MXPA97007018A - Procedure to increase the solar protection factor of fiber cellular materials - Google Patents
Procedure to increase the solar protection factor of fiber cellular materialsInfo
- Publication number
- MXPA97007018A MXPA97007018A MXPA/A/1997/007018A MX9707018A MXPA97007018A MX PA97007018 A MXPA97007018 A MX PA97007018A MX 9707018 A MX9707018 A MX 9707018A MX PA97007018 A MXPA97007018 A MX PA97007018A
- Authority
- MX
- Mexico
- Prior art keywords
- alkyl
- radical
- substituted
- hydrogen
- formula
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 31
- 239000000835 fiber Substances 0.000 title description 10
- 239000000463 material Substances 0.000 title description 5
- 230000001413 cellular Effects 0.000 title 1
- 239000006096 absorbing agent Substances 0.000 claims abstract description 53
- 239000000982 direct dye Substances 0.000 claims abstract description 40
- 239000002657 fibrous material Substances 0.000 claims abstract description 39
- 239000000516 sunscreening agent Substances 0.000 claims abstract description 21
- -1 polyazo, azo Polymers 0.000 claims description 232
- 150000003254 radicals Chemical class 0.000 claims description 108
- 125000000217 alkyl group Chemical group 0.000 claims description 88
- 229910052739 hydrogen Inorganic materials 0.000 claims description 66
- 239000001257 hydrogen Substances 0.000 claims description 66
- 125000003545 alkoxy group Chemical group 0.000 claims description 47
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 46
- 229910052736 halogen Inorganic materials 0.000 claims description 40
- 150000002367 halogens Chemical class 0.000 claims description 40
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 31
- 150000002431 hydrogen Chemical group 0.000 claims description 29
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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 26
- 125000002947 alkylene group Chemical group 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 17
- 125000005843 halogen group Chemical group 0.000 claims description 14
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 13
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- 229920000742 Cotton Polymers 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 125000004414 alkyl thio group Chemical group 0.000 claims description 7
- 239000000460 chlorine Chemical group 0.000 claims description 7
- 229910052801 chlorine Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 7
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 claims description 5
- 229920003043 Cellulose fiber Polymers 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 150000002790 naphthalenes Chemical class 0.000 claims description 5
- 125000004957 naphthylene group Chemical group 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- HWRLEEPNFJNTOP-UHFFFAOYSA-N OC1=CC=CC=C1C1=NC=NC=N1 Chemical compound OC1=CC=CC=C1C1=NC=NC=N1 HWRLEEPNFJNTOP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 125000004956 cyclohexylene group Chemical group 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 3
- RZVHIXYEVGDQDX-UHFFFAOYSA-N Anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000000987 azo dye Substances 0.000 claims description 3
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 3
- 150000004696 coordination complex Chemical class 0.000 claims description 3
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 235000021286 stilbenes Nutrition 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 125000004769 (C1-C4) alkylsulfonyl group Chemical group 0.000 claims description 2
- FJGQBLRYBUAASW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)phenol Chemical compound OC1=CC=CC=C1N1N=C2C=CC=CC2=N1 FJGQBLRYBUAASW-UHFFFAOYSA-N 0.000 claims description 2
- LVIYYTJTOKJJOC-UHFFFAOYSA-N Nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 2
- 125000005277 alkyl imino group Chemical group 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- 150000001559 benzoic acids Chemical class 0.000 claims description 2
- 150000001565 benzotriazoles Chemical class 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 230000001808 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 claims description 2
- 125000003170 phenylsulfonyl group Chemical group C1(=CC=CC=C1)S(=O)(=O)* 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N Heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- 238000010186 staining Methods 0.000 description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 125000005236 alkanoylamino group Chemical group 0.000 description 9
- 125000001589 carboacyl group Chemical group 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 8
- 230000035515 penetration Effects 0.000 description 8
- 210000003491 Skin Anatomy 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000001187 sodium carbonate Substances 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 4
- 125000004604 benzisothiazolyl group Chemical group S1N=C(C2=C1C=CC=C2)* 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 4
- 235000021190 leftovers Nutrition 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- QPFYXYFORQJZEC-FOCLMDBBSA-N Phenazopyridine Chemical group NC1=NC(N)=CC=C1\N=N\C1=CC=CC=C1 QPFYXYFORQJZEC-FOCLMDBBSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N Phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 2
- 229940072056 alginate Drugs 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000005036 alkoxyphenyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 125000002993 cycloalkylene group Chemical group 0.000 description 2
- 125000002704 decyl group Chemical group [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])* 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001400 nonyl 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])[H] 0.000 description 2
- 125000002071 phenylalkoxy group Chemical group 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000037072 sun protection Effects 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 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 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 125000002948 undecyl 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])[H] 0.000 description 2
- HQEPZWYPQQKFLU-UHFFFAOYSA-N (2,6-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(O)=C1C(=O)C1=CC=CC=C1 HQEPZWYPQQKFLU-UHFFFAOYSA-N 0.000 description 1
- BDACRXKSBPLSJG-UHFFFAOYSA-N (2-hydroxy-4-methoxyphenyl)-(4-methoxyphenyl)methanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O BDACRXKSBPLSJG-UHFFFAOYSA-N 0.000 description 1
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2R,3R,4S,5R,6S)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2S,3R,4S,5R,6R)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2R,3R,4S,5R,6R)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- GOZHNJTXLALKRL-UHFFFAOYSA-N (5-benzoyl-2,4-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(O)=C(C(=O)C=2C=CC=CC=2)C=C1C(=O)C1=CC=CC=C1 GOZHNJTXLALKRL-UHFFFAOYSA-N 0.000 description 1
- HAAVZTHWQHNDJJ-UHFFFAOYSA-N (6E)-6-[4,6-bis(4-methylphenyl)-1H-1,3,5-triazin-2-ylidene]-3-octoxycyclohexa-2,4-dien-1-one Chemical compound C1=CC(OCCCCCCCC)=CC(=O)\C1=C/1N=C(C=2C=CC(C)=CC=2)N=C(C=2C=CC(C)=CC=2)N\1 HAAVZTHWQHNDJJ-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-Triazine Chemical class C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- ONTODYXHFBKCDK-UHFFFAOYSA-N 2-(2,4-dimethylphenyl)-1,3,5-triazine Chemical compound CC1=CC(C)=CC=C1C1=NC=NC=N1 ONTODYXHFBKCDK-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- LCHMOPDIHALNRZ-UHFFFAOYSA-M 2-methoxycarbonyl-3-phenylprop-2-enoate Chemical compound COC(=O)C(C([O-])=O)=CC1=CC=CC=C1 LCHMOPDIHALNRZ-UHFFFAOYSA-M 0.000 description 1
- YTZPUTADNGREHA-UHFFFAOYSA-N 2H-benzo[e]benzotriazole Chemical class C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- DBOSBRHMHBENLP-UHFFFAOYSA-N 4-tert-Butylphenyl salicylate Chemical compound C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC=CC=C1O DBOSBRHMHBENLP-UHFFFAOYSA-N 0.000 description 1
- RTEZGDJVSNVRSV-UHFFFAOYSA-N 6-[2,6-bis(2,4-dimethylphenyl)-1H-1,3,5-triazin-4-ylidene]-3-dodecoxycyclohexa-2,4-dien-1-one Chemical compound C1=CC(OCCCCCCCCCCCC)=CC(=O)C1=C1N=C(C=2C(=CC(C)=CC=2)C)NC(C=2C(=CC(C)=CC=2)C)=N1 RTEZGDJVSNVRSV-UHFFFAOYSA-N 0.000 description 1
- FJLRFPXKMBEERQ-UHFFFAOYSA-N 6-[2,6-bis(2,4-dimethylphenyl)-1H-1,3,5-triazin-4-ylidene]-3-octoxycyclohexa-2,4-dien-1-one Chemical compound C1=CC(OCCCCCCCC)=CC(=O)C1=C1N=C(C=2C(=CC(C)=CC=2)C)NC(C=2C(=CC(C)=CC=2)C)=N1 FJLRFPXKMBEERQ-UHFFFAOYSA-N 0.000 description 1
- CGLBUBFYYYOMDH-UHFFFAOYSA-N 6-[4,6-bis(4-octoxy-6-oxocyclohexa-2,4-dien-1-ylidene)-1,3,5-triazinan-2-ylidene]-3-octoxycyclohexa-2,4-dien-1-one Chemical compound C1=CC(OCCCCCCCC)=CC(=O)C1=C(NC(N1)=C2C(C=C(OCCCCCCCC)C=C2)=O)NC1=C1C(=O)C=C(OCCCCCCCC)C=C1 CGLBUBFYYYOMDH-UHFFFAOYSA-N 0.000 description 1
- WBFZCIMFUFIIHX-UHFFFAOYSA-N 6-[6-(2,4-dimethylphenyl)-4-(6-oxo-4-propoxycyclohexa-2,4-dien-1-ylidene)-1H-1,3,5-triazin-2-ylidene]-3-propoxycyclohexa-2,4-dien-1-one Chemical compound C1=CC(OCCC)=CC(=O)C1=C(NC(=N1)C=2C(=CC(C)=CC=2)C)NC1=C1C(=O)C=C(OCCC)C=C1 WBFZCIMFUFIIHX-UHFFFAOYSA-N 0.000 description 1
- PLMJIYTVMZTCPO-UHFFFAOYSA-M CC1=C(C(=CC(=C1)C(C)(C)C)C(C)(C)C)C=1C(=C(C(=C(C(=O)[O-])C=1)C(C)(C)C)C(C)(C)C)O Chemical compound CC1=C(C(=CC(=C1)C(C)(C)C)C(C)(C)C)C=1C(=C(C(=C(C(=O)[O-])C=1)C(C)(C)C)C(C)(C)C)O PLMJIYTVMZTCPO-UHFFFAOYSA-M 0.000 description 1
- YTHQTKBAVNQRFN-UHFFFAOYSA-M COC1=CC=C(C(C)=C(C#N)C([O-])=O)C=C1 Chemical compound COC1=CC=C(C(C)=C(C#N)C([O-])=O)C=C1 YTHQTKBAVNQRFN-UHFFFAOYSA-M 0.000 description 1
