,4′-二氨基二苯基胺-2-磺酸、4,4′-二氨基二苯甲酮、4,4′-二氨基二苯基醚、3,3’,4,4’-四氨基二苯基、3,3′,4,4′-四氨基-二苯甲酮、1,3-二(2,4-二氨基苯氧基)丙烷、1,8-二(2,5-二氨基苯氧基)-3,6-二氧杂环辛烷、1,3-二(4-氨基苯基氨基)丙烷、1,3-二(4-氨基苯基氨基)-2-丙醇、1,3-二-[N-(4-氨基苯基)-2-羟乙基氨基]-2-丙醇、N,N-二[2-(4-氨基苯氧基)乙基]甲胺、N-苯基-1,4-苯二胺和二(5-氨基-2-羟苯基)甲烷。
该组份C的含氮杂环化合物优选选自2-氨基吡啶、3-氨基吡啶、4-氨基吡啶、2-氨基-3-羟基吡啶、2,6-二氨基吡啶、2,5-二氨基吡啶、2-(氨基乙基氨基)-5-氨基吡啶、2,3-二氨基吡啶、2-二甲基氨基-5-氨基吡啶、2-甲基氨基-3-氨基-6-甲氧基吡啶、2,3-二氨基-6-甲氧基吡、2,6-二甲氧基-3,5-二氨基吡啶、2,4,5-三氨基吡啶、2,6-二羟基-3,4-二甲基吡啶、N-[2-(2,4-二氨基苯基)氨乙基]-N-(5-氨基-2-吡啶基)胺、N-[2-(4-氨基苯基)氨乙基]-N-(5-氨基-2-吡啶基)胺、2,4-二羟基-5,6-二氨基嘧啶、4,5,6-三氨基嘧啶、4-羟基-2,5,6-三氨基嘧啶、2-羟基-4,5,6-三氨基嘧啶、2,4,5,6-四氨基嘧啶、2-甲基氨基-4,5,6-三氨基嘧啶、2,4-二氨基嘧啶、4,5-二氨基嘧啶、2-氨基-4-甲氧基-6-甲基-嘧啶、3,5-二甲基吡唑、3,5-二氨基-1,2,4-三唑、3-氨基吡唑、3-氨基-5-羟基吡唑、1-苯基-4,5-二甲基吡唑、1-(2-羟乙基)-4,5-二甲基吡唑、1-苯基-3-甲基-4,5-二氨基吡唑、4-氨基-2,3-二甲基-1-苯基-3-吡唑啉-5-酮(4-匹拉米洞)、1-苯基-3-甲基吡唑啉-5-酮、2-氨基喹啉、3-氨基喹啉、8-氨基喹啉、4-氨基喹哪啶、2-氨基烟酸、6-氨基烟酸、5-氨基异喹啉、5-氨基吲唑、6-氨基吲唑、5-氨基苯并咪唑、7-氨基苯并咪唑、5-氨基苯并噻唑、7-氨基苯并噻唑、2,5-二羟基-4-吗啉代-苯胺以及吲哚和二氢吲哚衍生物比如4-氨基吲哚、5-氨基吲哚、6-氨基吲哚、7-氨基吲哚、5,6-二羟吲哚、5,6-二羟二氢吲哚、4-羟基二氢吲哚。根据本发明能被使用的另外的杂环化合物是公开在DE-U1-29908573中的羟基嘧啶。上述的化合物可以它们游离的形式和它们生理学相容的盐的形式使用,例如无机酸比如盐酸或者硫酸的盐。
组份C的芳烃羟基化合物优选选自2-,4-,5-甲基间苯二酚、2,5-二甲基间苯二酚、间苯二酚、3-甲氧基苯酚、邻苯二酚、对苯二酚、焦性没食子酸、皮酚、苯三酚、2-,3-,4-甲氧基-、3-二甲基氨基-、2-(2-羟乙基)-、3,4-亚甲二氧基苯酚、2,4-,3,4-二羟基苯甲酸、-苯乙酸、五倍子酸、2,4,6-三羟基苯甲酸、-苯乙酮、2-,4-氯代间苯二酚、1-萘酚、1,5-,2,3-,2,7-二羟基萘、6-二甲基氨基-4-羟基-2-萘磺酸和3,6-二羟基-2,7-萘磺酸。
尤其包含至少一种含有1,2-二氢嘧啶鎓基团的化合物作为实质染料的染发剂对于所属技术领域的专业人员是熟知的,公开于印刷出版物EP-A2-998908和JP-A2-2002047153。在第三实施方式中,该染料包括至少一种由通式I得到的1,2-二氢嘧啶鎓和组分B的化合物,特别是根据通式II化合物的反应产物,用作直接染料。这样的反应产物RP可以通过例如在含水的、中性的到弱碱性的介质中加热两个反应对而得到,由此反应产物RP或作为固体从溶液中沉淀析出或者通过蒸发溶液从中分离出来。还有一种根据文献H.Baumann et al.J.LiebigsAnn.Chem.,1968,717,124-136或者DE-A1-2165913合成反应产物的可能性。
因此,本发明的试剂可以包含根据通式VIII的反应产物RP,
其中
■R1、R2、R5、Y和X-的定义如权利要求1,
■R23和R24彼此独立地代表氢原子、C1-C6烷基、通式IX的基团,
其中
●R6、R7、R8、R9、AR和Z如通式II所定义,
●R25代表氢原子或者C1-C5烷基,
附带条件是基团R23和R24的至少一种代表通式IX的基团。
组分B与根据通式I化合物的摩尔比对于反应产物RP的合成,方便地为约1∶1~约2∶1。对于根据通式I的1,2-二氢嘧啶鎓衍生物,当仅一种取代基R23或者R24不同于氢时,然后约1摩尔相当的量的组分B与1摩尔相当的量的1,2-二氢嘧啶鎓衍生物起反应。在这种情况下,通式VIII中R23或者R24的任何一个代表氢原子,另一个基团代表根据通式IX的基团。如果通式I中的两个取代基R3和R4都不同于氢原子,然后这些1,2-二氢嘧啶鎓衍生物可以与约1和约2摩尔相当的量的组分B起反应。在前一种情况下,在得到的反应产物RP中的两个基团R23和R24都代表根据通式IX的基团。
特别优选的是如果本发明的试剂包含这样的根据通式VIII的反应产物RP,其中AR,根据通式IX代表苯或者萘。
另外的特别优选的是如果本发明的试剂包括这样的根据通式VIII的反应产物RP,其中Z根据通式IX代表直接键合或者亚乙烯基。
另外的特别优选的是如果本发明的试剂包括这样的根据通式VIII的反应产物RP,其中R25根据通式IX代表氢原子。
另外的特别优选的是如果本发明的试剂包括这样的根据通式VIII的反应产物RP,其中R6根据通式IX代表氢原子。
另外的特别优选的是如果本发明的试剂包括这样的根据通式VIII的反应产物RP,其中R7、R8和R9根据通式IX彼此独立地代表氢原子。卤素原子、C1-C6烷基、羟基、C1-C6羟烷基、氨基、C1-C6烷基氨基、二(C2-C6羟烷基)氨基、二(C1-C6烷氧基C1-C6-烷基)氨基、C1-C6羟基烷氧基、磺酰基团、羧基、磺酰胺基团、氨甲酰基、C2-C6酰基、乙酰基、磺酸基、磺酰胺基团或者硝基。
另外的特别优选的是如果本发明的试剂包括这样的根据通式VIII的反应产物RP,其中R7、R8和R9根据通式IX彼此独立地代表氢原子、卤素原子、C1-C6烷基、羟基、C1-C6烷氧基、氨基、烷基氨基、二(C2-C6羟烷基)氨基、二(C1-C6烷基)氨基、C1-C6羟基烷氧基、磺酰基团、羧基、磺酰胺基团、氨甲酰基、C2-C6酰基、乙酰基、磺酸基、磺酰胺基团或者硝基,附带条件是如果AR代表苯,则基团R7、R8或者R9、Z之一代表氢原子、卤素原子、C1-C6烷氧基或者氨基,然后其他两个基团彼此独立地既不是氢原子也不是卤素原子。
另外的特别优选的是如果本发明的试剂包括这样的根据通式VIII的反应产物RP,其中R7、R8和R9根据通式IX彼此独立地代表氢原子、卤素原子、C1-C6烷基、羟基、C1-C6烷氧基、氨基、C1-C6烷基氨基、二(C2-C6羟烷基)氨基、二(C1-C6烷氧基C1~C6烷基)氨基、C1-C6羟基烷氧基、磺酰基团、羧基、磺酰胺基团、氨甲酰基团、C2-C6酰基、乙酰基、磺酸基、磺酰胺基团或者硝基,附带条件是如果AR代表苯,则基团R7、R8或者R9之一代表选自羟基、C1-C6烷基氨基、二(C2-C6羟烷基)氨基、二(C1-C6烷基)氨基和C1-C6羟基烷氧基的基团。
依据该实施方式,本发明试剂包括的根据通式VIII的相当特别优选的反应产物是选自如下至少之一的化合物:4-[2-[2-羟苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3-羟苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-硫酸氢嘧啶、4-[2-[4-羟苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,3-二羟苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,4-二羟苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,5-二羟苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-硫酸氢嘧啶、4-[2-[2,6-二羟苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3,4-二羟基苯基乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3,5-二羟苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3,6-二羟苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-2-[2,3,4-三羟基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-2-[2,3,5-三羟基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-硫酸氢嘧啶、4-[2-[2,3,6-三羟基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3,4,5-三羟基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-硫酸氢嘧啶、4-[2-[3,4,6-三羟基苯基]-乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-(2-[2,4,5-三羟基-苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,4,6-三羟基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-硫酸氢嘧啶、4-[2-[2,3-二甲氧基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,4-二甲氧基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,5-二甲氧基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,6-二甲氧基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3,4-二甲氧基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3,5-二甲氧基苯基)乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3,6-二甲氧基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,3,4-三甲氧基苯基]乙烯基)-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,3,5-三甲氧基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,3,6-三甲氧基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3,4,5-三甲氧基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3,4,6-三甲氧基苯基乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-硫酸氢嘧啶、4-[2-[2,4,6-三甲氧基苯基)乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2-羟基-3-甲基苯基]-乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2-羟基-4-甲基苯基)乙烯基)-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2-羟基-5-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2-羟基-6-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-硫酸氢嘧啶、4-[2-[3-羟基-2-甲氧基苯基乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3-羟基-4-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-硫酸氢嘧啶、4-[2-[3-羟基-5-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3-羟基-6-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-硫酸氢嘧啶、4-[2-[4-羟基-2-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[4-羟基-3-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,3-二羟基-4-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,3-二羟基-5-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,3-二羟基-6-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,4-二羟基-3-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,4-二羟基-5-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,4-二羟基-6-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-硫酸氢嘧啶、4-[2-[2,5-二羟基-3-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-硫酸氢嘧啶、4-[2-[2,5-二羟基-4-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