EP2268784B2 - Reduced spotting granules - Google Patents
Reduced spotting granules Download PDFInfo
- Publication number
- EP2268784B2 EP2268784B2 EP09737914.3A EP09737914A EP2268784B2 EP 2268784 B2 EP2268784 B2 EP 2268784B2 EP 09737914 A EP09737914 A EP 09737914A EP 2268784 B2 EP2268784 B2 EP 2268784B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- dyes
- dye
- granule
- sokalan
- violet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
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- 239000008187 granular material Substances 0.000 title claims description 42
- 239000000975 dye Substances 0.000 claims description 74
- 229920000642 polymer Polymers 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 16
- 239000003599 detergent Substances 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 239000003945 anionic surfactant Substances 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 11
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 239000000981 basic dye Substances 0.000 claims description 8
- 239000000980 acid dye Substances 0.000 claims description 7
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000000982 direct dye Substances 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001204 N-oxides Chemical class 0.000 claims description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 claims description 3
- 229920000768 polyamine Polymers 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 description 28
- VRVDFJOCCWSFLI-UHFFFAOYSA-K trisodium 3-[[4-[(6-anilino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-5-methoxy-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].COc1cc(N=Nc2cc(c3cccc(c3c2)S([O-])(=O)=O)S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O VRVDFJOCCWSFLI-UHFFFAOYSA-K 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- MHOFGBJTSNWTDT-UHFFFAOYSA-M 2-[n-ethyl-4-[(6-methoxy-3-methyl-1,3-benzothiazol-3-ium-2-yl)diazenyl]anilino]ethanol;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC(N(CCO)CC)=CC=C1N=NC1=[N+](C)C2=CC=C(OC)C=C2S1 MHOFGBJTSNWTDT-UHFFFAOYSA-M 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000013256 coordination polymer Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 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 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000001045 blue dye Substances 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 238000010186 staining Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 Bis-azo copper Chemical compound 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- 150000004056 anthraquinones Chemical class 0.000 description 3
- 239000000987 azo dye Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920002345 Sokalan® PA 20 Polymers 0.000 description 2
- 229920002334 Spandex Polymers 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 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 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000985 reactive dye Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- SCMDRBZEIUMBBQ-UHFFFAOYSA-N (1e)-1-[(8-amino-3,7-dimethyl-10-phenylphenazin-10-ium-2-yl)hydrazinylidene]naphthalen-2-one;chloride Chemical compound [Cl-].C=12C=C(N)C(C)=CC2=NC2=CC(C)=C(N\N=C\3C4=CC=CC=C4C=CC/3=O)C=C2[N+]=1C1=CC=CC=C1 SCMDRBZEIUMBBQ-UHFFFAOYSA-N 0.000 description 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- KZYAYVSWIPZDKL-UHFFFAOYSA-N 1,4-diamino-2,3-dichloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=C(Cl)C(Cl)=C2N KZYAYVSWIPZDKL-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- ZNQIAQXHADXXQI-UHFFFAOYSA-N 1-anilino-4-hydroxyanthracene-9,10-dione Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(O)=CC=C1NC1=CC=CC=C1 ZNQIAQXHADXXQI-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- CULIYQPRUGMRRT-UHFFFAOYSA-N 2-chloro-n-[2-[(2-cyano-4-nitrophenyl)diazenyl]-5-(diethylamino)phenyl]acetamide Chemical compound ClCC(=O)NC1=CC(N(CC)CC)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1C#N CULIYQPRUGMRRT-UHFFFAOYSA-N 0.000 description 1
- UWOFGIXNNCPENM-UHFFFAOYSA-N 3,3-difluoropentan-2-one Chemical compound CCC(F)(F)C(C)=O UWOFGIXNNCPENM-UHFFFAOYSA-N 0.000 description 1
- POELEEGOWIJNBI-UHFFFAOYSA-N 3-[2-[[4-(diethylamino)phenyl]diazenyl]-6-ethoxy-1,3-benzothiazol-3-ium-3-yl]propanamide;chloride Chemical compound [Cl-].S1C2=CC(OCC)=CC=C2[N+](CCC(N)=O)=C1N=NC1=CC=C(N(CC)CC)C=C1 POELEEGOWIJNBI-UHFFFAOYSA-N 0.000 description 1
- VZOOHWGPNLPIHR-UHFFFAOYSA-N 3-[2-[[4-[bis(2-chloroethyl)amino]phenyl]diazenyl]-6-methoxy-1,3-benzothiazol-3-ium-3-yl]propanamide;chloride Chemical compound [Cl-].S1C2=CC(OC)=CC=C2[N+](CCC(N)=O)=C1N=NC1=CC=C(N(CCCl)CCCl)C=C1 VZOOHWGPNLPIHR-UHFFFAOYSA-N 0.000 description 1