- 240000000218 Cannabis sativa Species 0.000 description 1
- 241001340526 Chrysoclista linneella Species 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N Cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 125000005118 N-alkylcarbamoyl group Chemical group 0.000 description 1
- BZQCIHBFVOTXRU-UHFFFAOYSA-N OC1=CC(OCC(O)COCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 Chemical compound OC1=CC(OCC(O)COCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 BZQCIHBFVOTXRU-UHFFFAOYSA-N 0.000 description 1
- FESJNIGBEZWAIB-UHFFFAOYSA-N OC1=CC(OCC(O)COCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 Chemical compound OC1=CC(OCC(O)COCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 FESJNIGBEZWAIB-UHFFFAOYSA-N 0.000 description 1
- PMXVVWWYQVYKOJ-UHFFFAOYSA-N OS(=O)(=O)C1=CC(OC)=CC(O)=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 Chemical compound OS(=O)(=O)C1=CC(OC)=CC(O)=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 PMXVVWWYQVYKOJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N Phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 229940005550 Sodium alginate Drugs 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 210000002268 Wool Anatomy 0.000 description 1
- HHFMFWAFQGUGOB-UHFFFAOYSA-N [5-(4-tert-butylbenzoyl)-2,4-dihydroxyphenyl]-(4-tert-butylphenyl)methanone Chemical compound C1=CC(C(C)(C)C)=CC=C1C(=O)C1=CC(C(=O)C=2C=CC(=CC=2)C(C)(C)C)=C(O)C=C1O HHFMFWAFQGUGOB-UHFFFAOYSA-N 0.000 description 1
- WBLXMRIMSGHSAC-UHFFFAOYSA-N [Cl].[Cl] Chemical compound [Cl].[Cl] WBLXMRIMSGHSAC-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K [O-]P([O-])([O-])=O Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- 125000005111 carboxyalkoxy group Chemical group 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 125000004977 cycloheptylene group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004979 cyclopentylene group Chemical group 0.000 description 1
- BVJSHQWNXSXIBK-UHFFFAOYSA-N di(ethyl)azanide Chemical group [CH2]C[N-]C[CH2+] BVJSHQWNXSXIBK-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000006627 ethoxycarbonylamino group Chemical group 0.000 description 1
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 235000012765 hemp Nutrition 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-O hydrazinium(1+) Chemical compound [NH3+]N OAKJQQAXSVQMHS-UHFFFAOYSA-O 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 125000005113 hydroxyalkoxy group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N iodine atom Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 235000012766 marijuana Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000434 metal complex dye Substances 0.000 description 1
- 125000006626 methoxycarbonylamino group Chemical group 0.000 description 1
- PFSMVSPKLRCNGS-UHFFFAOYSA-N methyl 2-methoxy-3-phenylprop-2-enoate Chemical compound COC(=O)C(OC)=CC1=CC=CC=C1 PFSMVSPKLRCNGS-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000001820 oxy group Chemical class [*:1]O[*:2] 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 238000009980 pad dyeing Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 239000011528 polyamide (building material) Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- FBBHPHRBJLLIFM-UHFFFAOYSA-O pyridin-1-ium-1-carboxylic acid Chemical compound OC(=O)[N+]1=CC=CC=C1 FBBHPHRBJLLIFM-UHFFFAOYSA-O 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 230000037380 skin damage Effects 0.000 description 1
- 150000003385 sodium Chemical group 0.000 description 1
- MSXHSNHNTORCAW-UHFFFAOYSA-M sodium 3,4,5,6-tetrahydroxyoxane-2-carboxylate Chemical compound [Na+].OC1OC(C([O-])=O)C(O)C(O)C1O MSXHSNHNTORCAW-UHFFFAOYSA-M 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- LJRGBERXYNQPJI-UHFFFAOYSA-M sodium;3-nitrobenzenesulfonate Chemical compound [Na+].[O-][N+](=O)C1=CC=CC(S([O-])(=O)=O)=C1 LJRGBERXYNQPJI-UHFFFAOYSA-M 0.000 description 1
- 238000005063 solubilization 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
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 230000000475 sunscreen Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
A method is described for increasing the sun protection factor of cellulosic fiber materials by treating the cellulosic fiber materials with at least one direct dye and at least one absorber
Description
PROCEDURE TO INCREASE THE SOLAR PROTECTION FACTOR OF CELLULOSE FIBER MATERIALS
DESCRIPTION OF THE INVENTION
The present invention relates to a method for increasing the sun protection factor of cellulosic fiber materials, which comprises treating the cellulose fiber materials with direct dyes in the presence of at least one UV absorber. The effect that damages the skin of UV radiation is well known. The protection of strong sunlight is usually sought by applying a sunscreen, a composition containing a UV absorber, directly to the skin. In particular, sunny climates, for example in Australia or America, however, the regimen of skin damage due to UV radiation has recently increased. Consequently, more attention has been paid in these countries to protect the skin from the sun's rays. Therefore, it has been proposed not only to protect the skin directly, but also to reduce the UV transmission capacity of clothing and also of other sun protection articles made of cellulosic fiber materials, such as awnings or umbrellas. Most non-dyed fiber materials are at least partially transparent to UV radiation, so that the mere use of clothing does not offer adequate protection to the skin from damage due to UV radiation. However, the results achieved hitherto with respect to the protection of UV radiation in the area of cellulosic fiber materials, in particular textile materials, have not been satisfactory and therefore the need to improve the sun protection factor of these materials. Surprisingly, it has now been found that an even better sun protection can be achieved if the cellulosic fiber materials are treated with a combination of direct dyes and UV absorbers. The present invention, therefore, provides a method for increasing the sun protection factor of cellulosic fiber materials, which comprises treating the cellulosic fiber materials with at least one direct dye and at least one UV absorber. In the process of the present invention, the amounts in which the direct dyes are used in the dye baths can vary with the desired depth of shade; in general, the advantageous amounts vary from 0.001 to 10% by weight, in particular from 0.001 to 55 by weight, based on the weight of fiber material. The amounts of UV absorbers used in the process of the present invention may vary from 0.001 to 5% by weight, based on the weight of the fiber material. In a preferred embodiment of the process of the present invention, the amount of UV absorber used depends on the total amount of the colorant used. For example, the amount of UV absorber used is from 0.2 to 5% by weight, in particular from 0.2 to 2% by weight, based on the weight of the fiber material, in the case of pale shades, from 0.05 to 0.2% by weight. weight in the case of medium leftovers and from 0.001 to 0.05% by weight in the case of deep leftovers The pale shades are understood to be those in which the amount of colorant is 0.001 to 0.2% by weight, based on the weight of the material of fiber. The average leftovers are those in which the amount of dye used is 0.2 to 2.0% by weight, and the profaned leftovers are those in which the amount of dye used is from 2 to 10% by weight, in particular from 2 to 5% by weight In a particularly preferred embodiment of the process of the present invention, the amount of direct dye used is from 0.2 to 2.0% by weight, based on the weight of the fiber material, and the amount of the UV absorber used is from 0.05 to 0.2% by weight, based on the weight of fiber material. In a particularly highly preferred embodiment of the process of the present invention, the amount of direct dye used is from 0.001 to 0.2% by weight, based on the weight of the fiber material, and the amount of UV absorber used is from 0.2 to 2% by weight, based on the weight of the fiber material. The method of the present invention makes it possible to achieve a suitable sun protection factor in the dyed or printed fiber material in any desired shade, a suitable sun protection factor is a sun protection factor with a value of at least 25. Advantageously , the amount of direct dye used is selected in order to present an increase of the sun protection factor of the cellulosic fiber materials by a factor of at least 5. Direct dyes are understood, for example, as those dyes that are describe as direct dyes in the Color Index, 3rd. edition (3rd revision, 1987, including additions and amendments up to No. 85). The direct dyes used are in particular phthalocyanine dyes, dioxazine dyes and dyes of the formula, wherein Bi is a bridging member, and A, and A2 are independently from each other, the radical of a monoazo dye, polyazo, azo complex of metal, stilbene or anthraquinone, or wherein B, and Ai each are as defined above, and A2 is a phenyl or naphthyl radical substituted by a heterocyclic radical or by a benzoylamino or phenylamino radical, or wherein B1 is a bond direct, and Ai and A2 are each the radical of an azo metal complex dye. Suitable bridge members of Bi in formula (1) include, for example: -NH- (2a), 0 II N- - C-N- (2b), Ri R2 O or II II N- - C-X , - c- -N 1 (2c), R? R1 -N -N- 1 1 (2d), R R2 Y
O / \ N N (2g),
-N = N- (2h) and -CH = CH- (2i),