,5-二羟基-6-甲基苯基]乙烯基)-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,6-二羟基-3-甲氧基苯基乙烯基)-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,6-二羟基-4-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,6-二羟基-5-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,3-二甲氧基-4-羟基-苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,3-二甲氧基-5-羟苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,3-二甲氧基-6-羟基-苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,4-二甲氧基-3-羟基-苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,4-二甲氧基-5-羟基-苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,4-二甲氧基-6-羟基-苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,5-二甲氧基-3-羟苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,5-二甲氧基-4-羟基-苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-硫酸氢嘧啶、4-[2-[2,5-二甲氧基-6-羟基-苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,6-二甲氧基-3-羟基-苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-硫酸氢嘧啶、4-[2-[2,6-二甲氧基-4-羟基-苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2,6-二甲氧基-5-羟基-苯基]乙烯基-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3,4-二甲氧基-3-羟基-苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-硫酸氢嘧啶、4-[2-[3,4-二甲氧基-5-羟基-苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3,4-二甲氧基-6-羟基-苯基]-乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-硫酸氢嘧啶、4-[2-[3,5-二甲氧基-2-羟基-苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3,5-二甲氧基-4-羟基-苯基乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3,5-二甲氧基-6-羟基-苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3,5-二甲基-4-羟基-苯基乙烯基)-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3,5-二甲基-2-羟基-苯基]-乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[4-(二甲基氨基)-2-羟苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[4-(二甲基氨基)-3-羟苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[4-(二乙基氨基)-2-羟苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[4-(二乙基氨基)-3-羟苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[4-(二乙基氨基)-2-甲基苯基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[4-(二乙基氨基)-3-甲基苯基]-乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2-羟基-萘-1-基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[3-羟基-萘-1-基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[4-羟基萘-1-基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-氯化嘧啶、4-[2-[2-甲氧基]-2,3-二氢-1,3,6-三甲基-2-氯化氧嘧啶、4-[2-[3-甲氧基萘-1-基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氯化氧嘧啶、4-[2-[4-甲氧基萘-1-基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氯化氧嘧啶、4-[2-[4-(二甲基氨基)萘-1-基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代-硫酸氢嘧啶、4-[2-[4-(二乙基氨基)-萘-1-基]乙烯基]-2,3-二氢-1,3,6-三甲基-2-氧代氯化嘧啶、4,6-二[2-[2-羟苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代氯化嘧啶、4,6-二[2-[3-羟苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[4-羟苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[2,3-二羟苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-硫酸氢嘧啶、4,6-二[2-[2,4-二羟苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[2,5-二羟苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[2,6-二羟苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-硫酸氢嘧啶、4,6-二[2-3,4-二羟苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[3,5-二羟苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-硫酸氢嘧啶、4,6-二[2-3,6-二羟苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[2,3,4-三羟基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[2,3,5-三羟基苯基)乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[2,3,6-三羟基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[3,4,5-三羟基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[2,4,6-三羟基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[2-甲基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[3-甲基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[4-甲基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[2-羟基-3-甲基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氯化氧嘧啶、4,6-二[2-[2-羟基-4-甲基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[2-羟基-5-甲基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[2-羟基-6-甲基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[2-羟基-3,4-二甲氧基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[2-羟基-3,5-二甲氧基苯基乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[2-羟基-3,6-甲基苯基]ethenyl]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[3-羟基-2,4-二甲氧基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[3-羟基-2,5-二甲氧基苯基)乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[3-羟基-2,6-二甲氧基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、 4,6-二[2-[4-羟基-2,3-二甲氧基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[4-羟基-2,5-二甲氧基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[4-羟基-2,6-二甲氧基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[4-羟基-3,5-二甲氧基苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶、4,6-二[2-[4-(二乙基氨基)苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶和4,6-二[2-[4-(二乙基氨基)-2-羟苯基]乙烯基]-2,3-二氢-1,3-二甲基-2-氧代-氯化嘧啶。
上述引用的通式1的化合物、组分B的化合物、组份C的化合物和反应产物RP每一个的优选用量,基于100g总着色剂为0.03~65mmol。
在第四实施方式中,本发明试剂包含,除了至少一种根据通式I的化合物和至少一种反应性羰基化合物外,至少一种显影组份和任选一种作为氧化染料前体的偶合剂组分。
根据本发明,优选使用对苯二胺衍生物或者其生理学相容的盐作为显影组份。通式(E1)的对苯二胺衍生物是特别优选的,
其中
-G1代表氢原子、C1~C4烷基、C1~C4单羟基烷基、C2~C4多羟烷基、(C1~C4)-烷氧基-(C1 to C4)-烷基、4′-氨基苯基或者可由含氮基团、苯基或者4′-氨基苯基取代的C1~C4烷基;
-G2代表氢原子、C1~C4烷基、C1~C4单羟基烷基、C2~C4多羟烷基、(C1~C4)-烷氧基-(C1~C4)-烷基、或者由含氮基团取代的C1~C4烷基;
-G3代表氢原子、卤素原子比如氯、溴、碘或者氟原子、C1~C4烷基、C1~C4单羟基烷基、C2~C4多羟烷基、C1~C4羟基烷氧基、C1~C4乙酰基氨基烷氧基、甲磺酰基氨基烷氧基或者C1~C4氨基甲酰基氨基烷氧基;
-G4是氢原子、卤素原子、C1~C4烷基,或者 如果G3和G4彼此位于邻位,它们可一起形成桥接α,ω-亚烷基二氧基比如亚乙基二氧基。
本发明化合物中引用的C1~C4烷基取代基的例子是甲基、乙基、丙基、异丙基和丁基。乙基和甲基是优选的烷基。根据本发明,优选的C1~C4烷氧基例如是甲氧基或者乙氧基。另外,C1~C4羟烷基优选的例子可引用作为羟甲基、2-羟乙基、3-羟丙基或者4-羟丁基。羟乙基是特别优选的。特别优选的C2~C4多羟烷基是1,2-二羟基乙基。根据本发明,卤素原子的例子是氟、氯或者溴原子,氯原子是相当特别优选的。根据本发明,随后使用的术语源自于这里给出的定义。通式(E1)含氮基团的例子特别是氨基、C1~C4单烷基氨基、C1~C4烷基氨基、C1~C4三烷基氨基、C1~C4单羟基烷基氨基、咪唑啉鎓和铵。
通式(E1)特别优选的对苯二胺选自:对-苯二胺、对-间甲苯二胺、2-氯代-对-苯二胺、2,3-二甲基-对-苯二胺、2,6-二甲基-对-苯二胺、2,6-二乙基-对-苯二胺、2,5-二甲基-对-苯二胺、N,N-二甲基-对苯二胺、N,N-二乙基-对苯二胺、N,N-二丙基-对苯二胺、4-氨基-3-甲基-(N,N-二乙基)-苯胺、N,N-二-(β-羟乙基)-对羟乙基)氨基-2-氯代苯胺、2-(β-羟乙基)-对-苯二胺、2-氟代-对-苯二胺、2-异丙基-对-苯二胺、正-(β-羟丙基)-对-苯二胺、2-羟甲基-对-苯二胺、N,N-二甲基-3-甲基-对苯二胺、N,N-(乙基-β-羟乙基)-对-苯二胺、N-(β,γ-二羟基丙基)-对苯二胺、N-(4′-氨基苯基)-对苯二胺、N-苯基-对苯二胺、2-(β-羟基乙基氧基)-对-苯二胺、2-(β-乙酰基氨基乙基氧基)-对-苯二胺、N-(β-甲氧基乙基)-对-苯二胺和5,8-二氨基苯基-1,4-二氧杂环己烷和它们生理学相容的盐。
根据本发明,相当于通式(E1)相当特别优选的对苯二胺衍生物是对苯二胺、对间甲苯二胺、2-(β-羟乙基)-对苯二胺和N,N-二(β-羟乙基)-对苯二胺。