wherein R.sup.1 and R.sup.2 are independently from each other C.sub.1 -C.sub.8 halogen-, hydroxyl-, cyano-, C.sub.1 -C.sub.-alkoxy, C.sub.1 -C.sub.4 -alkoxycarboxyl-, sulphamoyl-, sulfo- or sulfate- replaced or not replaced; or in particular hydrogen; X ^ and X2 are each bridge members; Y and Y1 are independently of each other hydroxyl, C?-C4 alkoxy, chlorine, bromine, C?-C 4 alkylthio, amino, or hydroxyl-, sulfo-, carboxyl-, or α-C --substituted alkoxy; substituted (in the alkyl portion), N-mono- or N, N-di-alkylamino of C? -C, cyclohexylamino, or unsubstituted phenylamino or Ci-C alkyl, C? -C- alkoxy, carboxyl-, sulfo-, and / or halogen-substituted (in the phenyl portion) or N-alkyl of C? -C-N-phenylamino, morpholino or 3-carboxy or 3-carbamoyl-pyridin-1-yl. The bridge member Xi in the formula (2c) is preferably an unsubstituted C2-C6 alkylene or hydroxyl-, sulfo-, sulfato-, C6-, C4-, carboxyl- or halo-substituted alkoxy; or unsubstituted C5-C9 cycloalkylene or hydroxyl-, sulfo-, sulfato-, C? -C4-, carboxyl- or halogen-substituted alkoxy; unsubstituted phenylene or C 1 -C 4 alkyl, C 1 -C 4 alkoxy, sulfo-, halogeno- or carboxyl-substituted; unsubstituted phenylene or C? -C4- alkyl, C? -C4-, sulfo-, halogeno-, or carboxyl-substituted alkoxy; or an unsubstituted naphthalene radical or C? -C- alkyl, C? -C4-, sulfo-, halogeno-, or carboxyl-substituted alkoxy. Xi is in particular unsubstituted or sulfo-substituted phenylene. A bridge member X2 in formula (2e) can be, for example, a radical of the formula, -NR, - (CH2) 2 ^ NR2- (3a),
and in particular,
wherein R1 and R2 are each subject to the definitions and preferences previously indicated. Preference is given to the use of direct dyes of the formula, wherein Ai is as defined under formula (1) and L ^ is a radical of the formulas,
wherein, X3 and X4 independently of each other are a direct bond, NH, NR5, O, or S; R3 and R4 are each independently hydrogen; radicals, aliphatic or cycloaliphatic, which are unsubstituted or substituted by halogen, OR5, COOR5, SO3H or aralkyl, which can be substituted by halogen, OR5, COOR5, or SO3H, and R5 is hydrogen or Ci-Cß alkyl R 3 and R 4 radicals in the formula (1a) are preferably C 1 -C 6 alkyls or alkyl, for example methyl, ethyl or isopropyl, which can be substituted, by carboxyl or phenyl; or phenols, which likewise can be substituted, for example by carboxyl; non-substituted or substituted benzyl radicals; or radicals of the formulas,
N N - R5 N O
wherein R5 is as defined under formula (1a). Preference is also given to the use of dyes of the formula (1), wherein B and Ai are each as defined above, and A2 is a phenyl radical benzothiazolyl-, benzisothiazolyl-, or naphthatriazolyl-substituted, wherein the radical phenyl and the benzothiazolyl, benzisothiazolyl and naphthotriazolyl substituents on the phenyl radical independently may be substituted by C?-C4 alkyl, C?-C, halogen, carboxyl, hydroxyl, sulfo, sulfamoyl, ureido, optionally substituted amino by C? -C4 alkyl, C? -C hydroxyalkyl, or C2-C6 alkanoyl, or optionally substituted C2-C6 alkanoylamino (in the alkyl portion) by hydroxyl. The radicals Ai and A2 in the formula (1) can be substituted, for example, by C 1 -C 4 alkyl, such as methyl, ethyl, propyl, isopropyl or butyl; C 1 -C 4 alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy; C? -C8 acylamino, in particular alkanoylamino
of C? -C8 unsubstituted or hydroxy-substituted (in the alkyl portion), such as acetylamino or propionylamino; unsubstituted or hydroxyl-substituted C 1 -C 8 alkoxycarbonylamino (in the alkyl portion), such as methoxy carbonylamino or ethoxycarbonylamino; benzoylamino; Phenylamino, N, N-di-β-hydoxyethylamino; N, N-di-β-sulfatoethylamino; sulfobenzylamino; N, N-disolfobenzylamino; unsubstituted or hydroxy-substituted C2-C6 alkanoyl (in the alkyl portion); phenylazo; naphotriazolyl; benzothiazolyl; benzisothiazolyl; C 1 -C 4 alkoxycarbonyl, such as methoxycarbonyl or ethoxycarbonyl; C 1 -C alkylsulfonyl, such as methylsulfonyl or ethylsulfonyl; trifluoromethyl; nitro; cyano; halogen such as fluorine, chlorine or bromine; carbamoyl, N-alkylcarbamoyl of C? -C4, such as N-methylcabamoyl or N-ethylcarbamoyl; sulfamoyl; N-C 1 -C 4 -alkylsulfamoyl, such as N-methylsulfamoyl, N-ethylsulphamoyl, N-propylsulfamoyl, N-isopropyl-sulfamoyl or N-butylsulfamoyl; N-phenylsulfamoyl; ureido; hydroxyl; carboxyl; sulfomethyl; sulfo; or C 1 -C 4 alkyl or substituted or unsubstituted C 1 -C 4 amino hydroxyalkyl; wherein the aforementioned heterocyclic radicals and also the groups containing a phenyl radical can be further substituted by one or more of the aforementioned groups as substituents for the radicals Ai and A2. Any of C, C 4 alkyl C 1 -C 6 alkyl or d C 8 alkyl in the formulas is for example, according to the established chain length, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl or octyl.
Any of C?-C 4 alkoxy in the formulas is for example methoxy, ethoxy, propoxy, isopropoxy, isobutoxy or tert-butoxy. Any of the hydroxyalkyl of C? -C in the formulas is for example 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl or 3,4-dihydroxybutyl. Any of N-mono-alkylamino of C? -C4 in the formulas is for example N-methylamino, N-ethylamino, N-propylamino or N-butylamino.
Any of N, N-di-alkylamino of C? -C4 in the formulas is for example N, N-dimethylamino, N, N-diethylamino, N, N-dipropylamino, N-methyl-N-ethylamino, N-ethyl- N-propylamino or N-ethyl-N-butylamino. Any of N-C 1 -C-N-phenylamino alkyl in the formulas is for example N-methyl-N-phenylamino, N-ethyl-N-phenylamino, N-propyl-N-phenylamino or N-butyl-N- phenylamino. Either C2-C6 alkanoylamino or C? -C8 alkanoylamino in the formulas is for example acetylamino, propionylamino or n-butyryl-amino. Any of C 1 -C 4 alkoxycarbonyl in the formulas is for example methoxycarbonyl, ethoxycarbonyl, or propoxycarbonyl. Any of C2-C6 alkylene in the formulas is for example methylene, ethylene, propylene, tetramethylene, pentamethylene or hexamethylene. Any of C3-C cycloalkylene in the formulas is for example cyclopentylene, cyclohexylene or cycloheptylene. Any of C2-C6 alkanoyl in the formulas is for example acetyl, propionyl or n-butyryl. Any of C 1 -C 4 alkylthio in the formulas is for example methylthio, ethylthio, propylthio or butylthio. - The azo dye radicals, A ^ and A2, are preferably radicals of the formula, D1-N = N- (M1-N = N) 0? - Ki- (4a)
- D? -N = N- (M? -N = N) 0-? - K, (4b), where Oi is the radical of a diazo component of the benzene or naphthalene series, Mi is the radical of a middle component of the benzene or naphthalene series, Ki is the radical of a coupling component of the benzene or naphthalene series, and Di, i, and Ki can be substituted by the substituents indicated above for Ai and A2, in particular by C? -C alkyl, C? -C4 alkoxy, halogen, carboxyl, hydroxyl, sulfo, sulfamoyl, ureido, or unsubstituted amino or C 1 -C 4 alkyl or C 1 -C 4 substituted hydroxyalkyl, or unsubstituted or hydroxy substituted C 2 -C 6 alkanoyl (in the alkyl portion), C 2 -C alkanoylamino Unsubstituted or hydroxyl-substituted C6 (in the alkyl portion), phenylamino-C1-C4 alkyl or unsubstituted -C? -C alkoxy or carboxyl-, halogen-, sulfo-, substituted (in the phenyl ring), or benzoylamino not substituted or carboxyl-, halogen-, sulfo-, C 1 -C 4 alkyl-, or C 1 -C 4 -alkoxy substituted (on the phenyl ring); - Azo dye radicals of metal complex, A! and A2 are preferably radicals of the formula,
wherein the oxygen or carboxyl group is linked to the radical Q1, Q2, or Q3 in an ortho position relative to the azo group, and Q ,, Q2, or Q3 each are independently of the others a radical of the benzene series or naphthalene, and 0 ^, Q2, and Q3 can be substituted by the substituents indicated above for Ai and A2, in particular by C? -C4 alkyl, C? -C alkoxy, halogen, carboxyl, hydroxyl, sulfo, sulfamoyl, ureido, or unsubstituted amino or C? -C4- alkyl or C? -C-substituted hydroxy alkyl, C2-C6 alkanoyl, unsubstituted or hydroxy-substituted (in the alkyl portion), C2-C? alkanoylamino not substituted or hydroxyl-substituted (in the alkyl portion), unsubstituted phenylamino or carboxyl-, halogen-, hydroxyl-, sulfo-, d-C4- alkyl, C? -C4- alkoxy, or C? -C4 carboxyalkoxy - substituted (on the phenyl ring), or unsubstituted benzoylamino or carboxyl-, halogen-, hydroxyl-, sulfo-, C1-C4- alkyl, C1-C4- alkoxy, or carboxyalc C1-C4-substituted oxy (on the phenyl ring, or unsubstituted phenylazo or carboxyl-, halogen-, hydroxyl-, sulfo-, C? -C4- alkyl, C? -C4- alkoxy, or C-carboxyalkoxy) ? -C4- substituted (on the phenyl ring); Stilbene dye radicals, Ai and A2, are preferably radicals of the formula,
wherein the benzene rings I and II can independently be substituted by the substituents indicated above for Ai and A2, in particular by C1-C4 alkyl, C? -C alkoxy, halogen, carboxyl, hydroxyl, sulfo, sulfamoyl, ureido, unsubstituted amino or C? -C- alkyl, or C? -C-substituted hydroxyalkyl, C2-C6 alkanoyl, unsubstituted or hydroxy-substituted (in the alkyl portion), unsubstituted C2-C6 alkanoylamino or hydroxyl-substituted (on the alkyl portion), or unsubstituted naphthotriazole or C 1 -C 4 alkyl, C 1 -C 4, halogen, or sulfo substituted alkoxy; - Anthraquinone dye radicals, Ai and A2, are preferably radicals of the formula,