根据本发明,可以另外优选使用的显影液成份是包括至少两个由氨基和、或羟基取代的芳基核的化合物。
根据本发明可以用于该着色组合物的双核显影液成份包括特定的相当于通式(E2)的化合物以及它们生理学相容的盐:
其中:-Z1和Z2彼此独立地代表羟基或者NH2基团,其任选由C1~C4烷基、C1~C4羟烷基和、或桥联基团Y所取代,或者是任选桥接环状系统的部分,
-该桥联基团Y是具有1~14个碳原子的亚烷基,例如直链的或者支链亚烷基链或者亚烷基环,可以由一个或多个含氮基团和、或一个或多个杂原子比如氧、硫或者氮原子间断或者终止,及可任选由一个或多个羟基或者C1~C8烷氧基团取代,或者桥联基团Y是直接键合,
-G5和G6彼此独立地代表氢、卤素原子、C1~C4烷基、C1~C4单羟基烷基、C2~C4多羟烷基、C1~C4氨基烷基或者与桥联基团Y结合的直接键合,
-G7、G8、G9、G10、G11和G12彼此独立地代表氢原子、与桥联基团Y结合的直接键合或者C1~C4烷基,
-附带条件是:通式(E2)的化合物每分子包含仅一种桥联基团Y,和
-通式(E2)的化合物包含至少一个载带至少一个氢原子的氨基。
根据本发明,用于通式(E2)的取代基如上文实施方式中所定义。
相当于通式(E2)优选的双核一级中间体特别是:N,N′-二-(β-羟乙基)-N,N-二-(4是-氨基苯基)-1,3-二氨基丙-2-醇、N,N′-二-(β-羟乙基)-N,N′-二-(4是-氨基苯基)-乙二胺、N,N′-二-(4-氨基苯基)1,4-丁二胺、N,N′-二-(β-羟基乙基)-N,N′-二-(4是-氨基苯基)1,4-丁二胺、N,N′-二-(4-甲基氨基苯基)1,4-丁二胺、N,N′-二-(乙基)-N,N′-二-(4′-氨基-3′-甲基苯基)乙二胺、二-(2-羟基-5-氨基苯基)甲烷、1,4-二-(4′-氨基-苯基)二氮环庚烷、N,N′-二-(2-羟基-5-氨基苯甲基)-哌嗪、N-(4′-氨基苯基)-对-苯二胺和1,10-二-(2′,5′-二氨基苯基)-1,4,7,10-四氧杂癸烷和它们生理学相容的盐。
相当特别优选的通式(E2)的双核显影液成份是:N,N′-二-(β-羟乙基)-N,N′-二-(4′-氨基苯基)-1,3-二氨基丙-2-醇、二-(2-羟基-5-氨基苯基)甲烷、N,N′-二-(4是-氨基苯基)-1,4-二氮环庚烷和1,10-二-(2是,5′-二氨基苯基)-1,4,7,10-四氧杂癸烷或者它们生理学相容的盐之一。
根据本发明,另外优选的是使用对氨基苯酚衍生物或者其生理学相容的盐之一作为显影组份。通式(E3)的对氨基苯酚衍生物特别优选为:
-其中:G13代表氢原子、卤素原子、C1~C4烷基、C1~C4单羟基烷基、C2~C4多羟烷基、(C1~C4)-烷氧基-(C1~C4)-烷基、C1~C4氨基烷基、羟基-(C1~C4)-烷基氨基、C1~C4羟基烷氧基、C1~C4羟烷基-(C1~C4)-氨基烷基或者(二-C1~C4烷基氨基)-(C1~C4)}-烷基,和
-G14代表氢原子、卤素原子、C1~C4烷基、C1~C4单羟基烷基、C2~C4多羟烷基、(C1~C4)烷氧基(C1~C4)烷基、C1~C4氨基烷基或者C1~C4氰烷基,
-G15代表氢、C1~C4烷基、C1~C4单羟基烷基、C2~C4多羟烷基、苯基、苄基,G16代表氢或者卤素原子。
根据本发明,用于通式(E3)的取代基如上文实施方式中所定义。
优选的通式(E3)的对氨基苯酚特别是:对-氨基苯酚、N-甲基-对-氨基苯酚、4-氨基-3-甲基苯酚、4-氨基-3-氟苯酚、2-羟基甲基氨基-4-氨基苯酚、4-氨基-3-羟基甲基酚、4-氨基-2-(2-羟基乙氧基)苯酚、4-氨基-2-甲基苯酚、4-氨基-2-羟基甲基苯酚、4-氨基-2-甲氧基甲基苯酚、4-氨基-2-氨基甲基苯酚、4-氨基-2-(β-羟基乙基氨基甲基)苯酚、4-氨基-2-(α,β-二羟基乙基)苯酚、4-氨基-2-氟代酚,4-氨基-2-氯酚、2,6-二氯-4-氨基苯酚、4-氨基-2-(二乙基氨甲基)酚和它们生理学相容的盐。
相当于通式(E3)相当特别优选的化合物是对氨基苯酚、4-氨基-3-甲基苯酚、4-氨基-2-氨基甲基苯酚、4-氨基-2-(α,β-二羟基乙基)苯酚和4-氨基-2-(二乙基氨甲基)苯酚。
该显影组份可也选自邻-氨基苯酚和其衍生物,例如,2-氨基-4-甲基苯酚、2-氨基-5-甲基苯酚或者2-氨基-4-氯酚。
该显影组份可也选自杂环的显影液成份,例如,吡啶、嘧啶、吡唑、吡唑-嘧啶衍生物和其生理学相容的盐。
优选的吡啶衍生物特别是描述在GB 1026978和GB 1153196中的化合物,比如2,5-二氨基吡啶、2-(4’-甲基苯基)氨基-3-氨基吡啶、2,3-二氨基-6-甲氧基吡啶、2-(β-甲氧基乙基)氨基-3-氨基-6-甲氧基吡啶和3,4-二氨基吡啶。
优选的嘧啶衍生物特别是描述在DE 2359399、日本公开专利JP02019576A2或者公开的专利WO 96、15765中的化合物,比如2,4,5,6-四氨基嘧啶、4-羟基-2,5,6-三氨基嘧啶、2-羟基-4,5,6-三氨基嘧啶、2-二甲基氨基-4,5,6-三氨基-嘧啶、2,4-二羟基-5,6-二氨基嘧啶和2,5,6-三氨基嘧啶。
优选的吡唑衍生物特别是描述在DE 3843892、DE 4133957和专利申请WO 94、08969、94、08970、EP 740931和DE 19543988中的化合物,比如:4,5-二氨基-1-甲基吡唑、4,5-二氨基-1-(β-羟乙基)吡唑、3,4-二甲基吡唑、4,5-二氨基-1-(4是-氯苄基)吡唑、4,5-二氨基-1,3-二甲基吡唑、4,5-二氨基-3-甲基-1-苯基吡唑、4,5-二氨基-1-甲基-3-苯基吡唑、4-氨基-1,3-二甲基-5-肼基吡唑、1-苯甲基-4,5-二氨基-3-甲基吡唑、4,5-二氨基-3-特丁基-1-甲基吡唑、4,5-二氨基-1-特丁基-3-甲基吡唑、4,5-二氨基-1-(β-羟乙基)-3-甲基吡唑、4,5-二氨基-1-乙基-3-甲基吡唑、4,5-二氨基-1-乙基-3-(4′-甲基苯基)吡唑、4,5-二氨基-1-乙基-3-羟基甲基吡唑、4,5-二氨基-3-羟甲基-1-甲基吡唑、4,5-二氨基-3-羟甲基-1-异丙基吡唑、4,5-二氨基-3-甲基-1-异丙基吡唑、4-氨基-5-(2′-氨乙基)-氨基-1,3-二甲基吡唑、3,4,5-三氨基吡唑、1-甲基-3,4,5-三氨基吡唑、3,5-二氨基-1-甲基-4-甲基氨基吡唑和3,5-二氨基-4-(β-羟乙基)-氨基-1-甲基吡唑。
优选的吡唑-嘧啶衍生物特别是相当于以下通式(E4)的吡唑-[1,5-a]-嘧啶的衍生物和其互变异构形式,在这个范围内存在互变异构平衡:
-其中:
-G17、G18、G19和G20彼此独立地代表氢原子、C1~C4烷基、芳基、羟烷基、C2~C4多羟烷基、(C1~C4)-烷氧基-(C1~C4)-烷基、任选可由乙酰基脲基或者磺酰基团保护的C1~C4氨基烷基、(C1~C4)-烷基氨基-(C1~C4)-烷基、二[(C1~C4)-烷基]-(C1~C4)-氨基烷基、任选形成5或者6元碳环或者杂环的二烷基、C1~C4羟烷基、二-(C1~C4)-[羟烷基]-(C1~C4)-氨基烷基;
-X基团彼此独立地代表氢原子、C1~C4烷基、芳基、C1~C4羟烷基、C2~C4多羟烷基、C1~C4氨基烷基、(C1~C4)-烷基氨基-(C1~C4)-烷基、二[(C1~C4)-烷基]-(C1~C4)-氨基烷基、任选形成5或者6元碳环杂环的二烷基团、C1~C4羟烷基、二-(C1~C4)-[羟烷基]-(C1~C4)-氨基烷基、氨基团、C1~C4烷基、二-(C1~C4-羟烷基)-氨基、卤素原子、羧酸原子团或者磺酸基,
-I的值为0、1、2或者3,
-p的值为0或者1,
-q的值为0或者1,和
-n的值为0或者1,
-附带条件是p+q的和不是0,
-当p+q=2,N的值为0,基团NG17G18和NG19G20位于(2,3);(5,6);(6,7);(3,5)或者(3,7)位;
-当p+q=1,N的值为1,基团NG17G18(或者NG19G20)和基团OH位于(2,3);(5,6);(6,7);(3,5)或者(3,7)位;
根据本发明,用于通式(E4)的取代基如上文实施方式中所定义。
如果相当于上述通式(E4)的吡唑-[1,5-a]-嘧啶在环体系2、5或者7位置之一包含羟基,例如在如下方案中举例说明存在的互变异构平衡:
在相当于上述通式(E4)的吡唑-[1,5-a]-嘧啶中,特别提到以下的化合物:
吡唑-[1,5-a]-嘧啶-3,7-二胺;
2,5-二甲基吡唑-[1,5-a]-嘧啶-3,7-二胺;
吡唑-[1,5-a]-嘧啶-3,5-二胺;-
2,7-二甲基吡唑-[1,5-a]-嘧啶-3,5-二胺;
-3-氨基吡唑-[1,5-a]-嘧啶-7-醇;
-3-氨基吡唑-[1,5-a]-嘧啶-5-醇;
-2-(3-氨基吡唑-[1,5-a]-嘧啶-7-基氨基)乙醇;
--2-(7-氨基吡唑-[1,5-a]-嘧啶-3-基氨基)乙醇;
--2-[(3-氨基吡唑-[1,5-a]-嘧啶-7-基)-(2-羟乙基)氨基]乙醇;
--2-[(7-氨基吡唑-[1,5-a]-嘧啶-3-基)-(2-羟乙基)氨基]乙醇;
-5,6-二甲基吡唑-[1,5-a]-嘧啶-3,7-二胺;
--2,6-二甲基吡唑-[1,5-a]-嘧啶-3,7-二胺;
--3-氨基-7-二甲基氨基-2,5-二甲基吡唑-[1,5-a]-嘧啶;
以及它们生理学相容的盐和它们的互变异构形式(如果存在互变异构平衡)。
如文献中描述,相当于上述通式(E4)的吡唑-[1,5-a]-嘧啶可以通过从氨基吡唑或者从肼环化制备。
任选包含在本发明试剂中的偶合剂组份优选选自:
-间-氨基苯酚和其衍生物,例如,5-氨基-2-甲基苯酚、N-环戊基-3-氨基苯酚、3-氨基-2-氯代-6-甲基苯酚、2-羟基-4-氨基苯氧基乙醇、2,6-二甲基-3-氨基苯酚、3-三氟乙酰基氨基-2-氯代-6-甲基苯酚、5-氨基-4-氯代-2-甲基苯酚、5-氨基-4-甲氧基-2-甲基苯酚、5-(2是-羟乙基)氨基-2-甲基苯酚、3-(二乙基氨基)酚、N-环戊基-3-氨基苯酚、1,3-二羟基-5-(甲基氨基)苯、3-(乙基氨基)-4-甲基苯酚和2,4-二氯-3-氨基苯酚,
-邻氨基苯酚和其衍生物,
-间-苯二胺和其衍生物,例如,2,4-二氨基苯氧基乙醇、1,3-二-(2′,4′-二氨基苯氧基)丙烷、1-甲氧基-2-氨基-4-(2是-羟乙基氨基)苯、1,3-二-(2′,4′-二氨基苯基)丙烷、2,6-二-(2是-羟乙基氨基)-1-甲苯和1-氨基-3-二-(2是-羟乙基)氨基苯,
-邻-苯二胺和其衍生物,例如,3,4-二氨基苯甲酸和2,3-二氨基-1-甲苯,
-二-和三羟基苯衍生物,例如,间苯二酚、间苯二酚一甲基醚、2-甲基间苯二酚、5-甲基间苯二酚、2,5-二甲基间苯二酚、2-氯代间苯二酚、4-氯代间苯二酚、焦性没食子酸和1,2,4-三羟基苯,
-吡啶衍生物,例如,2,6-二羟基吡啶、2-氨基-3-羟基吡啶、2-氨基-5-氯代-3-羟基吡啶、3-氨基-2-甲基氨基-6-甲氧基吡啶、2,6-二羟基-3,4-二甲基吡啶、2,6-二羟基-4-甲基吡啶、2,6-二氨基吡啶、2,3-二氨基-6-甲氧基吡啶和3,5-二氨基-2,6-二甲氧基吡啶,
-萘衍生物,例如,1-萘酚、2-甲基-1-萘酚、2-羟甲基-1-萘酚、2-羟乙基-1-萘酚、1,5-二羟基萘、1,6-二羟基萘、1,7-二羟基萘、1,8-二羟基萘、2,7-二羟基萘和2,3-二羟基萘,
-吗啉衍生物例如6-羟基苯并吗啉和6-氨基苯并吗啉,
-喹啉衍生物比如6-甲基-1,2,3,4-四氢喹啉,
-吡唑衍生物比如,1-苯基-3-甲基吡唑啉-5-酮,
-吲哚衍生物比如4-羟基吲哚、6-羟基吲哚和7-羟基吲哚,
-嘧啶衍生物比如,4,6-二氨基嘧啶、4-氨基-2,6-二羟基嘧啶,2,4-二氨基-6-羟基嘧啶,2,4,6-三羟基嘧啶、2-氨基-4-甲基嘧啶、2-氨基-4-羟基-6-甲基嘧啶和4,6-二羟基-2-甲基嘧啶,或者
-亚甲二氧基基苯衍生物例如1-羟基-3,4-亚甲二氧基基苯、1-氨基-3,4-亚甲二氧基基苯和1-(2′-羟乙基)-氨基-3,4-亚甲二氧基基苯。
根据本发明,特别优选的偶合组分是1-萘酚、1,5-,2,7-和1,7-二羟基萘、3-氨基苯酚、5-氨基-2-甲基苯酚、2-氨基-3-羟基吡啶、间苯二酚、4-氯代间苯二酚、2-氯代-6-甲基-3-氨基苯酚、2-甲基间苯二酚、5-甲基间苯二酚、2,5-二甲基间苯二酚和2,6-二羟基-3,4-二甲基吡啶。
在本发明第五实施方式的范围中,可以另外优选的是向本发明试剂中加入天然染料类似物的前体,比如至少包含一个羟基或者氨基,优选作为6元环上的取代基的吲哚和、或二氢吲哚。这些基团可载带另外的取代基,例如以醚化或者酯化的羟基或者烷基化氨基的形式。在第二优选实施方式中,着色剂包含至少一种吲哚和、或二氢吲哚衍生物。
通式Xa的5,6-二羟二氢吲哚的衍生物作为自然毛发染料类似物前体是特别良好的。
其中,彼此独立地
-G21是氢、C1-C4烷基或者C1-C4羟烷基,
-G22是氢或者COOH基团,COOH基团任选与生理学相容的阳离子一起作为盐,
-G23是氢或C1~C4烷基,
G24是氢、C1-C4烷基或者基团-CO-G26,其中G26为C1-C4烷基、
G25是对于G24提到的基团之一,和这些化合物与有机或者无机酸的生理学相容的盐。
特别优选的二氢吲哚衍生物是5,6-二羟二氢吲哚、N-甲基-5,6-二羟二氢吲哚、N-乙基-5,6-二羟二氢吲哚、N-丙基-5,6-二羟二氢吲哚、N-丁基-5,6-二羟二氢吲哚、5,6-二羟二氢吲哚-2-羧酸、6-羟基二氢吲哚、6-氨基二氢吲哚和4-氨基二氢吲哚。
在该基团之内,特别重点的是N-甲基-5,6-二羟二氢吲哚、N-乙基-5,6-二羟二氢吲哚、N-丙基-5,6-二羟基-二氢吲哚、N-丁基-5,6-二羟二氢吲哚,特别是5,6-二羟二氢吲哚。
其它特别适当的自然毛发染料类似物的前体是相当于通式(IIIb)的5,6-二羟吲哚:
-其中,彼此独立地
-G27是氢、C1-C4烷基或者C1-C4羟烷基,
-G28是氢或者COOH基团,COOH基团任选与生理学相容的阳离子一起作为盐,
-G29是氢或者C1-C4烷基,
-G30是氢、C1-C4烷基或者基团-CO-G32,其中G32为C1-C4烷基、
-G31是对于G30提到的基团之一,和
-这些化合物与有机或者无机酸的生理学相容的盐。
特别优选的吲哚衍生物是5,6-二羟吲哚、N-甲基-5,6-二羟吲哚、N-乙基-5,6-二羟吲哚、N-丙基-5,6-二羟吲哚、N-丁基-5,6-二羟吲哚、5,6-二羟吲哚-2-羧酸、6-羟基吲哚、6-氨基吲哚和4-氨基吲哚。
在该基团之内,特别重点的是N-甲基-5,6-二羟吲哚、N-乙基-5,6-二羟吲哚、N-丙基-5,6-二羟吲哚、N-丁基-5,6-二羟吲哚,特别是,5,6-二羟吲哚。
二氢吲哚和吲哚衍生物都作为游离碱可以用于本发明的着色剂中,而且以它们与无机的或者有机酸生理学相容的盐例如氢氯化物、硫酸盐和溴氢化合物的形式。在这些着色剂中吲哚或者二氢吲哚衍生物通常的量为0.05~10wt.%,优选为0.2~5wt.%。
在本发明第六实施方式中,本发明的毛发着色剂可包含,除包含本发明的化合物之外,还可包含另外的通常用于改性色调的直接染料比如硝基亚苯基二胺、硝基氨基酚、偶氮染料、蒽醌或者靛酚氧化酶。优选的直接染料是具有如下国际标准名称或者商业名称已知的化合物:HC Yellow 2、HC Yellow 4、HC Yellow 5、HC Yellow 6、HC Yellow12、Acid Yellow 1、Acid Yellow 10、Acid Yellow 23、Acid Yellow 36、HC Orange 1、Disperse Orange 3、Acid Orange 7、HC Red 1、HC Red 3、HC Red 10、HC Red 11、HC Red 13、Acid Red 33、Acid Red 52、HC RedBN、Pigment Red 57:1、HC Blue 2、HC Blue 12、Disperse Blue 3、AcidBlue 7、Acid Green 50、HC Violet 1、Disperse Violet 1、Disperse Violet4、Acid Violet 43、Disperse Black 9、Acid Black 1和Acid Black 52、以及1,4-二氨基-2-硝基苯、2-氨基-4-硝基苯酚、1,4-二-(β-羟乙基)氨基-2-硝基苯、3-硝基-4-(β-羟乙基)氨基苯酚、2-(2′,4′,4′,4′-羟乙基)氨基-4,6-二硝基酚、1-(2′-羟乙基)氨基-4-甲基-2-硝基苯、1-氨基-4-(2′-羟乙基)-氨基-5-氯代-2-硝基苯、4-氨基-3-硝基苯酚,1-(2′-脲基乙基)-氨基-4-硝基苯、4-氨基-2-硝基二苯胺-2′-羧酸、6-硝基-1,2,3,4-四氢喹啉、2-羟基-1,4-白花丹素、苦氨酸和其盐、2-氨基-6-氯代-4-硝基苯酚、4-乙基氨基-3-硝基苯甲酸和2-氯代-6-乙基氨基-1-羟基-4-硝基苯。
况且,根据本发明的组合物可包含阳离子的直接染料。因此特别优选的是
(a)阳离子的三苯甲烷染料例如基本蓝色7、基本蓝色26、基本紫罗兰2和基本紫罗兰14,
(b)由季氮基团取代的芳烃系统比如基本黄色57、基本红76、基本蓝色99、碱性棕16和碱性棕17,和
(c)含具有至少一个季氮原子杂环的直接染料,例如在EP-A2998908的权利要求6~11明确公开的那些。
(c)组优选的阳离子直接染料特别是以下的化合物:
相当于通式(DZ1)、(DZ3)和(DZ5)的化合物(c)组相当特别优选的阳离子直接染料。商业化的ARIanor阳离子直接染料是本发明特别优选的直接染料。
本发明依据这种实施方式的组合物优选包含基于着色剂总量含量为0.01~20wt.%的直接染料。
根据本发明的制剂也可包含天然染料比如指甲花红、指甲花无色、指甲花黑色、春黄菊花、檀香木、红茶、灰桤木树皮、鼠尾草属植物、苏木、茜草、儿茶、雪松和朱草根。
任选将直接染料包含于每一个代表性同类化合物中是不必要的。相反地,因为对于单独染料的合成过程而言,在本发明着色剂中存在微量另外的组份也是可能的,条件是这些组份不对着色结果产生不利的影响,或者出于其它的原因例如毒物学的原因必须除去。
为得到另外的而且更充分的着色,本发明的试剂可以包含另外的颜色增效剂。有利的是颜色增效剂选自:哌啶、哌啶-2-羧酸、哌啶-3-羧酸、哌啶-4-羧酸、吡啶、2-羟基吡啶、3-羟基吡啶、4-羟基吡啶、咪唑、1-甲基咪唑、精氨酸、组氨酸、吡咯烷、脯氨酸、吡咯烷酮、吡咯烷酮-5-羧酸、吡唑、1,2,4-三唑、哌嗪、它们的衍生物和它们生理学相容的盐。
上述提及的颜色增效剂每一个的用量基于100g着色剂总量为0.03~65mmol,特别是1~40mmol。
特别是如果本发明试剂不包含任何氧化染料前体,可以避免氧化剂例如H2O2的存在。如果本发明的试剂包含空气可氧化的氧化染料前体或者吲哚或者二氢吲哚衍生物,那么在这种情况下毫无疑义地可以避免该氧化剂。然而,在某种情形下,也许需要将过氧化氢或者其它的氧化剂加入到本发明的试剂中以得到比含角蛋白纤维着色轻的色调。基于本发明溶液氧化剂通常的加入量为0.01~6wt.%。头发优选的氧化剂是H2O2。也可使用多个氧化剂的混合物比如过氧化氢和碱金属和碱土金属的过二硫酸钠盐组合物,或者来自碘化物离子源比如碱金属碘化物和过氧化氢的混合物,或者上述的过二硫酸钠盐。根据本发明,氧化剂和氧化剂组合物可与氧化催化剂一起用于毛发着色剂中。示范性的氧化催化剂是金属盐、金属螯合物络合物或者金属氧化物,其可使金属离子在两种氧化态之间容易的转变。例子是铁、钌、锰和铜的盐、螯合物或者氧化物。其它可能的氧化催化剂是酶。适当的酶例如是过氧化物酶,其可显著增强微量过氧化氢的效果。根据本发明,而且这样的酶在空气中氧存在下适于直接氧化氧化染料前体,例如漆酶,或者原位产生微量的过氧化氢,用这样的方式生物催化活化氧化该染料前体。用于氧化该染料前体的特别适当的催化剂是所谓的与它们特定的如下底物相结合的2-电子氧化还原酶,例如:
-pyranose-oxidase and e.g.D-glucose or galactose,
-葡萄糖-氧化酶和D-葡萄糖,
-甘油-氧化酶和甘油,
-丙酮酸盐-氧化酶和丙酮酸或者它的盐,
-醇-氧化酶和醇(甲醇,乙醇),
-乳酸盐氧化酶和乳酸和它的盐,
-酪氨酸酶-氧化酶和酪氨酸,
-尿酸酶和尿酸或者它的盐,
-胆碱-氧化酶和胆碱,
-氨基酸-氧化酶和氨基酸。
本发明的着色剂可在生理学可接受的温度45℃以下已经产生充分的着色。它们因此特别适于染色头发。为用于头发,该着色剂通常混合到一种水性的化妆品载体中。适当的水性化妆品载体例如是奶油、乳状液、凝胶或者其它的包含表面活性剂的泡沫溶液,例如洗发剂或者其它的适于应用于含角蛋白纤维的制剂。当需要时,也可将着色剂混合到无水载体中。
根据本发明的着色剂也可包含任一种用于这种通常制剂已知的活性物质、添加剂和助剂。在许多情况下,着色剂包含至少一种表面活性剂,原则上阴离子的、两性离子的、两性的、非离子的和阳离子表面活性剂是适当的。然而在许多情况下,已经被认为有利的是表面活性剂选自阴离子的、两性离子的或者非离子型表面活化剂。
用于本发明制剂适当的阴离子表面活性剂是任何的适合用于人体的阴离子表面活性物质。这样的物质特征在于水增溶性阴离子基团,例如羰酸酯、硫酸酯、磺酸酯或者磷酸酯基团,和含大约10~22个碳原子的亲脂性的烷基。另外,乙二醇或者聚乙二醇醚基团、酯、醚、酰胺和羟基团也可存在于该分子中。以下是适当的阴离子表面活性剂的例子,每一个阴离子表面活性剂是以钠、钾和铵盐以及烷醇基团含2或者3个碳原子的单、二和三烷醇铵盐形式,
-含10~22个碳原子的直链的脂肪酸(肥皂)、
-具有通式R-O-(CH2-CH2O)x-CH2-COOH的醚羧酸,其中R是含10~22个碳原子直链的烷基,x=0或者1~16,
-含10~18个碳原子的酰基肌氨酸金属盐、
-在酰基团中含10~18个碳原子的酰基牛磺酸、
-在酰基团中含10~18个碳原子的酰基羟乙基磺酸盐,
-在烷基中含8~18个碳原子的单和二烷基磺基丁二酸酯和含1~6个氧乙基和烷基中含8~18个碳原子的单烷基聚氧乙基磺基丁二酸酯,
-含12~18个碳原子的直链链烷磺酸盐、
-含12~18个碳原子的直链α-烯基磺酸盐、从含12~18个碳原子的脂肪酸得到的α-磺基脂肪酸,
-烷基硫酸盐和烷基聚乙二醇醚硫酸盐相当于通式R-O(CH2-CH2O)x-OSO3H,其中R优选是直链的含10~18个碳原子的烷基,x=0或者1~12,
-根据DE-A-3725030的表面活性的羟基磺酸盐的混合物,
-根据DE-A-3723354的硫酸化羟基烷基聚乙烯-和、或羟基亚烷基丙烯乙二醇醚,
-根据DE-A-3926344的含12~24个碳原子和1~6个双键的不饱和脂肪酸的磺酸盐,
-酒石酸和柠檬酸与以含8~22个碳原子的脂肪醇与大约2~15分子的环氧乙烷和、或环氧丙烷加成物形式的醇的酯类,
优选的阴离子表面活性剂是烷基硫酸盐、烷基聚乙二醇醚硫酸盐和分子中含达到12个乙二醇醚基团及烷基中含10~18个碳原子的醚羧酸,以及特别是饱和的、特别是不饱和C8-C22羧酸比如油酸、硬脂酸、异硬脂酸和棕榈酸的盐。
两性离子表面活性剂定义为这样的表面活性物质,其分子中包含至少一种季铵基团和至少一种-COO(-)或者-SO3(-)基团。特别适当的两性离子表面活性剂是所谓的甜菜碱,比如N-烷基-N,N-二甲基铵甘氨酸盐,例如椰油基烷基二甲基铵甘氨酸盐,N-酰基氨基丙基-N,N-二甲基铵甘氨酸盐,例如椰油基酰基氨基丙基二甲基铵甘氨酸盐,和烷基中或者酰基中含8~18个碳原子的2-烷基-3-羧甲基-3-羟乙基咪唑啉和椰油基酰基氨基乙基羟乙基羧甲基甘氨酸盐。优选的两性离子表面活性剂是脂肪酸酰胺衍生物,名称为CTFA的椰油基氨基丙基甜菜碱。
两性表面活性剂应理解为这样的表面活性物质,在分子中除了C8-C18烷基或者酰基团,还包含至少一种自由氨基和至少一种COOH或者-SO3H基团,而且能够形成内盐。适当的两性表面活性剂的例子是N-烷基甘氨酸、N-烷基丙酸、N-烷基氨基丁酸、N-烷基亚氨基二丙酸、N-羟乙基-N-烷基氨基丙基甘氨酸、N-烷基牛磺酸、N-烷基肌氨酸、2-烷基丙氨酸和烷基甘氨酸,每一个在烷基中含大约8~18个碳原子。特别优选的两性表面活性剂是N-椰油基烷基氨基丙酸盐、椰油基酰基氨乙基氨基丙酸盐和C12-C18酰基肌氨酸。
非离子型表面活化剂包含作为亲水基的例如多羟基化合物基团、聚二醇醚基团或者多羟基化合物和聚乙二醇醚基团的组合物。这样的化合物的例子是:
-2~30摩尔环氧乙烷和、或0~5摩尔环氧丙烷加成作用到烷基中含8~22个碳原子直链的和支链脂肪醇、含12~22个碳原子的脂肪酸和含8~15个碳原子的烷基酚上得到的产物,
-1~30摩尔环氧乙烷加成作用在甘油上得到产物的C12-C22脂肪酸单酯和二酯,
-C8-C22烷基单和低聚甙和它们的乙氧基化类似物,5~60摩尔环氧乙烷加成作用在蓖麻油和氢化蓖麻油上的产物,
-环氧乙烷加成作用在失水山梨糖醇脂肪酸酯上得到的产物,环氧乙烷加成作用在脂肪酸链烷醇酰胺上的产物。
适于本发明的毛发处理试剂的阳离子表面活性剂的例子特别是季铵化合物。卤化铵,比如,烷基三甲基氯化铵、二烷基二甲氯化铵和三烷基甲基氯化铵,例如十六烷基三甲基氯化铵、硬脂酰三甲基氯化铵、二硬脂基二甲基氯化铵、月桂基二甲氯化铵、月桂基二甲基苯甲基氯化铵和三鲸烷基甲基氯化铵。其它本发明适当的阳离子表面活性剂由季铵化的蛋白水解产物代表。
根据本发明,阳离子的硅油也是适当的例如市场上可买到的产品:Q2-7224(厂商:Dow Corning;稳定的三甲代甲硅烷基氨基聚二甲基硅氧烷)、Dow Corning929乳状液(包括羟氨基改性的硅树脂,也称为氨基聚二甲基硅氧烷〔amodimethicone〕)、SM-2059(厂商:GeneralElectRIc)、SLM-55067(厂商:Wacker)和Abil-Quat 3270和3272(厂商:Th.Goldschmidt;双季铵聚二甲硅氧烷,Quaternium-80)。
烷基酰胺,特别是脂肪酸酰胺比如硬脂酰胺丙基二甲胺,以TegoAmidS18得到,特征在于良好的调节作用,特别是它们良好的生物降解性。
季酯化合物,通称“esterquats”,同样地具有良好的生物降解性,比如商品名为Stepantex的使商业化的甲基羟基烷基二烷酰氧基烷基铵硫酸二甲酯。
适当的阳离子表面活性剂季糖衍生物的例子是商品Glucquat100,根据CTFA命名法为“月桂基甲基葡萄糖甙十环氧乙烷-10羟丙基二铵氯化物”。
用作具有烷基的表面活性剂的化合物每一个可为同类的化合物。然而一般说来,这些化合物优选从自然界的蔬菜或者动物原料得到,导致含有取决于原料不同烷链长度的产品混合物。
代表环氧乙烷和、或环氧丙烷与脂肪醇的加成物或者这些加成物的衍生物的表面活性剂可以都是具有“标准的”同系物分布的产品及具有窄的同系物分布的产品。具有“标准的”同系物分布的产品是从脂肪醇和烯化氧使用碱金属、碱金属氢氧化物或者碱金属乙醇化物作为催化剂反应得到的同系物。相反,窄的同系物分布是当例如水滑石、醚羧酸的碱土金属盐、碱土金属氧化物、氢氧化物或者乙醇化物用作催化剂时得到的产品。使用具有窄的同系物分布的产品是优选的。
另外的活性产品、助剂和添加剂的例子是:
-非离子的聚合物比如,例如乙烯基吡咯烷酮、乙烯基丙烯酸酯橡胶、聚乙烯基吡咯烷酮和乙烯基吡咯烷酮、醋酸乙烯酯共聚物和聚硅氧烷,
-阳离子聚合物比如季铵化的纤维素醚、具有季铵化基团的聚硅氧烷、二甲基二烯丙基铵氯化物聚合物、丙烯酰胺-二甲基二烯丙基铵氯化物共聚物、用硫酸二乙酯季铵化的二甲基氨基乙基甲基丙烯酸酯-乙烯基吡咯烷酮共聚物、乙烯基吡咯烷酮-咪唑啉鎓甲氯化物共聚物和季铵化的聚乙烯醇,
-两性离子的和两性聚合物比如,例如丙烯酰胺丙基三甲基铵氯化物、丙烯酸酯橡胶和辛基丙烯酰胺、异丁烯酸甲酯、甲基丙烯酸特-丁基氨基乙基酯、2-甲基丙烯酸羟丙基酯共聚物,
-阴离子聚合物比如,例如聚丙烯酸、交联聚丙烯酸、醋酸乙烯酯、巴豆酸共聚物、乙烯基吡咯烷酮、醋酸乙烯酯共聚物、醋酸乙烯酯、丁基顺丁烯二酸、异冰片基丙烯酸酯橡胶、乙烯甲醚、马来酐共聚物和丙烯酸、丙烯酸乙酯、N-特丁基丙烯酰胺三元共聚物,
-增稠剂,比如冻琼脂、胍尔豆胶、藻朊酸盐、苍耳烷龈、阿拉伯树胶、刺梧桐树胶、角豆荚果面粉、亚麻子龈、右旋糖酐,纤维素衍生物,例如甲基纤维素、羟烷基细胞膜质和羧甲基纤维素,淀粉部分和衍生物,比如直链淀粉、支链淀粉和糊精,粘土比如,例如皂土或者完全合成的水状胶质比如,例如,聚乙烯醇,
-结构化剂比如葡萄糖和马来酸,
-毛发调理化合物,比如磷脂,例如大豆磷脂、卵磷酯和脑磷脂及硅油,
-水解蛋白精料,特别是弹性蛋白的水解产物、胶原、角蛋白、牛乳蛋白质、大豆蛋白质和小麦蛋白,它们与脂肪酸的缩合产物以及季铵化的蛋白水解产物,
-芳香油、二甲基异山梨糖醇和环化糊精,
-增溶剂比如乙醇、异丙醇、乙二醇、丙二醇、甘油和二甘醇,
-防头皮屑试剂,比如piroctone油胺和锌万亩定,
-另外的调节pH的物质,
-活性物质比如泛醇、泛酸、尿囊素、吡咯烷酮羧酸和它们的盐、植物浸出液和维生素,
-胆固醇,
-光稳定剂,