wherein G1 is C2-C6 alkylene, cyclohexylene, phenylenemethylene or preferably phenylene, the anthraquinone core can be replaced by an additional sulfo group, and phenylene-d can be substituted by C? -C alkyl, C? C4, halogen, carboxyl, or in particular sulfo; - Radical phenyl or substituted heterocyclic naphthyl, A2, is preferably a benzothiazolyl-, benzisothiazolyl- or naphthotriazolyl-substituted phenyl radical, wherein the phenyl radical and the benzothiazolyl, benzisothiazolyl and naphthotriazolyl substituents on the phenyl radical, can be independently of one another substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halogen, carboxyl, hydroxyl, sulfo, sulfamoyl, ureido, amino optionally further substituted by C 1 -C alkyl, or d 4 C 4 hydroxyalkyl, or C 2 alkanoyl -C6, or C2-C6 alkanoyl, or C-C6 alkanoylamino, optionally substituted (in the alkyl portion) by hydroxyl The dyes of the formula (1) wherein B1 is a bridging member, may contain identical or different radicals of the formulas (4a), (4b), (5a), (5b), (6) and (7) for Ai and A2. Similarly, the dyes of the formula (1) wherein B1 is a direct bond, may contain identical or different radicals of the formulas (5a), and (5b) for At and A2. The phthalocyanine direct dyes suitable for use in accordance with the present invention preferably contain the radical of the formula,, (S? 2W) k Pe ^ S02-N-E- < 8) 'wherein Pe is the radical of a nickel or cobalt phthalocyanine, W is -OH and / or -NR7Rβ, R7 and R8 are independently of each other hydrogen or unsubstituted C?-C 4 alkyl or hydroxyl - or sulfo-substituted, R6 is hydrogen or C? -C alkyl, E is unsubstituted phenylene or C? -C4-, halogen-, carboxyl-, or sulfo-substituted alkyl, or a C2-C6 alkylene, preferably a sulfophenylene or ethylene, and k is 1, 2 or 3. Direct dioxazine dyes suitable for use in accordance with the present invention, preferably contain radicals of the formulas,
wherein E1 is unsubstituted phenylene or C1-C4-, halogeno-, carboxyl-, or sulfo-substituted alkyl, or a C2-C6 alkylene; and the external benzene rings in formulas (9a) and (9b) can be further substituted by d-C4 alkyl, C? -C4 alkoxy, acetylamino, nitro, halogen, carboxyl or sulfo. Particular preference is given to the use of direct dyes of the formula (1), wherein Bi is a bridging member of the formulas (2a) to (2i) and At and Ai are independently of one another a radical of the formulas (4a), (4b), (5a), (5b), (6), and (7) or direct dyes of the formula (1) wherein Bi and Ai are each as defined, and A2 is a radical benzothiazolyl-, benzisothiazolyl- or naphthotriazolyl-substituted phenyl, wherein the phenyl radical and the substituents benzothiazolyl, benzisothiazolyl and naphthotriazolyl, on the phenyl radical, can, independently of one another, be substituted by C 1 -C 4 alkyl, C 1 alkoxy -C4, halogen, carboxyl, hydroxyl, sulfo, sulfamoyl, ureido, amino optionally substituted by C? -C alkyl, Ci-C4 hydroxyalkoxy, or C2-C6 alkanoyl, or C2-C6 alkanoylamino, optionally substituted (in the alkyl portion) by hydroxyl, or direct dyes of the formula (1) wherein Bi is a direct bond, and Ai and A2 are independently a radical of the formulas (5a) and (5b). Particular preference is also given to the use of direct dyes of the formula (1a) wherein Li is a radical of the formulas, wherein X6 is halogen and R5 is as defined under formula d). The direct dyes preferably contain a solubilization group in water, such as a sulfo or sulfate group, and are in this case either in the form of their free acid or preferably as salts thereof, for example, the alkali metal salts, of alkaline earth metal or ammonium metal, or as salts of an organic amine. Examples are the sodium, potassium, lithium, or ammonium salts, or the triatanolamine salt. The direct dyes are known or can be prepared analogously to known dyes. UV absorbers suitable for the process of the present invention are, for example, water-solubilized UV absorbers such as those known from, for example, US-A-4,141,903; US-A-4,230,867; US-A-4,698,064; and US-A-4,770,667 It is possible to use, for example, the following compounds. a) 2-hydroxybenzophenones of the formula,
wherein R9 is hydrogen, hydroxyl, C? -C, 4 alkoxy or phenoxy, Rio is hydrogen, halogen, C1-C4 alkyl or sulfo, Rn is hydrogen, hydroxyl, or C1-C4 alkoxy, and R12 is hydrogen , hydroxyl, or carboxyl; b) 2- (2'-hydroxyphenyl) -benzotriazoles of the formula, wherein R13 is hydrogen, chloro, sulfo, C? -C? 2 alkyl, C5-C6 cycloalkyl, (C? -C8 alkyl) phenyl , C7-C9 phenylaikyl, or sulfonated C-C9 phenylalkyl, R? 4 is hydrogen, chloro, C? -C4 alkyl, C? -C alkoxy, hydroxyl, or sulfo, R5 is C? -C alkyl? 2, chloro, sulfo, C? -C4 alkoxy, phenyl, (C? -C8 alkyl) phenyl, C5-C6 cycloalkyl, C2-C9 alkoxy, carboxyethyl, C7-C9 phenylalkyl, or C7 phenylalkyl Sulfonated -C9, R6 is hydrogen, chloro, C? -C4 alkyl, C? -C4 alkoxy, C2-C9 alkoxycarbonyl, carboxyl or sulfo, and Ri7 is hydrogen or chloro; c) 2- (2'-hydroxyphenyl) -s-triazines of the formula,
wherein Riß is hydrogen, halogen, C 1 -C 4 alkyl or sulfo, R 19 is hydrogen, C 1 -C 4 alkyl, C 1 -C alkoxy, or hydroxyl, R 20 is hydrogen or sulfo, and R 2? and R22 are independently of each other C? -C alkyl, d-d alkoxy, C5-C6 cycloalkyl, phenyl or C? -C4- and / or hydroxyl-substituted alkyl phenyl; d) s-triazine compounds of the formula, (13), 2 N 'R. 25
wherein at least one of the substituents R23, R24 and R25 is a radical of the formula,
wherein A is C3-C4 alkylene or 2-hydroxytrimethylene, and M 'is sodium, potassium, calcium, magnesium, ammonium, or tetra-C1-d-ammonium alkyl, and b is 1 or 2, and the remaining substituent is or the remaining substituents are independently of each other C?-C4 alkyl, phenyl, C?-C? 2 alkyl, or phenyl linked to the triazinyl radical by oxygen, sulfur, imino or C?-Cn alkylimino, or a radical of the formula (14), for example the potassium salt of the compound of the formula (13), wherein R23 is phenyl, and R2 and R25 are each the radical of the formula (14) or the sodium salt of the compound of the formula (13), wherein R23 is p-chlorophenyl, and R24 and R25 are each the radical of the formula (14). Alkoxy of C? -C4, R9, is for example methoxy, ethoxy, propoxy, n-butoxy, octyloxy, dodecyloxy or tetradecyloxy; Alkyl of C? -C, Rio, R? 4, Rie, Rie, R19, R2 ?, or R22 is methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl; Sulfo, Rio, R13, R4, R15, R16, R18, or R20 is present in free form or in salt form, for example, as alkali metal, alkaline earth metal, ammonium or amine salts; Alkoxy of C? -C, Rn, R? , Ris, Rie, R19, R21 or R22 is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy; Carboxyl, R 12 or R 6 can be present in free form or in salt form, for example, as the alkali metal, alkaline earth metal, ammonium or amine salt; C5-C6 cycloalkyl, R13, R15, R2? or R22 is, for example, cyclopentyl or cyclohexyl; (C 1 -C 8 alkyl) phenyl, for example, methylphenyl, tert-butylphenyl, tert-amylphenyl or tert-octylphenyl; Alkyl of C? -C? 2, R13, R15, R23, R24 or R25 is, for example, methyl, ethyl, amyl, tert-octyl, n-dodecyl, sec-butyl or tert-butyl; Phenylalkyl of C -C9, R13 or R? S is, for example, benzyl, a-methylbenzyl or preferably a, a-dimethylbenzyl; C2-C9 alkoxycarbonyl, R15 or R6 is, for example, ethoxycarbonyl, n-octoxycarbonyl or preferably methoxycarbonyl;
Alkylammonium Ci-Cn, R23, R24 or R2S is, for example, methyl-, ethyl-, butyl-, hexyl-, octyl-, decyl-, or undecyl-imino. e) Asymmetric oxalic diamines, soluble in water of the formula,
wherein R 6 is unsubstituted C 1 -C 5 alkyl or hydroxyl- or alkoxy-substituted, or unsubstituted benzyl or substituted C 1 -C 5 alkyl; R27 is hydrogen; halogen; C -C 2 alkyl, or C 1 -C 5 phenylalkyl; R28 is hydrogen; halogen; C 1 -C 2 alkyl, C 1 -C 5 phenylalkyl, or C 1 -C 5 alkoxy; B is a direct bond or a bivalent radical of the formula -O- L-, wherein L is alkylene of d-C6, unsubstituted or hydroxy-substituted; M "is hydrogen or an alkali metal, and r is 2, 1 or 0. C 1 -C 5 alkyl, R 2, is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl , amyl or isoamyl, a halogen, R27 or R28, is for example fluorine, bromine or chlorine.The preferred one is chlorine.C? -C? 2 alkyl radicals, R27 and R28 may be branched or unbranched radicals, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, pentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl or A Ci-d-phenyl alkyl, R 27 or R 28 is, for example, phenethyl, phenylpropyl, phenylbutyl or preferably benzyl, A C 1 -C 5 alkoxy, R 28 is, for example, methoxy, ethoxy, isopropoxy, isobutoxy, ter -butoxy or ter-amyloxy.D-C6alkylene, L, is a bivalent, saturated hydrocarbon radical, for example, methylene, ethylene, propylene, trimethylene, tetramethylene, ethylene, pentamethylene or hexamethylene. alkaline, M ", is for example, lithium, sodium or potassium. The preferred one is sodium. The UV absorber of the formula (15) is preferably a compound wherein L is trimethylene or -CH 2 -CH-CH 2 -I
OH. A further, preferred, oxyalic diarylamide conforms to the formula (15) previously indicated, wherein R28 is Ci-C2alkyl, or C1-C5alkoxy. A similarly preferred UV absorber (e) is a compound of the formula (15) previously indicated, wherein R 26 is C 1 -C 3 alkyl; R27 is hydrogen; C1-C3 alkyl, or C1-C3 alkoxy; B is a direct bond or the radical - [0 (CH2) 3] s; r is 0, 1 or 2; and s is 0 or 1 A particularly preferred UV absorber (e) is a compound of the formula (15) wherein r is 0 or 1, R26 is methyl; ethyl; methoxy or ethoxy; R27 is hydrogen or ethyl; R28 is hydrogen or C1-C3 alkoxy; B is the radical - [O (CH2) 3] s, and s is 0 or 1. Emphasis is given to use as UV absorber (e) the compound of the formula,
The oxalic diarylamides according to (e) are known from for example EP-A 0 507 732, or can be obtained by the methods described therein.