-稠度系数,比如糖酯、多羟基化合物酯类或者多羟基化合物烷基醚,
-脂和蜡,比如鲸蜡、蜂蜡、褐煤蜡和烷烃,
-脂肪酸烷醇酰胺,
-络合剂,比如乙二胺四乙酸、次氮基三乙酸和膦酸,
-溶胀和穿透剂,比如甘油、丙二醇单甲醚、碳酸酯、重碳酸盐、胍、碳酰胺和一代,二代和三代磷酸盐、咪唑、丹宁酸、吡咯,
-遮光剂,比如乳液,
-常用珠光剂,比如乙二醇单和二硬脂酸酯,
-推进剂比如丙烷、丁烷混合物、N2O、二甲醚、CO2和空气,和
-抗氧化剂。
为制造本发明的着色剂,对于本发明以通常的量加入水性载体成分;例如加入的乳化剂浓度为着色剂总量的0.5~30wt.%,增稠剂浓度为总量的0.1~25wt.%。
对于颜色效果,有利的是向着色剂中加入铵或者金属盐。适当的金属盐例如是甲酸盐、碳酸盐、卤化物、硫酸盐、丁酸盐、缬草酸盐、己酸盐、醋酸盐、乳酸盐、甘醇酸盐、酒石酸盐、柠檬酸盐、葡萄糖酸盐、丙酸盐、碱金属,比如钾、钠或者锂,碱土金属比如镁、钙、锶或者钡,或者铝、锰、铁、钴、铜或者锌的磷酸盐和膦酸盐,其中乙酸钠、溴化锂、溴化钙、葡萄糖酸钙、氯化锌、硫酸锌、氯化镁、硫酸镁、碳酸铵、氯化铵和乙酸铵是优选的。这些盐的含量优选基于100g着色剂总量为0.03~65mmol,特别是1~40mmol。
现成的染料制剂的pH通常位于2~11之间,优选5~10之间。
本发明的第二主题是用于含角蛋白的纤维特别是头发的着色剂,包括作为着色组分的通式VIII的反应产物RP,
其中
■R1、R2、R5、Y和X-如通式I的定义,
■R23和R24彼此独立地代表氢原子、C1-C6烷基、通式IX的基团,
其中
■R6、R7、R8、R9、AR和Z如通式II定义,
■R25代表氢原子或者C1-C5烷基,
附带条件是R23和R24的至少一个代表通式IX的基团。
特别优选的是如果本发明的试剂包含这样的根据通式VIII的反应产物RP,其中根据通式IX的AR代表苯或者萘。
另外的特别优选的是如果本发明的试剂包括这样的根据通式VIII的反应产物RP,其中根据通式IX的Z代表直接键合或者亚乙烯基。
另外的特别优选的是如果本发明的试剂包括这样的根据通式VIII的反应产物RP,其中根据通式IX的R25代表氢原子。
另外的特别优选的是如果本发明的试剂包括这样的根据通式VIII的反应产物RP,其中根据通式IX的R6代表氢原子。
另外的特别优选的是如果本发明的试剂包括这样的根据通式VIII的反应产物RP,其中根据通式IX的R7、R8和R9彼此独立地代表氢原子、卤素原子、C1-C6烷基、羟基、C1-C6烷氧基、氨基、C1-C6烷基氨基、二(C2-C6羟烷基)氨基、二(C1-C6烷氧基C1~C6烷基)氨基、C1-C6羟基烷氧基、磺酰基团、羧基、磺酰胺基团、氨甲酰基团、C2-C6酰基团、乙酰基、磺酸基、磺酰胺基团或者硝基。
另外的特别优选的是如果本发明的试剂包括这样的根据通式VIII的反应产物RP,其中根据通式IX的R7、R8和R9彼此独立地代表氢原子、卤素原子、C1-C6烷基、羟基、C1-C6烷氧基、氨基、C1-C6烷基氨基、二(C2-C6羟烷基)氨基、二(C1-C6烷氧基C1~C6烷基)氨基、C1-C6羟基烷氧基、磺酰基团、羧基、磺酰胺基团、氨甲酰基团、C2-C6酰基团、乙酰基、磺酸基、磺酰胺基团或者硝基,附带条件是如果AR代表苯,基团R7、R8、R9或Z的一个代表氢原子、卤素原子、C1-C6烷氧基、或者氨基,那么其他两个基团彼此独立地既不为氢原子也不为卤素原子。
另外的特别优选的是如果本发明的试剂包括这样的根据通式VIII的反应产物RP,其中根据通式IX的R7、R8和R9彼此独立地代表氢原子、卤素原子、C1-C6烷基、羟基、C1-C6烷氧基、氨基、C1-C6烷基氨基、二(C2-C6羟烷基)氨基、二(C1-C6烷氧基C1~C6烷基)氨基、C1-C6羟基烷氧基、磺酰基团、羧基、磺酰胺基团、氨甲酰基团、C2-C6酰基团、乙酰基、磺酸基、磺酰胺基团或者硝基,附带条件是R7、R8或者R9或Z的一个代表选自如下的基团:羟基、C1-C6烷基氨基团、二(C2-C6羟烷基)氨基、二(C1-C6烷基)氨基和C1-C6羟基烷氧基团。
根据通式VIII特别优选的化合物是本发明第一主题引用的化合物。
优选反应产物RP在试剂中的含量基于100g的着色剂总量为0.03~65mmol,特别是1~40mmol。
这些着色剂另外包含:
a)至少一种另外的前面提到的直接染料和、或
b)至少一种前面提到的氧化染料前体和、或至少一种前面提到的二氢吲哚或者吲哚的衍生物,和
c)任选的氧化剂比如过氧化氢。
而且,已经如上所述的所有的表面活性剂、颜色增效剂、金属盐氧化剂以及另外的助剂、活性物质和添加剂可以加入到本发明第二主题的试剂中。
本发明的第三主题涉及通式1和、或它的烯胺形式的至少一种1,2-二氢嘧啶鎓衍生物,
其中R1、R2、R3、R4、R5、Y和X-定义如上,与至少一种作为着色组份的反应性羰基化合物(组分B)结合用于毛发着色剂中。
在优选实施方式中,通式I的1,2-二氢嘧啶鎓衍生物与选自上述优选引用的特别优选典型的至少一种反应性羰基化合物的组分B结合作为着色组份用于毛发着色剂中。
而且,优选的是使用至少一种根据通式I的1,2-二氢吡啶鎓衍生物和组分B的化合物的反应产物RP在毛发着色剂中作为着色组分。
本发明的第四主题涉及染色含角蛋白纤维特别是头发的方法,其中着色剂包括至少一种通式1和或它的烯胺形式的1,2-二氢嘧啶鎓衍生物,
其中R1、R2、R3、R4、R5、Y和X-定义如上,和至少一种反应性羰基(组分B)化合物及通常的化妆品成分,被施加到含角蛋白纤维停留一段时间通常15-30分钟,随后用洗发剂漂洗或者冲洗。在试剂与纤维接触时间内,有利的是通过加热促进染色过程。热可以从外部加热源提供,比如来自吹风器的暖空气,特别通过受试人的体温在活的受试人上进行毛发着色。后者的选择通常是通过兜帽覆盖要着色的部分进行的。
这样,通式I的1,2-二氢吡啶衍生物和组分B的化合物,特别它们上述优选的和特别优选引用的典型,作为颜色提供组分同时或者相继地施加到毛发上,,那就是说,在多步骤方法中,其中哪个组分首先施加并不重要。任选包含的铵或者金属盐可加入到通式I的化合物或者组分B的化合物中。在施加单个组分之间间隔最多为30分钟。同样可以用盐溶液预处理纤维。
如果希望,要着色的含角蛋白纤维进行预处理,之后用本发明的方法施加本发明的试剂。所需预处理步骤的时序和本发明试剂的施加不必一个紧接着一个,因为在预处理步骤和施加本发明的试剂之间间隔最大为两星期。许多的预处理方法适于该目的。优选纤维经如下处理:
V1在施加本发明的试剂之前进行漂白,或者
V2在施加本发明的试剂之前氧化着色。
在预处理V1的情况下,用漂白剂处理含角蛋白纤维。除了氧化剂,通常为过氧化氢,漂白剂优选包含至少一种无机的过氧盐作为活性的氧化助促进剂和漂白剂漂白剂助促进剂,比如钠、钾或者铵的过二硫酸盐。根据本发明的方法预处理V1可给着色提供特别的亮度和色浓度。
在预处理V2的情况下,纤维用包括前面提到的作为显色剂的氧化染料前体、任选的偶合剂组分和任选的前面提到的吲哚或者二氢吲哚衍生物的组合物进行处理,任选的向毛发中加入适当的前面提到的氧化剂,在该角蛋白纤维上停留5~45分钟的接触时间。然后洗涤该毛发。通过最后施加本发明的试剂,可赋予现有氧化着色新的色调。通过选择与氧化着色相同色调的本发明试剂的色度,这可在使用本发明的方法之后可使现有的氧化着色的着色被恢复。结果表明根据本发明方法的润色或者发色调整在颜色亮度和色浓度方面优于仅仅用通常的直接染料得到的润色或者发色调整。
如果除了通式I的化合物和任选的组分B之外,毛发着色剂包含过氧化氢或者包括含过氧化氢的氧化剂混合物,那么含过氧化氢的毛发着色剂的pH优选为7~11,特别优选为8~10。在使用之前氧化剂与毛发着色剂立即混合,将混合物施加到该毛发。当通式I的化合物和组分B以两步法施加到毛发上时,氧化剂与相应的着色组分在两个过程步骤中的之一中一起使用。为该目的,优选的是在容器中使氧化剂与一个着色组分混合。
通式I的1,2-二氢嘧啶鎓衍生物和组分B的化合物可以分别地存储或者存储在一起,以液体到糊状的制剂(水性的或者无水的)或者作为干粉的形式。如果组分以液体药剂形式存储在一起,那么这应基本上无水以减少组分的任何反应。对于单独贮藏,在它们的使用之前立即充分地将反应性组分混合在一起。对于干贮藏,通常在使用之前加入确定量的温水(30℃~80℃),制备均匀混合物。
本发明的第五主题是至少一种通式1和或它的烯胺形式的1,2-二氢嘧啶鎓衍生物,
其中,R1、R2、R3、R4、R5、Y和X-定义如上,与至少一种反应性羰基化合物(组分B)结合用于发色调整含角蛋白纤维特别是头发的氧化着色。一经使用,如果发色调整与氧化着色同时发生或者如果氧化着色在发色调整之前发生,这是不重要的。
本发明的第六主题是至少一种通式1和或它的烯胺形式的1,2-二氢嘧啶鎓衍生物,
其中,R1、R2、R3、R4、R5、Y和X-定义如上,与至少一种反应性羰基化合物(组分B)结合用于恢复用氧化着色剂着色的含角蛋白纤维的颜色。
熟知的是含角蛋白纤维的着色受环境的影响,比如光、摩擦或者洗涤,因此损失亮度和色浓度。在最坏条件下,发生色调的颜色变化。当用户希望,这样的含角蛋白纤维的老化着色可以通过润色从而被恢复以提供接近于初始着色的颜色。根据本发明,至少一种通式I的化合物和至少一种反应性羰基化合物的组合物可用于这样的润色。
实施例
着色剂溶液的制剂。
在大约50℃用在30ml水中3mmol的通式I(组分A)的1,2-二氢嘧啶鎓与0.41g乙酸钠的制备每一个浆料或者溶液。在即将使用之前将3mmol的组分B的化合物加入该混合物中。用10%氢氧化钠水溶液调节混合物的pH为9,或者用盐酸调节pH为4或者6(见表1)。
着色试验
一股90%灰色位未预处理的头发在30℃置于新鲜制备的着色剂溶液中30分钟。该股头发然后用温水漂洗30秒,用暖空气干燥(30℃~40℃),最后进行梳理。
颜色试验实施例的每一个色度和色浓度列于以下的表1。
组分A的化合物(在表1中):
A1 1,2-二氢-1,3,4,6-四甲基-2-氧代-氯化嘧啶
A2 1,2-二氢-1,3,4-三甲基-2-氧代-氯化嘧啶
A3 1,2-二氢-4,6-二甲基-1,3-二丙基-2-氧代-氯化嘧啶
A4 1,2-二氢-1,3,4,6-四甲基-2-硫代-硫酸氢嘧啶
A5 1,2-二氢-1,3,4,6-四甲基-2-氧代-硫酸氢嘧啶
A6 1,2-二氢-1,3,4,5,6-五甲基-2-氧代-氯化嘧啶
组分B的化合物(在表1中):
B1 2,4-二羟基苯甲醛
B2 香草醛
B3 靛红
B4 3-吲哚醛
B5 松柏醛
B6 3,5-二甲氧基-4-羟基苯甲醛
B7 4-二甲基氨基-1-萘甲醛
B8 4-羟基苯甲醛
B9 4-羟基-1-萘甲醛
B10 4-二乙基氨基-2-羟基苯甲醛
B11 4-二甲氨基苯甲醛
B12 4-羟基-2-甲氧基苯甲醛
B13 3,4-二羟基苯甲醛
B14 4-二甲基氨基亚肉桂醛
B15 3,5-二甲基-4-羟基苯甲醛
B16 2,3,4-三羟基苯甲醛
B17 2,4,6-三羟基苯甲醛
B18 3-羟基-4-甲氧基苯甲醛
B19 2-羟基-2-甲氧基苯甲醛
B20 2,3-二甲氧基苯甲醛
B21 2,4-二甲氧基苯甲醛
B22 2,3,4-三甲氧基苯甲醛
B23 2,4,5-三甲氧基苯甲醛
B24 3-溴代-4-甲氧基苯甲醛
B25 3-甲基-4-甲氧基苯甲醛
B26 4-二甲基氨基-2-甲氧基苯甲醛
B27 4-甲酰基-1-甲基喹啉鎓对-甲苯磺酸盐
B28 吡咯-2-甲醛
B29 1-甲基吡咯-2-甲醛
B30 2-糠醛
B31 4-二乙基氨基苯甲醛
B32 2,5-二羟基苯甲醛
B33 3-羟基-4-硝基苯甲醛
B34 2-羟基-3-甲氧基-5-硝基苯甲醛
B35 5-溴代-4-羟基-3-甲氧基苯甲醛
B36 4-甲氧基苯甲醛
B37 2-羟基-1-萘甲醛
B38 2-甲氧基-1-萘甲醛
B39 4-甲氧基-1-萘甲醛
B40 2-{[(4-甲基苯基)亚甲基]氨基}乙醇
B41 4-{[(2-羟乙基)亚氨基]甲基}-2,6-二甲氧基酚
B42 1-(二乙氧基甲基)-4-茴香醚
B43 4-(二乙氧基甲基)-2,6-二甲氧基酚
表1
组份A | 组份B | 颜色 | pH |
A1 | B1 | 正红violet | 9 |
A1 | B2 | 明亮的紫罗兰 | 9 |
A1 | B3 | 正橙色 | 9 |
A1 | B4 | intense orange | 9 |
A1 | B5 | 暗灰色 | 9 |
A1 | B6 | 正黑blue | 9 |
A1 | B7 | 淡灰 | 9 |
A1 | B8 | 正紫红 | 9 |
A1 | B9 | 灰黑 | 9 |
A1 | B10 | 浅粉红色 | 9 |
A1 | B11 | 正红紫罗兰 | 9 |
组份A | 组份B | 颜色 | pH |
A1 | B15 | 明亮的紫罗兰 | 9 |
A1 | B16 | 棕红色 | 9 |
A1 | B17 | 浅桃红 | 9 |
A1 | B18 | 褐色 | 9 |
A1 | B19 | 暗红 | 9 |
A1 | B20 | 黄褐色 | 9 |
A1 | B21 | 鲜橙色 | 9 |
A1 | B22 | 橙棕 | 9 |
A1 | B23 | 正橙红 | 9 |
A1 | B24 | 黄色 | 9 |
A1 | B25 | 褐橙色 | 9 |
A1 | B26 | 正紫罗兰 | 9 |
A1 | B27 | 褐色 | 9 |
A1 | B28 | 棕红色 | 9 |
A1 | B29 | 橙色 | 9 |
A1 | B30 | 米褐色 | 9 |
A2 | B1 | 红 | 9 |
A2 | B2 | 明亮的紫罗兰 | 9 |
A2 | B3 | 橙色 | 9 |
A2 | B4 | 橙色 | 9 |
A2 | B6 | 土耳其玉色 | 9 |
A2 | B8 | 粉红色 | 9 |
A2 | B9 | 黑色 | 9 |
A2 | B12 | 明亮的粉红色 | 9 |
A2 | B13 | 正深蓝色 | 9 |
A2 | B14 | 黄褐色 | 9 |
组份A | 组份B | 颜色 | pH |
A2 | B15 | 紫罗兰 | 9 |
A3 | B1 | 正暗红 | 9 |
A3 | B2 | 正紫罗兰 | 9 |
A4 | B1 | 粉红色 | 9 |
A4 | B2 | 中蓝色 | 9 |
A4 | B6 | 深蓝色、绿松石 | 9 |
A4 | B9 | 蓝黑色 | 6 |
A4 | B10 | 正暗红 | 6 |
A4 | B11 | 黑色 | 6 |
A4 | B15 | 明亮的紫罗兰 | 6 |
A4 | B23 | 大红 | 6 |
A4 | B25 | 正红 | 6 |
A4 | B27 | 褐色 | 6 |
A4 | B31 | 深蓝色 | 6 |
A4 | B40 | 橙黄 | 9 |
A4 | B41 | 深蓝色 | 9 |
A4 | B42 | 橙黄 | 4 |
A4 | B43 | 深蓝色 | 6 |
A5 | B9 | 深蓝色 | 6 |
A5 | B32 | 绿褐色 | 9 |
A5 | B33 | 褐橙色 | 9 |
A5 | B34 | 黑色 | 9 |
A5 | B35 | 明亮的紫罗兰 | 9 |
A5 | B36 | 鲜橙色 | 9 |
A5 | B37 | 深蓝色 | 9 |
A5 | B38 | 灰粉红色 | 9 |
组份A | 组份B | 颜色 | pH |
A6 | B1 | 粉红色 | 9 |
A6 | B2 | 正紫罗兰 | 9 |
A6 | B6 | 正绿蓝色 | 9 |
A6 | B8 | 粉红色 | 9 |
A6 | B9 | 绿色 | 9 |
A6 | B12 | 粉红色 | 9 |
A6 | B13 | 正灰蓝色 | 9 |
A6 | B15 | 紫罗兰 | 9 |
Claims (34)
1.一种用于染色含角蛋白纤维特别是头发的试剂,包括根据通式1和、或其烯胺形式的至少一种1,2-二氢嘧啶鎓衍生物,
■其中,R1和R2彼此独立地代表直链的或者环状的C1-C6烷基、C2-C6链烯基团、任选取代的芳基、任选取代的杂芳基、芳基C1-C6烷基、C1-C6羟烷基、C2-C6多羟烷基、C1-C6烷氧基-CI-C6烷基、基团RIRIIN-(CH2)m-,其中RI和RII彼此独立地代表氢原子、C1-C4烷基、C1-C4羟烷基或者芳基C1-C6烷基,其中RI和RII与氮原子一起可形成5-,6-或者7-元环,和m代表2,3,4,5或者6。
■R3和R4彼此独立地代表氢原子或者C1-C6烷基,其中基团R3和R4的至少一种是指C1-C6烷基,
■R5代表氢原子、C1-C6烷基、C1-C6羟烷基、C2-C6多羟烷基团、C1-C6烷氧基、C1-C6羟基烷氧基、基团RIIIRIVN-(CH2)q-,其中RIII和RIV彼此独立地代表氢原子、C1-C6烷基、C1-C6羟烷基或者芳基C1-C6烷基,及q代表1、2、3、4、5或者6,其中基团R5与R3或者R4基团之一一起可形成5-或者6-元芳烃或者脂肪族的环,而且所述的环可以任选被如下的基团取代,卤素原子、C1-C6烷基、C1-C6羟烷基、C2-C6多羟烷基团、C1-C6烷氧基、C1-C6羟基烷氧基、硝基、羟基、基团RVRVIN-(CH2)s-,其中RV和RVI彼此独立地代表氢原子、C1-C6烷基、C1-C6羟烷基或者芳基C1-C6烷基,s代表0、1、2、3、4、5或者6,
■Y代表氧原子、硫原子或者基团NRVII,其中RVII代表氢原子、芳基、杂芳基、C1-C6烷基或者C1-C6芳烷基,
■X-代表卤化物、苯磺酸盐、对甲苯磺酸盐、C1-C4链烷磺酸盐、三氟甲烷磺酸盐、高氯酸盐、0.5硫酸盐、硫酸氢盐、四氟硼酸盐、六氟磷酸盐或者四氯锌酸盐,
和至少一种含有反应性羰基(组分B)的化合物。
2.根据权利要求1的试剂,特征在于Y代表氧原子或者硫原子。
3.根据权利要求1或者2的试剂,特征在于Y代表氧原子。
4.根据权利要求1~3之一的试剂,特征在于基团R3或者R4的至少一个代表甲基。
5.根据权利要求1~4之一的试剂,特征在于X-代表氯化物、溴化物、碘化物、硫酸氢盐或者对甲苯磺酸盐。
6.根据权利要求1~5之一的试剂,特征在于根据通式I的化合物选自1,2-二氢-1,3,4,6-四甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3-二乙基-4,6-二甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3-二丙基-4,6-二甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3-二(2-羟乙基)-4,6-二甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3-联苯-4,6-二甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3,4,6-四甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-二乙基-4,6-二甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-二丙基-4,6-二甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-二(2-羟乙基)-4,6-二甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-联苯-4,6-二甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3,4-三甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3,4-三甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-二乙基-4-甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3-二乙基-4-甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-二丙基-4-甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3-二丙基-4-甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-二(2-羟乙基)-4-甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3-二(2-羟乙基)-4-甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-联苯-4-甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3-联苯-4-甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3,4,5,6-五甲基-2-氧代-氯化嘧啶、1,2-二氢-1,3,4,6-四甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3-二乙基-4,6-二甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3-二丙基-4,6-二甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3-二(2-羟乙基)-4,6-二甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3-联苯-4,6-二甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3,4,6-四甲基-2-氧代-硫酸氢嘧啶、1,2-二氢-1,3-二丙基-4,6-二甲基-2-硫代-硫酸氢嘧啶、1,2-二氢-1,3-二(2-羟乙基)-4,6-二甲基-2-硫代-硫酸氢嘧啶、1,2-二氢-1,3-联苯-4,6-二甲基-2-硫代-硫酸氢嘧啶、1,2-二氢-1,3,4-三甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3,4-三甲基-2-硫代-硫酸氢嘧啶、1,2-二氢-1,3-二乙基-4-甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3-二乙基-4-甲基-2-硫代-硫酸氢嘧啶、1,2-二氢-1,3-二丙基-4-甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3-二丙基-4-甲基-2-硫代-硫酸氢嘧啶、1,2-二氢-1,3-二(2-羟乙基)-4-甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3-二(2-羟乙基)-4-甲基-2-硫代-硫酸氢嘧啶、1,2-二氢-1,3-联苯-4-甲基-2-硫代-氯化嘧啶、1,2-二氢-1,3-联苯-4-甲基-2-硫代-硫酸氢嘧啶、1,2-二氢-3,4-二甲基-2-氧代-氯化喹唑啉、1,2-二氢-3,4-二甲基-2-氧代-对甲苯磺酸喹唑啉、1,2-二氢-3,4-二甲基-2-硫代-氯化喹唑啉、1,2-二氢-3,4-二甲基-2-硫代-对甲苯磺酸喹唑啉、1,2-二氢-1,3,4-三甲基-2-硫代-硫酸氢喹唑啉、1,3,4-三甲基-2-氧代-2,3,5,6,7,8-硫酸氢六氢喹啉、1,3,4-三甲基-2-硫代-2,3,5,6,7,8-硫酸氢六氢喹啉、1,3,4-三甲基-2-氧代-3,5,6,7-四氢-2H-环戊二烯并硫酸氢嘧啶和1,3,4-三甲基-2-硫代-3,5,6,7-四氢-2H-环戊二烯并硫酸氢嘧啶。
7.根据权利要求1~6之一的试剂,特征在于组分B选自根据通式II的化合物,
■其中AR代表苯、萘、吡啶、嘧啶、吡嗪、哒嗪、咔唑、吡咯、吡唑、呋喃、噻吩、1,2,3-三嗪、1,3,5-三嗪、喹啉、异喹啉、吲哚、二氢吲哚、中氮茚、二氢化茚、咪唑、1,2,4-三唑、1,2,3-三唑、四唑、苯并咪唑、1,3-噻唑、苯并噻唑、吲唑、苯并恶唑、喹喔啉、喹唑啉、喹嗪、噌啉、吖啶、久洛尼定、苊、芴、联苯基、二苯基甲烷、二苯甲酮、二苯醚、偶氮苯、色酮、香豆素、二苯胺、芪,其中N-杂原子还可以被季铵化,
■R6代表氢原子、C1-C6烷基、C2-C6酰基、C2-C4链烯基、C1-C4全氟烷基、任选取代的芳基或者杂芳基,
■R7、R8和R9互相独立地代表氢原子、卤素原子、C1-C6烷基、C1-C6烷氧基、C1-C6氨基烷基、C1-C6羟烷基、C1-C6烷氧基C1-C6烷基氧基、C2-C6酰基,乙酰基、羧基、羧酸根合、氨甲酰基、磺基、硫酸根合、磺酰胺、磺酰氨基、C2-C6链烯基、芳基、芳基C1-C6烷基、羟基、硝基、吡咯烷基、吗啉代、哌啶基、氨基、胺基或者1-咪唑啉基,其中后三个基团可以被一种或多种C1-C6烷基、C1-C6羧烷基C1-C6羟烷基、C2-C6链烯基、C1-C6烷氧基C1-C6烷基取代,用任选取代的苄基、磺基(C1-C4)烷基或者杂环(C1-C4)烷基取代,
其中基团R7、R8、R9和-Z-Y-R6的两个也和该分子的残基一起形成缩合的任选取代的5-、6-或者7-元环,所述的环上同样可有缩合的芳环,其中体系AR取决于环尺寸可以有另外的取代基,所述的取代基彼此独立地代表相同的基团如R7、R8和R9,
■Z代表直接键合、羰基、羧基(C1-C4)亚烷基、任选取代的C2-C6链烯基、C4-C6链二烯、亚呋喃基、亚噻吩基、亚芳基、亚乙烯基亚芳基、亚乙烯基亚呋喃基、亚乙烯基亚噻吩基,其中Z与-Y-R6基团还可以一起形成任选取代的5-6-或者7-元环。
■Y代表选自羰基、根据通式III的基团和根据通式IV的基团,
■其中R10代表氢原子、羟基、C1-C4烷氧基、C1-C6烷基、C1-C6羟烷基、C2-C6多羟烷基、C1-C6烷氧基C1-C6烷基,
■R11和R12彼此独立地代表C1-C6烷基、芳基或者与通式IV的结构元素O-C-O一起形成5-或者6-元环。
8.根据权利要求1~7之一的试剂,特征在于组分B选自苯乙酮、苯丙酮、2-羟苯乙酮、3-羟苯乙酮、4-羟苯乙酮、2-羟苯丙酮、3-羟苯丙酮、4-羟苯丙酮、2-羟苯丁酮、3-羟苯丁酮、4-羟苯丁酮、2,4-二羟基苯乙酮、2,5-二羟基苯乙酮、2,6-二羟基苯乙酮、2,3,4-三羟基苯乙酮、3,4,5-三羟基苯乙酮、2,4,6-三羟基苯乙酮、2,4,6-三甲氧基苯乙酮、3,4,5-三甲氧基苯乙酮、3,4,5-三甲氧基苯乙酮-二乙基缩酮、4-羟基-3-甲氧基-苯乙酮、3,5-二甲氧基-4-羟苯乙酮、4-氨基苯乙酮、4-二甲基氨基苯乙酮、4-吗啉基苯乙酮、4-哌啶基苯乙酮、4-咪唑基苯乙酮、2-羟基-5-溴代-苯乙酮、4-羟基-3-硝基苯乙酮、苯乙酮-2-羧酸、苯乙酮-4-羧酸、二苯甲酮、4-羟基二苯甲酮、2-氨基二苯甲酮、4,4′-二羟基二苯甲酮、2,4-二羟基-二苯甲酮、2,4,4′-三羟基二苯甲酮、2,3,4-三羟基二苯甲酮、2-羟基-1-萘乙酮、1-羟基-2-萘乙酮、色酮、色酮-2-羧酸、黄酮、3-羟基黄酮、3,5,7-三羟基黄酮、4′,5,7-三羟基黄酮、5,6,7-三羟基黄酮、五羟黄酮、1-2,3-二氢-1-茚酮、9-芴酮、3-羟基芴酮、蒽酮、1,8-二羟基蒽酮、香草醛、松柏醛、2-甲氧基苯甲醛、3-甲氧基苯甲醛、4-甲氧基苯甲醛、2-乙氧基苯甲醛、3-乙氧基苯甲醛、4-乙氧基苯甲醛、4-羟基-2,3-二甲氧基-苯甲醛、4-羟基-2,5-二甲氧基-苯甲醛、4-羟基-2,6-二甲氧基-苯甲醛、4-羟基-2-甲基苯甲醛、4-羟基-3-甲基-苯甲醛、4-羟基-2,3-二甲基苯甲醛、4-羟基-2,5-二甲基-苯甲醛、4-羟基-2,6-二甲基苯甲醛、4-羟基-3,5-二甲氧基-苯甲醛、4-羟基-3,5-二甲基苯甲醛、3,5-二乙氧基-4-羟基-苯甲醛、2,6-二乙氧基-4-羟基苯甲醛、3-羟基-4-甲氧基-苯甲醛、2-羟基-2-甲氧基苯甲醛、2-乙氧基-4-羟基-苯甲醛、3-乙氧基-4-羟基-苯甲醛、4-乙氧基-2-羟基-苯甲醛、4-乙氧基-3-羟基-苯甲醛、2,3-二甲氧基苯甲醛、2,4-二甲氧基苯甲醛、2,5-二甲氧基苯甲醛、2,6-二甲氧基苯甲醛、3,4-二甲氧基苯甲醛、3,5-二甲氧基苯甲醛、2,3,4-三甲氧基苯甲醛、2,3,5-三甲氧基苯甲醛、2,3,6-三甲氧基苯甲醛、2,4,6-三甲氧基苯甲醛、2,4,5-三甲氧基苯甲醛、2,5,6-三甲氧基苯甲醛、2-羟基苯甲醛、3-羟基苯甲醛、4-羟基苯甲醛、2,3-二羟基苯甲醛、2,4-二羟基苯甲醛、2,5-二羟基苯甲醛、2,6-二羟基苯甲醛、3,4-二羟基苯甲醛、3,5-二羟基苯甲醛、2,3,4-三羟基苯甲醛、2,3,5-三羟基苯甲醛、2,3,6-三羟基苯甲醛、2,4,6-三羟基苯甲醛、2,4,5-三羟基苯甲醛、2,5,6-三羟基苯甲醛、4-羟基-2-甲氧基苯甲醛、4-二甲氨基苯甲醛、4-二乙基氨基