Preferably, the UV absorbers used in the process of the present invention are reactive UV absorbers. The reactive UV absorbers are understood to represent those UV absorbers, which contain one or more reactive groups. The reactive groups are understood to represent radicals reactive to fibers, which are capable of reacting with the cellulose hydroxyl groups, the amino, carboxyl, hydroxyl and thiol groups of wool and silk, or with the amine and possibly carboxyl groups of polyamides synthetic, to form covalent chemical bonds. The reactive groups are generally linked to the UV absorber radical directly or through a bridge member. Suitable reactive groups are, for example, those containing at least one separable substituent attached to an aliphatic, aromatic or heterocyclic radical, or in which the radicals mentioned contain a radical suitable for the reaction with the fiber material, for example , a triazine radical. Additional suitable reactive groups are those containing at least one activated, unsaturated group, in particular an unsaturated aliphatic group, for example, a vinyl, halogenovinyl, styryl, acryloyl, or methacryloyl group, or at least one targeting system. polymerizable ring. Examples of such groups are unsaturated groups containing halogen atoms, such as halo-maleic acid radicals and halo-propionic acid radicals, a-, or β-bromo or chloro-acryloyl groups, vinyl acetyl halogenated, halogeno-crotonyl or halogeno-methacryloyl groups. Also suitable are those groups, which are easily converted, for example, by the elimination of hydrogen halide, to unsaturated groups containing halogen, for example, dichloropropionyl or dibromopropionyl. In the present, the halogen atoms are understood to represent fluorine, chlorine, bromine and iodine atoms, but also pseudohalogen atoms, for example, cyano. Examples of further additional separable atoms or groups are ammonium including hydrazinium, sulfate, thiosulfate, phosphate, acetoxy, propionoxy or carboxypyridinium. Reactive UV absorbers suitable for the process of the present invention are preferably compounds of the formula,
U (B4, _ (w,) - (B3) -W2 - i ^ N ^ j T5 (26),
X7 wherein B3 and B4 are each independently of the other an aliphatic bridge member; U is the radical of a UV absorber of the group of 2-hydroxybenzophenones, benzotriazoles, 2-hydroxyphenyl-1, 3,5-triazines, oxalodiamines, acrylates, substituted or unsubstituted benzoic acids and esters and radicals of the formula,
(27) «
26 wherein (R40) or -3 represents 0 to 3 identical or different radicals, R40 is selected from the group consisting of sulfo, C? -C alkyl, Ci-d alkoxy, halogen, hydroxyl, carboxyl, nitro and alkylcarbonyl of Ci-C4, R4? is hydrogen, sulfo, C1-C4 alkyl, or Ci-d alkoxy, M2 is a group -NR30-CO- or -NR30-SO2-, R30 is hydrogen or C1-C4 alkyl, W2 is a group -NR42 -, -O- or -S-, R42 is hydrogen or substituted or unsubstituted C1-C4 alkyl, W1 is a radical -C (O) O-, -0 (O) C-, -C (O) NH- or -HN (0) C-, X7 is halogen, hydroxyl, sulfo, C 1 -C 4 alkylsulfonyl, phenylsulfonyl, substituted or unsubstituted amino, 3-carboxypyridin-1-yl or 3-carbapyridin-1-yl, T5 independently has one of the meanings indicated for X7 or is optionally an alkoxy, aryloxy, alkylthio or substituted arylthio radical, or is a heterocyclic radical containing nitrogen or is a reactive radical of the formula,
143 • N-alq-SO2-Y2 (28a), R44
N-alq-W3-alq 'SO2-Y2 (28b), R45
N-arylene-SO2-Y2 (28c), ^ 5
N - aiilen - (alq) f - W4 - alq "- SO2 - Y2 (28d), R45
N r ~ N alq-S02-Y2 (28e) or
wherein B5 is an aliphatic, cycloaliphatic, aromatic or aromatic-aliphatic bridging member, or together with -NR e- or -NR47- is a heterocyclic ring, Rβ and R47 are each independently of the other hydrogen or C1- alkyl C4 substituted or unsubstituted, X8 is halogen, hydroxyl, substituted or unsubstituted amino, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl, T6 independently has one of the meanings indicated for X8, or is optionally a radical alkoxy, aryloxy, alkylthio or substituted arylthio, or is a heterocyclic radical containing nitrogen or independently a radical U- (B4) c- (W?) d- (B3) e-W2-, where U, B, B3, Wi and W2 are each as defined above, R4 is hydrogen, or C1-C4 alkyl hydroxyl-, sulfo-, sulfato-, carboxyl-, or cyano-substituted, or a radical,
-alq-S02-Y2, R45 is hydrogen or C1-C4 alkyl, R3 is hydrogen, hydroxyl, sulfo, sulfate, carboxyl, cyano, halogen, C1-C4 alkoxycarbonyl, C? -C4 alkanoyloxy, carbamoyl or the group -S02-Y2, alk and alk "are independently of each other C1-C7 alkylene, arylene is a phenylene or unsubstituted naphthylene or sulfo-, carboxyl-, C? -C4- alkyl, C? -C4 alkoxy -, or halogen-substituted, Y2 is vinyl or a radical CH2-CH2-Z2 and Z2 is a leaving group, W3 is -O- or -NR45-, W4 is a group -SO2-NR44-, -CONR44-, or -NR4 CO-, and c, d, e and f are each independently of the other 0 or 1, d being 0 when e is 0, provided that the compounds of the formula (26) have at least one sulfo or sulfate group and by at least one alkaline cleavable group An aliphatic bridge member B3 or B4 is, for example, a straight or branched chain C al-C? alkylene, preferably a straight or branched chain d-C6 alkylene. radicals of B3 and alkylene B4 Particularly preferred are methylene, 1,2-ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 2-methyl-1,5-pentylene and 1,6-hexylene, in particular methylene and , 2-ethylene. An aliphatic bridge member, B5, can be, for example, straight or branched chain C2-C2 alkylene and optionally substituted with hydroxyl, sulfo, or sulfate, and / or -O-interrupted. Preferably, B is a straight or branched chain C2-C6 alkylene, which may be substituted by hydroxyl, sulfo or sulfate. Examples of particularly preferred alkylene B5 radicals are 1,2-ethylene, 1,2-propylene, 1,3-propylene, 2-hydroxy-1,3-propylene, 1,4-butylene, 2-methyl-1, 5 -pentylene and 1,6-hexylene. A cycloaliphatic bridge member B5 is, for example, cyclohexylene or the radical of the formula,
or -NR46- and NR47- are combined with B5 in a ring, for example, a piperazine ring. Examples of aromatic bridge members, B5, are unsubstituted C1-C4 alkyl or, for example, sulfo-, carboxyl-, 1,2-, 1,3- or 1,4-phenylene-C1-C4 alkoxy- or halogen-substituted, or sulfo-substituted naphthylene or a radical of the formula, wherein Z3 is for example -CO-, -NHCO-, -NHCONH-, - (CH2)? 4-, -NH-, -CH = CH-, -O-, -SO2- or -N = N-; and (R48) o-2 and (R49) o-2 independently of one another represent 0 to 2 identical or different radicals selected from the group consisting of sulfo, methyl, methoxy and chloro. Preferred to be used as the aromatic bridging member, B5, are 1,3- or 1,4-unsubstituted phenylene or sulfo-, carboxyl-, chloro-, methyl-, or methoxy-substituted, naphthylene substituted by one or two groups sulfo, or a radical of the formula,
wherein Z4 is -NHCONH-, -O-, -NH-, -CH = CH-, or -CH2-; and R50 is hydrogen or sulfo. Examples of particularly preferred aromatic bridge members, B5, are 1,3-phenylene, 1,4-phenylene, 4-methylphenylene-1, 3,4-sulfophenylene-1,3,3-sulfophenylene-1,4,3, 6-disulfophenylene-1,4,6,6-disulfophenylene-1,3,3,7-d-sulfonaphthylene-1, 5-4,8-dispholunaphthylene-2,6, 2,2'-disulfodiphenylene-4,4 ', 4,4'-phenylene-2,2'-sulphonic acid, or 2,2'-disulphostyylbenylene-4, 4 \ and in particular 4-sulfophenylene-1,3,3-sulfophenylene-1,4,6,6-disulfophenylene-1,4 or 4,6-disulfophenylene-1,3. An example of aromatic-aliphatic bridge members, B5, is C 1 -C 4 phenylene alkylene, unsubstituted or substituted in the phenylene moiety, for example by sulfo, methyl, methoxy, carboxyl or chloro. An aromatic-aliphatic bridge member, B, is preferably unsubstituted phenylethmethylene or phenylenemethylene substituted by sulfo, methyl or methoxy in the phenylene moiety. B5 is preferably C2-d alkylene, which can be substituted by unsubstituted hydroxyl, sulfo or sulfate or sulfo-, carboxyl-, chloro-, methyl-, or methoxy-substituted 1,3- or 1,4-phenylene , naphthylene substituted by one or two sulfo groups, or a radical of the formula,
wherein Z4 is -NHCONH-, -O-, -NH-, -CH = CH-, or -CH2-; and R50 is hydrogen or sulfo. Particularly preferable Bs is 4-sulfophenylene-1,3,3-sulfophenylene-1,4,6,6-disulfophenylene-1,4 or 4,6-disulfophenylene-1,3. R4ß and 47 are each independently of the other,
example, hydrogen or unsubstituted C?-C 4 alkyl or, for example, halogen-, hydroxyl-, cyano-, C?-C alco alkoxy, C alco-d-, carboxyl-, sulfamoyl-, sulfo- , or sulfate-substituted. Preferably, R46 and R7 are each independently of the other hydrogen or Ci-d alkyl, preferably particularly hydrogen, methyl or ethyl. c and d are each preferably 0. R 2 is, for example, hydrogen or unsubstituted C 1 -C 4 alkyl, or, for example, halogen, hydroxyl, cyano, C 1 -C 6 alkoxy, alkoxy carbonyl C? -C4-, carboxyl-, sulphamoyl-, sulfo-, or sulfate-substituted. Preferably, R42 is hydrogen or d-d alkyl, preferably particularly hydrogen, methyl or ethyl. A 2-hydroxyphenyl-1, 3,5-triazine radical, U, has, for example, the formula,
wherein z is an integer from 1 to 3, and Q4, Q5 and Q6 are independently of the other hydrogen, hydroxyl, d-C12 alkyl, C1-C18 alkoxy, or C?-C4 alkoxy of Ci-alkoxy; unsubstituted or hydroxyl-substituted d.