苯甲醛、4-二甲基氨基-2-羟基苯甲醛、4-二乙基氨基-2-羟基苯甲醛、4-吡咯烷基苯甲醛、4-吗啉基苯甲醛、2-吗啉基苯甲醛、4-哌啶基苯甲醛、2-甲氧基-1-萘甲醛、4-甲氧基-1-萘甲醛、2-羟基-1-萘甲醛、2,4-二羟基-1-萘甲醛、4-羟基-3-甲氧基-1-萘甲醛、2-羟基-4-甲氧基-1-萘甲醛、3-羟基-4-甲氧基-1-萘甲醛、2,4-二甲氧基-1-萘甲醛、3,4-二甲氧基-1-萘甲醛、4-羟基-1-萘甲醛、4-二甲基氨基-1-萘甲醛、4-二甲基氨基亚肉桂醛、2-二甲氨基苯甲醛、2-氯代-4-二甲氨基苯甲醛、4-二甲基氨基-2-甲基苯甲醛、4-二乙基氨基亚肉桂醛、4-二丁基氨基苯甲醛、4-二苯基氨基-苯甲醛、4-二甲基氨基-2-甲氧基苯甲醛、4-(1-咪唑基)-苯甲醛、胡椒醛、2,3,6,7-四氢化-1H,5H-苯并[ij]喹嗪-9-甲醛、2,3,6,7-四氢化-8-羟基-1H,5H-苯并[ij]喹嗪-9-甲醛、N-乙基咔唑-3-醛、2-甲酰基亚甲基-1,3,3-三甲基二氢吲哚(Fischer醛或者tribasen醛)、2-吲哚醛、3-吲哚醛、1-甲基吲哚-3-醛、2-甲基吲哚-3-醛、1-乙酰基吲哚-3-醛、3-乙酰基吲哚、1-甲基-3-乙酰基吲哚、2-(1′,3′,3′-三甲基-2-二氢亚吲哚基)乙醛、1-甲基吡咯-2-醛、1-甲基-2-乙酰基吡咯、4-嘧啶醛、2-嘧啶醛、3-嘧啶醛、4-乙酰基吡啶、2-乙酰基吡啶、3-乙酰基吡啶、吡哆醛、喹啉-3-醛、喹啉-4-醛、安替比林-4-醛、糠醛、5-硝基糠醛、2-噻吩甲酰-三氟丙酮、色酮-3-醛、3-(5′-硝基-2′-呋喃基)-丙烯醛、3-(2′-呋喃基)-丙烯醛和咪唑-2-醛、1,3-二乙酰基苯、1,4-二乙酰基苯、1,3,5-三乙酰基苯、2-苯甲酰基-苯乙酮、2-(4′-甲氧苯甲酰)苯乙酮、2-(2′-糠酰)苯乙酮、2-(2′-吡啶酰基)苯乙酮和2-(3′-吡啶酰基)苯乙酮、亚苄基丙酮、4-羟基苯亚甲基丙酮、2-羟基苯亚甲基丙酮、4-甲氧亚苄基丙酮、4-羟基-3-甲氧亚苄基丙酮、4-二甲基氨基亚苄基丙酮、3,4-亚甲二氧基亚苄基丙酮、4-吡咯烷基亚苄基丙酮、4-哌啶基亚苄基丙酮、4-吗啉基苯亚甲基丙酮、4-二乙基氨基苯亚甲基丙酮、3-亚苄基-2,4-戊二酮、3-(4′-羟基苯亚甲基)-2,4-戊二酮、3-(4′-二甲基氨基亚苄基丙酮)-2,4-戊二酮、2-苯亚甲基环己酮、2-(4′-羟基苯亚甲基)环己酮、2-(4’-二甲基氨基亚苄基)环己酮、2-亚苄基-1,3-环己二酮、2-(4′-羟基苯亚甲基)-1,3-环己二酮、3-(4’-二甲基氨基亚苄基)-1,3-环己二酮、2-亚苄基-5,5-二甲基-1,3-环己二酮、2-(4′-羟基苯亚甲基)-5,5-二甲基-1,3-环己二酮、2-(4′-羟基-3-甲氧亚苄基)-5,5-二甲基-1,3-环己二酮、2-(4’-二甲基氨基亚苄基)-5,5-二甲基-1,3-环己二酮、2-苯亚甲基环戊酮、2′-(4-羟基苯亚甲基)-环戊酮、2-(4’-二甲基氨基亚苄基)环戊酮、5-(4-甲基氨基苯基)戊-2,4-二烯醛、5-(4-乙基氨基苯基)戊-2,4-二烯醛、5-(4-甲基苯基)戊-2,4-二烯醛、5-(3,4-二甲氧基苯基)戊-2,4-二烯醛、5-(2,4-二甲氧基苯基)戊-2,4-二烯醛、5-(4-哌啶基苯基)戊-2,4-二烯醛、5-(4-吗啉基苯基)戊-2,4-二烯醛、5-(4-吡咯烷基苯基)戊-2,4-二烯醛、6-(4-二甲基氨基苯基)六-3,5-二烯-2-酮、6-(4-二乙基氨基苯基)六-3,5-二烯-2-酮、6-(4-甲氧基苯基)六-3,5-二烯-2-酮、6-(3,4-二甲氧基苯基)六-3,5-二烯-2-酮、6-(2,4-二甲氧基苯基)六-3,5-二烯-2-酮、6-(4-哌啶基苯基)六-3,5-二烯-2-酮、6-(4-吗啉基苯基)六-3,5-二烯-2-酮、6-(4-吡咯烷基苯基)六-3,5-二烯-2-酮、5-(4-二甲基氨基-1-萘基)戊-3,5-二烯醛、2-硝基苯甲醛、3-硝基苯甲醛、4-硝基苯甲醛、4-甲基-3-硝基苯甲醛、3-羟基-4-硝基苯甲醛、4-羟基-3-硝基苯甲醛、5-羟基-2-硝基苯甲醛、2-羟基-5-硝基苯甲醛、2-羟基-3-硝基苯甲醛、2-氟代-3-硝基苯甲醛、3-甲氧基-2-硝基苯甲醛、4-氯代-3-硝基苯甲醛、2-氯代-6-硝基苯甲醛、5-氯代-2-硝基苯甲醛、4-氯代-2-硝基苯甲醛、2,4-二硝基苯甲醛、2,6-二硝基苯甲醛、2-羟基-3-甲氧基-5-硝基苯甲醛、4,5-二甲氧基-2-硝基苯甲醛、6-硝基胡椒醛、2-硝基胡椒醛、5-硝基香草醛、2,5-二硝基水杨醛、5-溴代-3-硝基水杨醛、3-硝基-4-甲酰基苯磺酸、4-硝基-1-萘甲醛、2-硝基肉桂醛、3-硝基肉桂醛、4-硝基肉桂醛、9-乙基-3-咔唑醛、3-乙酰基咔唑、3,6-二乙酰基-9-乙基咔唑、3-乙酰基-9-甲基咔唑、1,4-二甲基-3-咔唑醛、1,4,9-三甲基-3-咔唑醛、4-甲酰基-1-甲基吡啶鎓、2-甲酰基-1-甲基吡啶鎓-、4-甲酰基-1-乙基吡啶鎓-、2-甲酰基-1-乙基吡啶鎓-、4-甲酰基-1-苯基吡啶鎓-、2-甲酰基-1-苯基吡啶鎓-、4-甲酰基-1,2-二甲基吡啶鎓-、4-甲酰基-1,3-二甲基吡啶鎓-、4-甲酰基-1-甲基喹啉鎓-、2-甲酰基-1-甲基喹啉鎓-、4-乙酰基-1-甲基吡啶鎓-、2-乙酰基-1-甲基吡啶鎓-、4-乙酰基-1-甲基喹啉鎓-、5-甲酰基-1-甲基喹啉鎓-、6-甲酰基-1-甲基喹啉鎓-、7-甲酰基-1-甲基喹啉鎓-、8-甲酰基-1-甲基喹啉鎓-、5-甲酰基-1-乙基喹啉鎓-、6-甲酰基-1-乙基喹啉鎓-、7-甲酰基-1-乙基喹啉鎓-、8-甲酰基-1-乙基喹啉鎓-、5-甲酰基-1-苯基喹啉鎓-、6-甲酰基-1-苯基喹啉鎓-、7-甲酰基-1-苯基喹啉鎓-、8-甲酰基-1-苯基喹啉鎓、5-甲酰基-1-烯丙基喹啉鎓-、6-甲酰基-1-烯丙基喹啉鎓-、7-甲酰基-1-烯丙基喹啉鎓-和8-甲酰基-1-烯丙基喹啉鎓-、5-乙酰基-1-甲基喹啉鎓-、6-乙酰基-1-甲基喹啉鎓-、7-乙酰基-1-甲基喹啉鎓-、8-乙酰基-1-甲基喹啉鎓、5-乙酰基-1-乙基喹啉鎓-、6-乙酰基-1-乙基喹啉鎓-、7-乙酰基-1-乙基喹啉鎓-、8-乙酰基-1-乙基喹啉鎓、5-乙酰基-1-苯基喹啉鎓-、6-乙酰基-1-苯基喹啉鎓-、7-乙酰基-1-苯基喹啉鎓、8-乙酰基-1-苯基喹啉鎓-、5-乙酰基-1-烯丙基喹啉鎓-、6-乙酰基-1-烯丙基喹啉鎓-、7-乙酰基-1-烯丙基喹啉鎓-和8-乙酰基-1-烯丙基喹啉鎓-、9-甲酰基-10-甲基吖啶鎓-、4-(2′-甲酰基乙烯基)-1-甲基吡啶鎓-、1,3-二甲基-2-(4′-甲酰基苯基)苯并咪唑鎓-、1,3-二甲基-2-(4′-甲酰基苯基)咪唑鎓-、2-(4′-甲酰基苯基)-3-甲基苯并噻唑鎓-、2-(4′-乙酰基苯基)-3-甲基苯并噻唑鎓-、2-(4′-甲酰基苯基)-3-甲基苯并恶唑鎓-、2-(5′-甲酰基-2′-呋喃基)-3-甲基苯并噻唑鎓-、2-(5′-甲酰基-2′-呋喃基)-3-甲基苯并噻唑鎓-、2-(5′-甲酰基-2′-噻吩基)-3-甲基苯并噻唑鎓-、2-(3′-甲酰基苯基)-3-甲基苯并噻唑鎓-、2-(4′-甲酰基-1-萘基)-3-甲基苯并噻唑鎓-、5-氯代-2-(4′-甲酰基苯基)-3-甲基苯并噻唑鎓-、2-(4′-甲酰基苯基)-3,5-二甲基苯并噻唑鎓苯磺酸盐、-对-甲苯磺酸盐、-甲烷磺酸盐、-高氯酸盐、-硫酸盐、-氯化物、-溴化物、-碘化物、-四氯锌酸盐、-甲基磺酸盐、-三氟甲烷磺酸盐、-四氟硼酸盐、靛红、1-甲基-靛红、1-烯丙基-靛红、1-羟甲基-靛红、5-氯代-靛红、5-甲氧基-靛红、5-硝基靛红、6-硝基靛红、5-磺基靛红、5-羧基靛红、奎靛红、1-甲基奎靛红和上述化合物的任何混合物。
9.根据权利要求1~8之一的试剂,特征在于组分B选自香草醛、松柏醛、2-甲氧基苯甲醛、3-甲氧基苯甲醛、4-甲氧基苯甲醛、2-乙氧基苯甲醛、3-乙氧基苯甲醛、4-乙氧基苯甲醛、4-羟基-2,3-二甲氧基-苯甲醛、4-羟基-2,5-二甲氧基苯甲醛、4-羟基-2,6-二甲氧基苯甲醛、4-羟基-2-甲基苯甲醛、4-羟基-3-甲基苯甲醛、4-羟基-2,3-二甲基苯甲醛、4-羟基-2,5-二甲基苯甲醛、4-羟基-2,6-二甲基苯甲醛、4-羟基-3,5-二甲氧基苯甲醛、4-羟基-3,5-二甲基苯甲醛、3,5-二乙氧基-4-羟基苯甲醛、2,6-二乙氧基-4-羟基苯甲醛、3-羟基-4-甲氧基苯甲醛、2-羟基-2-甲氧基苯甲醛、2-乙氧基-4-羟基苯甲醛、3-乙氧基-4-羟基苯甲醛、4-乙氧基-2-羟基-苯甲醛、4-乙氧基-3-羟基苯甲醛、2,3-二甲氧基苯甲醛、2,4-二甲氧基苯甲醛、2,5-二甲氧基苯甲醛、2,6-二甲氧基苯甲醛、3,4-二甲氧基苯甲醛、3,5-二甲氧基苯甲醛、2,3,4-三甲氧基苯甲醛、2,3,5-三甲氧基苯甲醛、2,3,6-三甲氧基苯甲醛、2,4,6-三甲氧基苯甲醛、2,4,5-三甲氧基苯甲醛、2,5,6-三甲氧基苯甲醛、2-羟基苯甲醛、3-羟基苯甲醛、4-羟基苯甲醛、2,3-二羟基苯甲醛、2,4-二羟基苯甲醛、2,5-二羟基苯甲醛、2,6-二羟基苯甲醛、3,4-二羟基苯甲醛、3,5-二羟基苯甲醛、2,3,4-三羟基苯甲醛、2,3,5-三羟基苯甲醛、2,3,6-三羟基苯甲醛、2,4,6-三羟基苯甲醛、2,4,5-三羟基苯甲醛、2,5,6-三羟基苯甲醛、4-羟基-2-甲氧基苯甲醛、4-二甲氨基苯甲醛、4-二乙基氨基苯甲醛、4-二甲基氨基-2-羟基苯甲醛、4-二乙基氨基-2-羟基苯甲醛、4-吡咯烷基苯甲醛、4-吗啉基苯甲醛、2-吗啉基苯甲醛、4-哌啶基苯甲醛、2-甲氧基-1-萘甲醛、4-甲氧基-1-萘甲醛、2-羟基-1-萘甲醛、2,4-二羟基-1-萘甲醛、4-羟基-3-甲氧基-1-萘甲醛、2-羟基-4-甲氧基-1-萘甲醛、3-羟基-4-甲氧基-1-萘甲醛、2,4-二甲氧基-1-萘甲醛、3,4-二甲氧基-1-萘甲醛、4-羟基-1-萘甲醛、4-二甲基氨基-1-萘甲醛、4-二甲基氨基亚肉桂醛、2-二甲氨基苯甲醛、2-氯代-4-二甲氨基苯甲醛、4-二甲基氨基-2-甲基苯甲醛、4-二乙基氨基亚肉桂醛、4-二丁基氨基苯甲醛、4-二苯基氨基苯甲醛、4-二甲基氨基-2-甲氧基苯甲醛、4-(1-咪唑基)-苯甲醛和胡椒醛。
10.根据权利要求1~9之一的试剂,特征在于其包括至少一种化合物作为组分C,所述的组分C选自(a)CH-酸化合物和(b)含有一级或者二级氨基或者羟基的化合物,其选自芳烃羟基化合物、一级或者二级芳香胺和含氮杂环化合物。
11.根据权利要求10的试剂,特征在于组份C的CH-酸化合物选自1,2,3,3-四甲基-3H-碘化吲哚、1,2,3,3-四甲基-3H-对甲苯磺酸吲哚、1,2,3,3-四甲基-3H-甲烷磺酸吲哚、1,3,3-三甲基-2-亚甲基二氢吲哚(Fischer碱)、2,3-二甲基-苯并噻唑鎓碘化物、2,3-二甲基苯并噻唑鎓吲哚对甲苯磺酸盐、2,3-二甲基-萘并[1,2-d]噻唑鎓对甲苯磺酸盐、3-乙基-2-甲基-萘并[1,2-d]对甲苯磺酸噻唑鎓盐、绕丹宁、绕丹宁-3-乙酸、1,4-碘化二甲基喹啉鎓、1,2-碘化二甲基喹啉鎓、巴比土酸、硫代巴比土酸、1,3-二甲基硫代巴比土酸、1,3-二乙基硫代巴比土酸、1,3-二乙基巴比妥酸、2-羟基吲哚、3-乙酸吲羟酯、2-香豆冉酮、5-羟基-2-香豆冉酮、6-羟基-2-香豆冉酮、3-甲基-1-苯基-吡唑啉-5-酮、二氢化茚-1,2-二酮、二氢化茚-1,3-二酮、茚满-1-酮、苯甲酰乙腈、3-二氰亚甲基茚满-1-酮、2-氨基-4-亚氨基-1,3-盐酸噻唑啉化物、5,5-二甲基环己烷-1,3-二酮、2H-1,4-苯并恶嗪-4H-3-酮、3-乙基-2-甲基-苯并恶唑鎓碘化物、3-乙基-2-甲基苯并噻唑鎓碘化物、1-乙基-4-甲基喹啉鎓碘化物、1-乙基-2-甲基喹啉鎓碘化物、1,2,3-三甲基喹啉鎓碘化物、3-乙基-2-苯并恶唑鎓对甲苯磺酸盐、3-乙基-2-甲基-苯并噻唑鎓对甲苯磺酸盐、1-乙基-4-甲基-喹啉鎓对甲苯磺酸盐、1-乙基-2-甲基喹啉鎓对甲苯磺酸盐和1,2,3-三甲基喹喔啉鎓对甲苯磺酸盐。
12.根据权利要求10的试剂,特征在于组份C的一级和二级芳香胺选自:N,N-二甲基-对苯二胺、N,N-二乙基-对苯二胺、N-(2-羟乙基)-N-乙基-对苯二胺、N,N-二(2-羟乙基)-对苯二胺、N-(2-甲氧基乙基)-对苯二胺、2,3-二氯-对苯二胺、2,4-二氯-对苯二胺、2,5-二氯-对苯二胺、2-氯代-对苯二胺、2,5-二羟基-4-吗啉基苯胺、2-氨基苯酚、3-氨基苯酚、4-氨基苯酚、2-氨甲基-4-氨基苯酚、2-羟甲基-4-氨基苯酚、邻苯二胺、间苯二胺、对苯二胺、2,5-二氨基甲苯、2,5-二氨基苯酚、2,5-二氨基茴香醚、2,5-二氨基苯乙醇、4-氨基-3-甲基苯酚、2-(2,5-二氨基苯基)乙醇、2,4-二氨基苯氧基乙醇、2-(2,5-二氨基苯氧基)乙醇、3-氨基-4-(2-羟乙氧基)苯酚、3,4-亚甲二氧基苯酚、3,4-亚甲二氧基苯胺、3-氨基-2,4-二氯苯酚、4-甲基氨基苯酚、2-甲基-5-氨基苯酚、3-甲基-4-氨基苯酚、2-甲基-5-(2-羟乙基氨基)酚、3-氨基-2-氯代-6-甲基苯酚、2-甲基-5-氨基-4-氯酚、5-(2-羟乙基氨基)-4-甲氧基-2-甲基苯酚、4-氨基-2-羟基甲基苯酚、2-(二乙基氨甲基)-4-氨基苯酚、4-氨基-1-羟基-2-(2-羟基乙基氨基甲基)苯、1-羟基-2-氨基-5-甲基-苯、1-羟基-2-氨基-6-甲基-苯、2-氨基-5-乙酰胺基苯酚、1,3-二甲基-2,5-苯二胺、5-(3-羟基丙基氨基)-2-甲基苯酚、5-氨基-4-甲氧基-2-甲基苯酚、N,N-二甲基-3-氨基苯酚、N-环戊基-3-氨基苯酚、5-氨基-4-氟代-2-甲基苯酚、2,4-二氨基-5-氟代甲苯、2,4-二氨基-5-(2-羟基乙氧基)-甲苯、2,4-二氨基-5-甲基苯乙醚、3,5-二氨基-2-甲氧基-1-甲苯、2-氨基-4-(2-羟乙基氨基)茴香醚、2,6-二(2-羟乙基氨基)-1-甲苯、1,3-二氨基-2,4-二甲氧基苯、3,5-二氨基-2-甲氧基-甲苯、2-氨基苯甲酸、3-氨基苯甲酸、4-氨基苯甲酸、2-氨基苯乙酸、3-氨基苯乙酸、4-氨基苯乙酸、2,3-二氨基苯甲酸、2,4-二氨基苯甲酸、2,5-二氨基苯甲酸、3,4-二氨基苯甲酸、3,5-二氨基苯甲酸、4-氨基水杨酸、5-氨基水杨酸、3-氨基-4-羟基苯甲酸、4-氨基-3-羟基苯甲酸、2-氨基苯磺酸、3-氨基苯磺酸、4-氨基苯磺酸、3-氨基-4-羟基苯磺酸、4-氨基-3-羟基萘-1-磺酸、6-氨基-7-羟基萘-2-磺酸、7-氨基-4-羟基萘-2-磺酸、4-氨基-5-羟基萘-2,7-二磺酸、3-氨基-2-萘甲酸、3-氨基酞酸、5-氨基间苯二甲酸、1,3,5-三氨基苯、1,2,4-三氨基苯、1,2,4,5-四氨基苯、2,4,5-三氨基酚、五氨基苯、六氨基苯、2,4,6-三氨基间苯二酚、4,5-二氨基邻苯二酚、4,6-二氨基连苯三酚、1-(2-羟基-5-氨基苯甲基)-2-咪唑啉酮、4-氨基-2((4-[(5-氨基-2-羟苯基)甲基]-哌嗪基)甲基)苯酚、3,5-二氨基-4-羟基邻苯二酚、1,4-二(4-氨基苯基)-1,4-二氮环庚烷、芳腈比如2-氨基-4-羟基苯腈、4-氨基-2-羟基苯腈、4-氨基苯基腈、2,4-二氨基苯基腈、含有硝基的氨基化合物比如3-氨基-6-甲基氨基-2-硝基吡啶、苦氨酸、[8-[(4-氨基-2-硝基苯基)-偶氮基]-7-羟基-萘--2-基]三甲基氯化铵、[8-[(4-氨基-3-硝基苯基)-偶氮基)-7-羟基-萘-2-基]]三甲基氯化铵(碱性棕17)、1-羟基-2-氨基-4,6-二硝基苯、1-氨基-2-硝基-4-[二(2-羟乙基)氨基]苯、1-氨基-2-[(2-羟乙基)氨基]-5-硝基苯(HC