Examples of 2-hydroxyphenyl-1, 3,5-triazine radicals, U, are the 2,4,6-tris (2-hydroxy-4-octyloxy phenyl) -1, 3,5-triazine, 2- ( 2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-di hydroxy in) -4,6-bis (2 , 4-di methylphenyl) -1, 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2 - (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2, 4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3 , 5-triazine, 2- (2-hydroxy-4-methoxy-6-sulfophenyl) -4,6-bis (phenyl) -1, 3,5-triazine or 2- [2-hydroxy-4- (2- hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine. The radical benzotriazole U has, for example, the formula,
where R5? and R52 are independently hydrogen; Ci-d alkyl; Ci-d alkoxy; halogen; hydroxyl; nitro; sulfo or carboxyl. A radical 2-hydroxybenzophenone U has, for example, the formula,
wherein (A3) 0-3 represents from 0 to 3 identical or different radicals selected from the group consisting of halogen, hydroxyl, sulfo, C? -C? 2 alkoxy, or C1-C4 phenylalkoxy, and (A) or -2 represents 0 to 2 identical or different radicals selected from the group consisting of halogen, hydroxyl, sulfo, C? -C? 2 alkoxy, or Ci-d phenylalkoxy Examples of suitable 2-hydroxybenzophenone radicals U are the radicals of 2,4-d ihydroxy-, 2-hydroxy-4-methoxy-, 2-hydroxy-4-octoxy-, 2-hydroxy-4-decyloxy-, 2-hydroxy-4-dodecyloxy-, 2-hydroxy-4 -methoxy-sulfo-, 2-hydroxy-4-benzyloxy-, 4,2 ', 4'-trihydroxy-, or 2'-hydroxy-4,4'-dimethoxy-benzophenone. An oxalanilide radical U has, for example, the formula,
wherein x and y are each independently of the other an integer from 0 to 3, provided that the sum of (x + y) _1, and each substituent L2 is independently of the other sulfa; alkyl, alkoxy, or alkylthio each having 1 to 22 carbon atoms and unsubstituted or substituted in the alkyl portion by sulfo; or phenoxy or phenylthio not substituted or substituted on the phenyl ring by sulfo Examples of suitable oxalanilide radicals U are the radical of 4,4'-dioctyloxyoxanilide, 2,2'-diatoxioxanilide, 2,2'-dioctyloxy-5,5-di -te-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyloxanilide, 2-methoxy-5-sulfooxanilide, 2- ethoxy-5-sulfo-oxanilide, 2,5-dimethoxyoxanilide, 2-ethoxy-tert-butyl-2'-ethyloxanilide alone or mixed with the radical 2-ethoxy-2'-ethyl-5,4'-di-ter- butyl-oxanilide, or mixtures of the o- and p-methoxy radicals, and also of disubstituted o- and p-ethoxy-oxanilides. Suitable acrylate radicals U are C1-C10 alkyl acrylates, which are unsubstituted or substituted by cyano or C1-C4 carboalkoxy in the a-position, bear a phenyl, C-C4 alkoxyphenyl, or an indolinyl radical in a β-position and are substituted or unsubstituted by phenyl, alkoxyphenyl of C1-C4, or C1-C4 alkyl in another position β. Examples of U-acrylate radicals are the radical of α-cyano-β, β-diphenylacrylate of ethyl or isooctyl, α-carbomethoxycinnamate of methyl, α-cyano-β-methyl-p-methoxycinnamate of methyl or butyl, β-carbomethoxy-p methyl methoxycinnamate, or N- (β-carbomethoxy-β-cyanovinyl) -2-methylindolino. A substituted or unsubstituted benzoic acid or benzoic acid radical U is, for example, a radical of unsubstituted benzoic acid or hydroxyl-, or C 1 -C 4 -substituted alkyl, or its phenyl ester, Ci-Cβ-phenyl alkyl , or alkyl of C? -C? 8. Examples are the benzoic acid radical, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4- 2,4-di-tert-butylphenyl hydroxybenzoate, 3, 5-di-tert-butyl-4-hydroxybenzoate hexadecyl, 3, 5-di-tert-butyl-4-hydroxybenzoate octadecyl, or 3, 5 2-methyl-4,6-di-tert-butylphenyl-di-tert-butyl-4-hydroxybenzoate. When U is a radical of formula (27) above, (R4o) or -3 preferably denotes 0 to 3 identical or different radicals, R40 is selected from the group consisting of sulfo, methyl, methoxy, hydroxyl and carboxyl, and R ? is preferably halogen, and 2 is preferably a group -N H-CO- or -N H-SO2-. U is in this case preferably a radical of the formula,
where (R53) or-? denotes 0 or 1 radical, R23 is selected from the group consisting of sulfo, methyl, methoxy, hydroxyl and carboxyl, and M3 is a group -N H-CO- or -NH-SO2-. Particularly preferably U is the radical of an oxalic diarylamide of the formula,
wherein R 3 is unsubstituted or hydroxyl- or alkoxy-substituted alkyl, or unsubstituted or substituted alkyl with C 1-d alkyl; R39 is hydrogen; halogen; C? -C? 2 alkyl; C 1 -C 5 phenylalkyl, or C 1 -C 3 alkoxy; B2 is a direct bond or a bivalent radical of the formula -O-L3-, wherein L3 is unsubstituted or substituted with hydroxyl d-C6 alkylene; M "is hydrogen or an alkali metal, and v is 2, 1 or 0. A C 1 -C 5 alkyl R 37 is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl , amyl or isoamyl; A halogen R39 is, for example, fluorine, bromine or chlorine Chlorine is preferred A C? -C? 2 R39 alkyl can be branched or unbranched radicals, for example, methyl, ethyl, -propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, pentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl or dodecyl. C1-C5 R39 is, for example, phenethyl, phenylpropyl, phenylbutyl or preferably benzyl.A C1-C5 alkoxy R39 is, for example, methoxy, ethoxy, isopropoxy, isobutoxy, tert-butoxy or tert-amyloxy. ? -C6 L3 is a divalent saturated hydrocarbon radical, for example, methylene, ethylene, propylene, trimethylene, tetramethylene, ethylethylene, pentamethylene or hexamethylene.An alkali metal M "is, for example plo, lithium, sodium or potassium. Sodium is preferred. Particularly suitable for use as a radical of the oxyalic diarylamide of the formula (35) is a compound wherein L3 is trimethylene or, -CH2-CH-CH2- I
OH. An additional preferred oxalic diarylamide radical is conformed to the formula (35) indicated above, wherein R39 is hydrogen, alkyl
C? -C? 2, or C1-C5 alkoxy. Also preferred is an oxyalic diarylamide radical of the formula (35) indicated above, wherein, R37 is C1-C3 alkyl, R3 is hydrogen, C1-C3 alkyl, or C1-C3 alkoxy; B2 is a direct bond or the radical - [O- (CH2) 3] m; and m is 0 or 1. Particularly preferred to be used as a diarylamide oxalic radical is a compound of the formula (35), wherein, v is 0 or 1; R37 is methyl or ethyl; R39 is hydrogen or C1-C3 alkoxy; and B2 is a direct link. The reactive UV absorbers of the formula (26) are known or can be prepared, for example, by reacting a compound of the formula, U- (B4) e- (W,) d- (B3) .- W2-H ( 36), and a compound of the formula,
(37) and a compound of the formula, T5 * -H (38), wherein U, B3, B4, Wi, W2, X, c, d and e are each as defined above, Hal is halogen, preferably fluorine or chlorine, and Ts * has the meanings indicated above for Ts different from halogen, with each other, the order of the elementary reactions being freely selectable in relation to the starting compounds that will react with each other. The application of the reactive UV absorbers can be carried out before, during or after the application of the direct dyes (staining), through an exhausted or continuous process. The application is preferred during staining. Particular preference is given to the application of UV absorbers together with direct dyes. Preference is given, for the process of the present invention, to dye combinations containing radicals of the formulas (4a), (4b), (5a), (6), (7), (8), (9a) or (9b) with UV absorbers of formulas (10), (11), (12) or (13).
Preference is given, for the process of the present invention, to dye combinations containing radicals of the formulas (4a), (4b), (5a), (6), (7), (8), (9a) or (9b) with reactive UV absorbers of the formula (26). Particular preference is given, for the process of the present invention, to combinations of dyes containing radicals of the formulas (4a), (4b), (5a), (6), (7), (8), (9a) or (9b) with reactive UV absorbers of the formula (26), wherein U is the radical of the formula (35) ). It is understood that cellulosic fiber radicals represent, for example, natural cellulose fiber, such as cotton, linen and hemp, and also cellulose pulp and regenerated cellulose. Direct dyes are also suitable for treating hydroxyl-containing fibers present in fabrics in admixture, for example, blends of cotton with polyester fibers or polyamide fibers. For use in accordance with the present invention, cellulosic fiber materials having a density of between 30 and 200 g / m2 are preferred. Cotton is the preferred cellulosic fiber material. The mentioned fibers can be present in various forms, for example, staple fiber or yarn or as fabrics or stitches. The direct dyes can be applied to the fiber material and fixed on the fiber in various forms, in particular in the form of aqueous dye solutions and printing pastes. They are suitable not only for the exhausted process, but also for dyeing through a pad dyeing process, whereby the material is impregnated with aqueous dye solutions with or without a salt content and the dyes are fixed after an alkali treatment or in the presence of alkali with or without heating. After fixing, the dyes or prints are thoroughly rinsed with cold and hot water in the presence or absence of an agent, which has a dispersing effect and promotes diffusion of the unfixed portions. Custom staining and printing procedures are employed. The dye liquors may contain the generally customary additives, for example, aqueous solutions of inorganic salts, for example of alkali metal chlorides or alkali metal sulfates, alkali metal hydroxides, ureas, thickeners, for example, alginate thickeners, water-soluble cellulose alkyl ethers and also dispersing, leveling and deaerating aids, defoamers, penetration accelerators and migration inhibitors, also sodium m-nitrobenzenesulfonate, and, like other thickeners, for example, methylcellulose, starch ethers , emulsion thickeners, preferably an alginate, for example, sodium alginate and also wetting agents. Preference is given to use according to the present invention, to the staining through the exhausted method. Exhausted staining generally occurs in an aqueous medium, at a liquor ratio of, for example, 2: 1 to 60: 1, in particular a liquor ratio of 5: 1 to 20: 1, a pH of dye bath of, for example, 6 to 13 and a temperature of, for example, 40 to 120 ° C, in particular a temperature of 60 to 95 ° C. The cellulose fiber materials treated with the direct dyes and UV absorbers are remarkable for a very high sun protection factor. The sun protection factor is defined as the ratio of the harmful dose of UV energy on the protected skin to the harmful dose of UV energy in the unprotected skin.
Accordingly, a sun protection factor is also a measure of UV transmission of untreated fiber materials and fiber materials treated with direct dyes and UV absorbers used in this invention. The UV transmission capacity of fiber materials can be measured, for example, in a transmission measurement using a double monochromatic spectrophotometer equipped with an Ulbricht sphere. The sun protection factor can be calculated, for example, by the method described by B. L. Diffey and J. Robson in J Soc. Cosmet. Chem. 40, 127-133 (May / June 1989). The following examples illustrate the invention. Temperatures are indicated in degrees Celsius. The parts and percentages are by weight, unless otherwise indicated. Parts by weight refer to parts by volume such as kilogram to liter.
EXAMPLE 1
two specimens were individually treated, each weighing 10 g of a bleached cotton tricot having a weight of 185 g / m2 and a thickness of 0.85 mm, in a dyeing machine AHIBA®, at a liquor ratio of 25: 1 in twelve different liquors. Liquor 1. contains 0.013 g of a direct dye which, in the form of the free acid, conforms to the following formula:
0 5 g / 1 of a commercial staining aid, for example, a penetration accelerator, and 0.5 g / 1 of calcined sodium carbonate. Liquor 2, corresponds to liquor 1, but also contains 0.075 g of a UV absorber of the formula,
Liquor 3, contains 0.011 g of a direct dye which, in the free acid form, conforms to the following formula: 0.5 g / 1 of a commercial staining aid, for example, a penetration accelerator, and 0.5 g / 1 of calcined sodium carbonate. Liquor 4. corresponds to liquor 3, but also contains 0.075 g of a UV absorber of the formula (200). Liquor 5. contains 0.01 g of a direct dye which, in the free acid form, conforms to the following formula:
0. 5 g / 1 of a commercial staining aid, for example, a penetration accelerator and 0.5 g / l of calcined sodium carbonate. Liquor 6. corresponds to liquor 5, but also contains 0.075 g of a UV absorber of the formula (200).
Liquor 7. contains 0.008 g of a direct dye which, in the form of the free acid, conforms to the following formula:
0. 5 g / 1 of a commercial staining aid, for example a penetration accelerator, and 0.5 g / 1 of calcined sodium carbonate. Liquor 8. corresponds to liquor 7, but also contains 0.075 g of a UV absorber of the formula (200). Liquor 9. contains 0.009 g of a direct dye, which, in the form of the free acid, conforms to the following formula:
0. 5 g / l of a commercial staining aid, for example, a penetration accelerator and 0.5 g / l of a commercial staining aid, for example, a penetration accelerator, and 0.5 g / l of calcined sodium carbonate. Liquor 10. corresponds to liquor 9, but also contains 0.075 g of a UV absorber of the formula (200). Liquor 11, contains 0.008 g of a direct dye which, in the free acid form, conforms to the following formula:
0. 5 g / l of a commercial staining aid, for example a penetration accelerator, and 0.5 g / l of calcined sodium carbonate. Liquor 12 corresponds to liquor 11, but also contains 0.075 g of a UV absorber of formula (200). The cotton tricot specimens were introduced to the 40 ° C dye liquors; after 5 minutes, the dye bath was heated at a rate of 2 ° C / minute, at a temperature of 95 ° C, and left at that temperature for 60 minutes. At 10 minutes and 20 minutes from the achievement of 95 ° C, 5 g / l of sodium chloride was added at each time. After a total time of 45 minutes staining, liquors were cooled to 60 ° C, and stained specimens were removed from the liquor, rinsed with cold water, centrifuged and then dried at 100 ° C. Then, the transmission spectra of the specimens in the UV region were measured and the sun protection factors were determined. The sun protection factors found are presented in Table 1
TABLE 1
EXAMPLE 2
Example 1 was repeated, except that in liquors 2, 4, 6, 8, 10 and 12 the 0.075 g of the UV absorber of the formula (200) was replaced by the same amount of a UV absorber of the formula, ( 201).
The sun protection factors found for the twelve specimens are presented in Table 2.
TABLE 2
EXAMPLE 3
Examples 1 and 2 were repeated, the bleached cotton knit of 185 g / m2 and 0.85 mm was replaced by a cotton creton with a weight of 135 g / m2 and a thickness of 0.2 mm. The sun protection factors found for the 18 specimens are presented in Table 3.
TABLE 3
Claims (23)
1. - A method for increasing the sun protection factor of cellulosic fiber materials, which comprises treating the cellulosic fiber materials with at least one direct dye and at least one UV absorber.
2. A process according to claim 1, wherein the amount of direct dye used is 0.01 to 10% by weight, based on the weight of the fiber material.
3. A process according to claim 1, wherein the amount of UV absorber used is 0.001 to 5% by weight, based on the weight of the fiber material.
4. A process according to claim 1, wherein the amount of direct dye used is 0.001 to 0.2% by weight, based on the weight of the fiber material, and the amount of UV absorber used is 0.2 to 2. % by weight, based on the weight of the fiber material.
5 - A method according to claim 1, wherein the amount of direct dye used is from 0.2 to 2% by weight, based on the weight of the fiber material, and the amount of UV absorber used is from 0.05 to 0.2% by weight, based on the weight of the fiber material.
6. A method according to claim 1, wherein the UV absorber is used together with the direct dye.
7. A process according to any of claims 1 or 3 to 6, wherein the UV absorber used is a reactive UV absorber.
8. A process according to any of claims 1,2 or 4 to 6, wherein the direct dye used has the formula, A? -B? -A2 (1) wherein B1 is a bridge member, and Ai and A2 are independently from each other, the radical of a monoazo dye, polyazo, azo metal complex, stilbene or anthraquinone, or wherein B1 and Ai are each as defined above, and A2 is a phenyl or naphthyl radical substituted by a heterocyclic radical or a benzoylamino or phenylamino radical, or wherein B1 is a direct bond, and Ai and A2 are each the radical of an azo dye metal complex.