Yellow Nr.5)、1-氨基-2-硝基-4-[(2-羟乙基)氨基]苯(HC Red Nr.7)、2-氯代-5-硝基-N-2-羟乙基-1,4-苯二胺、1-[(2-羟乙基)氨基]-2-硝基-4-氨基苯(HC Red Nr.3)、4-氨基-3-硝基苯酚、4-氨基-2-硝基苯酚、6-硝基-邻甲苯胺、1-氨基-3-甲基-4-[(2-羟乙基)氨基]-6-硝基苯(HC Violet Nr.1)、1-氨基-2-硝基-4-[(2,3-二羟基丙基)氨基]-5-氯苯(HC Red Nr.10)、2-(4-氨基-2-硝基苯胺基)苯甲酸、6-硝基-2,5-二氨基吡啶、2-氨基-6-氯代-4-硝基苯酚、1-氨基-2-(3-硝基苯基偶氮)-7-苯基偶氮-8-萘酚-3,6-二磺酸的二钠盐(acid blueNr.29)、1-氨基-2-(2-羟基-4-硝基苯基偶氮)-8-萘酚-3,6-二磺酸的二钠盐(Palatinchrome green)、1-氨基-2-(3-氯代-2-羟基-5-硝基苯基偶氮)-8-萘酚-3,6-二磺酸的二钠盐(Gallion)、4-氨基-4′-硝基芪-2,2′-二磺酸的二钠盐、2,4-二氨基-3’,5’-二硝基-2’-羟基-5-甲基偶氮苯(Mordant brown4)、4′-氨基-4-硝基二苯胺-2-磺酸、4′-氨基-3′-硝基苯基-2-羧酸、1-氨基-4-硝基-2-(2-硝基苯亚甲基氨基)苯、2-[2-(二乙基氨基)乙基氨基]-5-硝基苯胺、3-氨基-4-羟基-5-硝基苯磺酸、3-氨基-3′-硝基联苯基-1,3-氨基-4-硝基苊、2-氨基-1-硝基萘、5-氨基-6-硝基苯并-1,3-二羰基合成醇、苯胺、特别是含硝基的苯胺比如4-硝基苯胺、2-硝基苯胺、1,4-二氨基-2-硝基苯、1,2-二氨基-4-硝基苯、1-氨基-2-甲基-6-硝基苯、4-硝基-1,3-苯二胺、2-硝基-4-氨基-1-(2-羟乙基氨基)苯、2-硝基-1-氨基-4-[二(2-羟乙基)氨基]苯、4-氨基-2-硝基二苯胺-2′-羧酸、1-氨基-5-氯代-4-(2-羟乙基氨基)-2-硝基苯、含有另外的芳基的芳香苯胺或者酚,如在通式VI中举例说明,
■其中R16代表羟基或者氨基,可以用C1-C6烷基-、C1-C6羟烷基-、C1-C6烷氧基-或C1-C6烷氧基-C1-C6烷基取代,
■R17、R18、R19、R20和R21彼此独立地代表氢原子、羟基或者氨基,可以由C1-C6烷基-、C1~C6羟烷基、C1-C6烷氧基-、C1-C6氨基烷基或C1-C6烷氧基-C1-C6烷基取代,和
■Z”是直接键合、1~4个碳原子的饱和的或者不饱和碳链,任选用羟基、羰基-、磺酰基或亚氨基、氧或硫原子或者通式VII的基团取代,
-Q′-(CH2-Q-CH2-Q″)o- (VII)
■其中Q是指直接键合、CH2-或者CHOH基团,
■Q’和Q”彼此独立地代表氧原子、NR22基团,其中R22是指氢原子、C1-C6烷基或者C1-C6羟烷基,其中两个基团也可与分子的残基一起形成5-、6-或者7-元环,及基团O--(CH2)p-NH或者NH--(CH2)p’-O,其中p和p’是2或者3,O是指1~4的数字,
比如4,4′-二氨基芪和它的盐酸盐、4,4′-二胺基芪-2,2′-二磺酸的单或二钠盐、4-氨基-4′-二甲基氨基芪和它的盐酸盐、4,4’-二氨基二苯基甲烷,4,4’-二氨基二苯基硫化物、4,4′二氨基二苯基亚砜、4,4′-二氨基二苯基胺、4,4′-二氨基二苯基胺-2-磺酸、4,4′-二氨基二苯甲酮、4,4′-二氨基二苯基醚、3,3’,4,4’-四氨基二苯基、3,3′,4,4′-四氨基-二苯甲酮、1,3-二(2,4-二氨基苯氧基)丙烷、1,8-二(2,5-二氨基苯氧基)-3,6-二氧杂环辛烷、1,3-二(4-氨基苯基氨基)丙烷、1,3-二(4-氨基苯基氨基)-2-丙醇、1,3-二-[N-(4-氨基苯基)-2-羟乙基氨基]-2-丙醇、N,N-二[2-(4-氨基苯氧基)乙基]甲胺、N-苯基-1,4-苯二胺和二(5-氨基-2-羟苯基)甲烷。
13.根据权利要求10的试剂,特征在于组份C的芳烃羟基化合物选自2-,4-,5-甲基间苯二酚、2,5-二甲基间苯二酚、间苯二酚、3-甲氧基苯酚、邻苯二酚、对苯二酚、焦性没食子酸、皮酚、苯三酚、2-,3-,4-甲氧基-、3-二甲基氨基-、2-(2-羟乙基)-、3,4-亚甲二氧基苯酚、2,4-,3,4-二羟基苯甲酸、-苯乙酸、五倍子酸、2,4,6-三羟基苯甲酸、-苯乙酮、2-,4-氯代间苯二酚、1-萘酚、1,5-,2,3-,2,7-二羟基萘、6-二甲基氨基-4-羟基-2-萘磺酸和3,6-二羟基-2,7-萘磺酸。
14.根据权利要求10的试剂,特征在于组份C的含氮杂环化合物优选选自2-氨基吡啶、3-氨基吡啶、4-氨基吡啶、2-氨基-3-羟基吡啶、2,6-二氨基吡啶、2,5-二氨基吡啶、2-(氨基乙基氨基)-5-氨基吡啶、2,3-二氨基吡啶、2-二甲基氨基-5-氨基吡啶、2-甲基氨基-3-氨基-6-甲氧基吡啶、2,3-二氨基-6-甲氧基吡啶、2,6-二甲氧基-3,5-二氨基吡啶、2,4,5-三氨基吡啶、2,6-二羟基-3,4-二甲基吡啶、N-[2-(2,4-二氨基苯基)氨乙基]-N-(5-氨基-2-吡啶基)胺、N-[2-(4-氨基苯基)氨乙基]-N-(5-氨基-2-吡啶基)胺、2,4-二羟基-5,6-二氨基嘧啶、4,5,6-三氨基嘧啶、4-羟基-2,5,6-三氨基嘧啶、2-羟基-4,5,6-三氨基嘧啶、2,4,5,6-四氨基嘧啶、2-甲基氨基-4,5,6-三氨基嘧啶、2,4-二氨基嘧啶、4,5-二氨基嘧啶、2-氨基-4-甲氧基-6-甲基-嘧啶、3,5-二甲基吡唑、3,5-二氨基-1,2,4-三唑、3-氨基吡唑、3-氨基-5-羟基吡唑、1-苯基-4,5-二甲基吡唑、1-(2-羟乙基)-4,5-二甲基吡唑、1-苯基-3-甲基-4,5-二氨基吡唑、4-氨基-2,3-二甲基-1-苯基-3-吡唑啉-5-酮(4-匹拉米洞)、1-苯基-3-甲基吡唑啉-5-酮、2-氨基喹啉、3-氨基喹啉、8-氨基喹啉、4-氨基喹哪啶、2-氨基烟酸、6-氨基烟酸、5-氨基异喹啉、5-氨基吲唑、6-氨基吲唑、5-氨基苯并咪唑、7-氨基苯并咪唑、5-氨基苯并噻唑、7-氨基苯并噻唑、2,5-二羟基-4-吗啉代-苯胺以及吲哚和二氢吲哚衍生物比如4-氨基吲哚、5-氨基吲哚、6-氨基吲哚、7-氨基吲哚、5,6-二羟吲哚、5,6-二羟二氢吲哚、4-羟基二氢吲哚及上述化合物的羟基嘧啶和它们生理学相容的盐。
15.根据权利要求1~14之一的试剂,特征在于通式1的该化合物,在试剂中组分B的化合物和组份C的化合物的含量每一种基于100g的着色剂总量为0.03~65mmol,特别是1~40mmol。
18.根据权利要求16或者17的试剂,特征在于通式IX的AR代表苯或者萘。
19.根据权利要求16~18之一的试剂,特征在于通式IX的Z代表直接键合或者亚乙烯基。
20.根据权利要求16~19之一的试剂,特征在于通式IX的R25代表氢原子。
21.根据权利要求16~20之一的试剂,特征在于通式IX的R7、R8和R9彼此独立地代表氢原子、卤素原子、C1-C6烷基、羟基、C1-C6烷氧基、氨基、C1-C6烷基氨基、二(C2-C6羟烷基)氨基、二(C1-C6烷氧基C1~C6烷基)氨基、C1-C6羟基烷氧基、磺酰基团、羧基、磺酰胺基团、氨甲酰基团、C2-C6酰基、乙酰基、磺酸基、磺酰胺基团或者硝基。
22.根据权利要求16~21之一的试剂,特征在于反应产物RP的含量基于100g的着色剂总量为0.03~65mmol,特别是1~40mmol。
23.根据权利要求1~22之一的试剂,特征在于它包括选自如下的颜色改进剂:哌啶、哌啶-2-羧酸、哌啶-3-羧酸、哌啶-4-羧酸、吡啶、2-羟基吡啶、3-羟基吡啶、4-羟基吡啶、咪唑、1-甲基咪唑、精氨酸、组氨酸、吡咯烷、脯氨酸、吡咯烷酮、吡咯烷酮-5-羧酸、吡唑、1,2,4-三唑、哌嗪或它们的混合物。
24.根据权利要求1~23之一的试剂,特征在于它包括至少一种直接染料,优选含量基于着色剂总量为0.01~20wt.%。
25.根据权利要求1~24之一的试剂,特征在于它包括至少一种显色剂组份,和任选至少一种作为氧化染料前体的偶合剂组分。
26.根据权利要求1~25之一的试剂,特征在于加入铵或金属盐,选自碱金属比如钾、钠或者锂,碱土金属比如镁、钙、锶或者钡,或者铝、锰、铁、钴、铜或者锌的甲酸盐、碳酸盐、卤化物、硫酸盐、丁酸盐、缬草酸盐、己酸盐、醋酸盐、乳酸盐、羟乙酸盐、酒石酸盐、柠檬酸盐、葡萄糖酸盐、丙酸盐、磷酸盐和膦酸盐。
27.根据权利要求1~26之一的试剂,特征在于它包括氧化剂,特别是H2O2,基于施加溶液的含量为0.01~6wt.%。
28.根据权利要求1~27的之一的试剂,特征在于它包括阴离子的、两性离子的或者非离子型表面活化剂。
29.一种根据权利要求1通式I的化合物和根据权利要求1至少一种组分B的化合物在毛发着色剂中作为染色组份的用途。
30.一种染色含角蛋白纤维特别是头发的方法,其中权利要求1的着色剂以及通常的化妆品成分施加在含角蛋白纤维上一段时间,通常约15-30分钟,停留在纤维上,随后用洗发剂漂洗或者冲洗。
31.根据权利要求30的方法,特征在于在两步方法中,在施加通式I的化合物之前或之后,组分B施加在含角蛋白纤维上,毛发上得到的混合物在纤维上停留一段时间,通常约15-30分钟,随后用洗发剂漂洗或者冲洗。
32.根据权利要求30或者31的方法,特征在于在施加权利要求1的着色剂之前,含角蛋白纤维在预处理期间用漂白组合物进行漂白或者用氧化着色剂染色。
34.通式1和、或它的烯胺形式的至少一种1,2-二氢嘧啶鎓衍生物的用途,
其中,R1、R2、R3、R4、R5、Y和X-定义如上,与至少一种反应性羰基化合物(组分B)结合用于恢复用氧化着色剂着色的含角蛋白纤维的颜色。
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DE10241076A DE10241076A1 (de) | 2002-09-05 | 2002-09-05 | Mittel zum Färben von keratinhaltigen Fasern |
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EP (1) | EP1534227B1 (zh) |
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- 2002-09-05 DE DE10241076A patent/DE10241076A1/de not_active Withdrawn
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2003
- 2003-08-23 AT AT03793751T patent/ATE349246T1/de active
- 2003-08-23 JP JP2004533392A patent/JP2006508915A/ja active Pending
- 2003-08-23 WO PCT/EP2003/009366 patent/WO2004022016A1/de active IP Right Grant
- 2003-08-23 AU AU2003266308A patent/AU2003266308B2/en not_active Ceased
- 2003-08-23 DE DE50306124T patent/DE50306124D1/de not_active Expired - Lifetime
- 2003-08-23 CN CN03821158.0A patent/CN1681470A/zh active Pending
- 2003-08-23 EP EP03793751A patent/EP1534227B1/de not_active Expired - Lifetime
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CN103249455A (zh) * | 2010-12-20 | 2013-08-14 | 莱雅公司 | 在热存在下使用羟基苯甲醛衍生物、氧化剂和碱化剂对角蛋白纤维进行染色的方法 |
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JP2006508915A (ja) | 2006-03-16 |
AU2003266308B2 (en) | 2007-05-10 |
DE50306124D1 (de) | 2007-02-08 |
EP1534227A1 (de) | 2005-06-01 |
US20050144740A1 (en) | 2005-07-07 |
US7105032B2 (en) | 2006-09-12 |
AU2003266308A1 (en) | 2004-03-29 |
DE10241076A1 (de) | 2004-03-11 |
ATE349246T1 (de) | 2007-01-15 |
WO2004022016A1 (de) | 2004-03-18 |
EP1534227B1 (de) | 2006-12-27 |
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