9. A process according to claim 8, wherein Ai and A2 are radicals of the formulas, D? -N = N- (M1-N = N) 0? - K, - (4a) or - D1-N = N- (M1-N = N) 0.? - K1 (4b), where Di is the radical of a diazo component of the benzene or naphthalene series, Mi is the radical of a middle component of the benzene or naphthalene series, K1 is the radical of a coupling component of the series benzene or naphthalene.
10. A process according to claim 8, wherein Ai and A2 are radicals of the formulas, wherein the oxygen or carboxyl group is linked to the radical Q1, Q2, or Q3 in an ortho position relative to the azo group, and Q ,, Q2, or Q3 each are independently of the others a radical of the benzene series or naphthalene.
11 - A method according to claim 8, wherein A and A2 are radicals of the formula,
12. - A method according to claim 8, wherein Ai and A2 are radicals of the formula, wherein G1 is a C2-C6 alkylene, cyclohexylene, phenylenemethylene or phenylene. 13 -.
13 - A process according to any of claims 1,2 or 4 to 6, wherein the direct dye used is a direct phthalocyanide dye containing the radical of the formula, (SO ^ / \ S02-NE- (8 ), wherein Pe is the radical of a copper or nickel phthalocyanine, W is -OH and / or -NR7R8, R7 and R8 are independently of each other hydrogen or unsubstituted or unsubstituted C 1 -C 4 alkyl or sulfo-substituted , R6 is hydrogen or C? -C alkyl, E is unsubstituted phenylene or C? -C-, halogeno-, carboxyl-, or sulfo-substituted alkyl, or an alkylene of dd, preferably a sulfophenylene or ethylene, and is 1, 2 or 3.
14. A process according to any of claims 1,2 or 4 to 6, wherein the direct dye used is a direct dye of dioxazine containing the radicals of the formulas, (9a) or wherein Ei is unsubstituted phenylene or C 1 -C 4 alkyl, halogen, carboxyl, or sulfo substituted alkyl or a C 2 -C 6 alkylene.
15. A process according to any of claims 1 or 3 to 6, wherein the UV absorber used is a 2-hydroxybenzophenone of the formula, wherein R9 is hydrogen, hydroxyl, C? -C? 4 alkoxy or phenoxy, R? 0 is hydrogen, halogen, C? -C4 alkyl or sulfo, Rn is hydrogen, hydroxyl, or Ci-d alkoxy, and R 2 is hydrogen, hydroxyl, or carboxyl.
16. A process according to any of claims 1 or 3 to 6, wherein the UV absorber used is a 2- (2'-hydroxyphenyl) benzotriazole of the formula, wherein R 3 is hydrogen, chloro, sulfo, C? -C? 2 alkyl, C5-C6 cycloalkyl, (C? -C8 alkyl) phenyl, C7-C9 phenylalkyl, or sulfonated C-9 phenylalkyl, Ri4 is hydrogen, chloro, Ci-d alkyl, C 1 -C 4 alkoxy, hydroxyl, or sulfo, R 5 is C 1 -C 2 alkyl, chloro, sulfo, Ci-d alkoxy, phenyl, (C 1 -C 8 alkyl) phenyl, C 5 -C 6 cycloalkyl , C2-C9 alkoxycarbonyl, carboxyethyl, phenylalkyl of dd, or sulfonated C7-C9 phenylalkyl, R6 is hydrogen, chloro, C1-C4 alkyl, C1-C4 alkoxy, C2-C9 alkoxycarbonyl, carboxyl or sulfo, and R17 is hydrogen or chlorine.
17. A process according to any of claims 1 or 3 to 6, wherein the UV absorber used is a 2- (2'-hydroxyphenyl) -s-triazine of the formula, wherein R, s is hydrogen, halogen, C 1 -C 4 alkyl or sulfo, Ri 9 is hydrogen, C 1 -C 4 alkyl, Ci-d alkoxy, or hydroxyl, R 20 is hydrogen or sulfo, and R 2 and R 22 are independently yes C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 5 -C 6 cycloalkyl, phenyl or phenyl C 4 alkyl- and / or hydroxyl substituted. 18 -.
18 - A method according to any of claims 1 or 3 to 6, wherein the UV absorber used is a s-triazine compound of the formula, (13),? 24 25 wherein at least one of the substituents R23, R24, and R25 is a radical of the formula, wherein A is dd alkyl or 2-hydroxytrimethylene, and M 'is sodium, potassium, calcium, magnesium, ammonium, or tetraalkyl of C? -C4-ammonium, and b is 1 or 2, and the remaining substituent is or the remaining substituents are independently of each other C 1 -C 4 alkyl, phenyl, C 1 -C 2 alkyl, or phenyl linked to the triazinyl radical via oxygen, sulfur, imino or C 1 -C 11 alkylimino, or a radical of the formula (14).
19. A process according to claim 7, wherein the reactive UV absorber used is a compound of the formula, U < B4, _ (w.J- (B3) rW2 f ^ T5 (26), 7 wherein B3 and B4 are each independently of the other an aliphatic bridge member; U is the radical of a UV absorber of the group of 2-hydroxybenzophenones, benzotriazoles, 2-hydroxyphenyl-1, 3, 5-triazines, oxalodiamines, acrylates, substituted or unsubstituted benzoic acids and esters and radicals of the formula, wherein (R4o) or -3 represents 0 to 3 identical or different radicals, R40 is selected from the group consisting of sulfo, C1-C4 alkyl, C1-C4 alkoxy, halogen, hydroxyl, carboxyl, nitro and C1-C4 alkylcarbonyl; -d, R41 is hydrogen, sulfo, C? -C4 alkyl, C? -C4 alkoxy, M2 is a group -NR30-CO- or -NR3o-SO2-, R30 is hydrogen or C1-C4 alkyl , W2 is a group -NR42-, -O- or -S-, R42 is hydrogen or substituted or unsubstituted dC4 alkyl, W1 is a radical -C (O) O-, -O (O) C- , -C (O) NH- or -HN (O) C-, X7 is halogen, hydroxyl, sulfo, C 1 -C 4 alkylsulfonyl, phenylsulfonyl, substituted or unsubstituted amino, 3-carboxypyridin-1-yl or 3- carbamoylpyridin-1-yl, T5 independently has one of the meanings indicated for X7 or is optionally an alkoxy, aryloxy, alkylthio or substituted arylthio radical, or is a heterocyclic radical containing nitrogen or is a reactive radical of the formula, ? 43 N-alq-SO2-Y2 (28a), R44 N-alq-W3-alq "-SO2-Y2 (28b), R45 -N-arylene-SO2-Y2 (28c), R 45 N - aiylene - (alq) f - W4 - alq "- SO2 - Y2 (28d), R 5 wherein B5 is an aliphatic, cycloaliphatic, aromatic or aromatic-aliphatic bridging member, or together with -NR 6- or -NR 7- is a heterocyclic ring, R 6 and R 7 are each independently of the other hydrogen or alkyl of substituted or unsubstituted d-C4, X8 is halogen, hydroxyl, substituted or unsubstituted amino, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl, T6 independently has one of the meanings indicated for X8, or is optionally an alkoxy, aryloxy, alkylthio or substituted arylthio radical, or is a heterocyclic radical containing nitrogen or independently a radical U- (B4) c- (W?) d- (B3)? -W2-, where U, B4, B3, Wi and W2 are each as defined above, R is hydrogen, or C1-C4 alkyl hydroxyl-, sulfo-, sulfato-, carboxyl-, or cyano-substituted, or a radical, -alk-SO2-Y2, R5 is hydrogen or C1-C4 alkyl, R43 is hydrogen, hydroxyl, sulfo, sulfate, carboxyl, cyano, halogen, C?-C4 alkoxycarbonyl, C?-C4 alkanoyloxy, carbamoyl or the group -SO2-Y2, alk and alq "are independently of each other C1-C7 alkylene, arylene is a phenylene or unsubstituted naphthylene or sulfo-, carboxyl-, C? -C4- alkyl, C? C-, or halogen-substituted, Y2 is vinyl or a radical CH2-CH2-Z2 and Z2 is a leaving group, W3 is -O- or -NR4S-, W4 is a group -SO2-NR 4-, -CONR44- , or -NR44CO-, and c, d, e and f are each independently of the other 0 or 1, d being 0 when e is 0, provided that the compounds of the formula (26) have at least one sulfo or sulfate group and
20. A process according to claim 19, wherein the reactive UV absorber is the compound of the formula (26), wherein U is a radical of an oxalic diarylamide of the formula, wherein R37 is unsubstituted or hydroxyl- or alkoxy-substituted alkyl, or benzyl unsubstituted or substituted with C1-C5 alkyl; R39 is hydrogen; halogen; C? -C? 2 alkyl; phenylalkyl of d-C3, or C1-C5 alkoxy; B2 is a direct bond or a bivalent radical of the formula -O-L3-, wherein L3 is unsubstituted or substituted by C6-C6 alkylene with hydroxyl; M "is hydrogen or an alkali metal, and v is 2, 1 or 0.
21. A process according to claim 1, wherein the sun protection factor of cellulosic fiber materials is increased by at least a factor of 5.
A method according to claim 1, wherein the sun protection factor of cellulosic fiber materials used is cotton
23. A method according to claim 1, wherein the sun protection factor of Used cellulose fiber materials have a density between 30 and 200 g / m '
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH770/95 | 1995-03-17 | ||
| CH77095 | 1995-03-17 | ||
| PCT/EP1996/000896 WO1996029461A1 (en) | 1995-03-17 | 1996-03-04 | Process for increasing the sun protection factor of cellulosic fibre materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MX9707018A MX9707018A (en) | 1997-11-29 |
| MXPA97007018A true MXPA97007018A (en) | 1998-07-03 |
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