- IHZXTIBMKNSJCJ-UHFFFAOYSA-N 3-{[(4-{[4-(dimethylamino)phenyl](4-{ethyl[(3-sulfophenyl)methyl]amino}phenyl)methylidene}cyclohexa-2,5-dien-1-ylidene)(ethyl)azaniumyl]methyl}benzene-1-sulfonate Chemical compound C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 IHZXTIBMKNSJCJ-UHFFFAOYSA-N 0.000 description 1
- AOMZHDJXSYHPKS-DROYEMJCSA-L Amido Black 10B Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC2=CC(S([O-])(=O)=O)=C(\N=N\C=3C=CC=CC=3)C(O)=C2C(N)=C1\N=N\C1=CC=C(N(=O)=O)C=C1 AOMZHDJXSYHPKS-DROYEMJCSA-L 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004382 Amylase Substances 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002341 Sokalan® CP 13 S Polymers 0.000 description 1
- 229920002344 Sokalan® PA 110 S Polymers 0.000 description 1
- 229920002355 Sokalan® PA 40 Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- IURGIPVDZKDLIX-UHFFFAOYSA-M [7-(diethylamino)phenoxazin-3-ylidene]-diethylazanium;chloride Chemical compound [Cl-].C1=CC(=[N+](CC)CC)C=C2OC3=CC(N(CC)CC)=CC=C3N=C21 IURGIPVDZKDLIX-UHFFFAOYSA-M 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N aconitic acid Chemical compound OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000001668 ameliorated effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- LHRXTFDXJQAGAV-UHFFFAOYSA-L disodium 3-hydroxy-4-(naphthalen-1-yldiazenyl)naphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].Oc1c(cc2cc(ccc2c1N=Nc1cccc2ccccc12)S([O-])(=O)=O)S([O-])(=O)=O LHRXTFDXJQAGAV-UHFFFAOYSA-L 0.000 description 1
- QCWPZYSLMIXIHM-UHFFFAOYSA-L disodium 4-amino-5-hydroxy-3-[(3-nitrophenyl)diazenyl]-6-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].Nc1c(N=Nc2cccc(c2)[N+]([O-])=O)c(cc2cc(c(N=Nc3ccccc3)c(O)c12)S([O-])(=O)=O)S([O-])(=O)=O QCWPZYSLMIXIHM-UHFFFAOYSA-L 0.000 description 1
- NJPXFJXCALXJCX-UHFFFAOYSA-L disodium 7-anilino-3-[[4-[(2,4-dimethyl-6-sulfonatophenyl)diazenyl]-2,5-dimethylphenyl]diazenyl]-4-hydroxynaphthalene-2-sulfonate Chemical compound [Na+].[Na+].Cc1cc(C)c(N=Nc2cc(C)c(cc2C)N=Nc2c(O)c3ccc(Nc4ccccc4)cc3cc2S([O-])(=O)=O)c(c1)S([O-])(=O)=O NJPXFJXCALXJCX-UHFFFAOYSA-L 0.000 description 1
- LARMRMCFZNGNNX-UHFFFAOYSA-L disodium 7-anilino-3-[[4-[(2,4-dimethyl-6-sulfonatophenyl)diazenyl]-2-methoxy-5-methylphenyl]diazenyl]-4-hydroxynaphthalene-2-sulfonate Chemical compound [Na+].[Na+].COc1cc(N=Nc2c(C)cc(C)cc2S([O-])(=O)=O)c(C)cc1N=Nc1c(O)c2ccc(Nc3ccccc3)cc2cc1S([O-])(=O)=O LARMRMCFZNGNNX-UHFFFAOYSA-L 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- DMMDCPMHDXAIRV-UHFFFAOYSA-N n-[5-[bis(2-methoxyethyl)amino]-2-[(2-cyano-4-nitrophenyl)diazenyl]phenyl]acetamide Chemical compound CC(=O)NC1=CC(N(CCOC)CCOC)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1C#N DMMDCPMHDXAIRV-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- QQBPIHBUCMDKFG-UHFFFAOYSA-N phenazopyridine hydrochloride Chemical group Cl.NC1=NC(N)=CC=C1N=NC1=CC=CC=C1 QQBPIHBUCMDKFG-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical class CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- KUIXZSYWBHSYCN-UHFFFAOYSA-L remazol brilliant blue r Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=C2C(=O)C3=CC=CC=C3C(=O)C2=C1NC1=CC=CC(S(=O)(=O)CCOS([O-])(=O)=O)=C1 KUIXZSYWBHSYCN-UHFFFAOYSA-L 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- FJBHGWADYLMEJG-UHFFFAOYSA-M sodium;3-[[4-[[4-(diethylamino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]cyclohexa-2,5-dien-1-ylidene]methyl]-n-ethylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC=1C=C(C=CC=1)S([O-])(=O)=O)=C(C=C1)C=CC1=[N+](CC)CC1=CC=CC(S([O-])(=O)=O)=C1 FJBHGWADYLMEJG-UHFFFAOYSA-M 0.000 description 1
- 239000000992 solvent dye Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3792—Amine oxide containing polymers
Definitions
- the present invention relates to the delivery of shading dyes to fabrics.
- WO 2005/003274 discloses that shading dyes are added to laundry detergents to increase whiteness.
- One drawback with these powders is that under certain conditions localised spotting occurs on fabric treated with the detergent powder.
- WO 2006 /020162 and WO 2006/053598 disclose laundry compositions comprising granules containing a dye.
- a shading dye granule present in a laundry detergent formulation is susceptible to providing unwanted spotting of fabrics.
- the present invention provides a shading dye granule comprising:
- the present invention provides a granular laundry detergent composition
- a granular laundry detergent composition comprising:
- the surfactant that comes from the base powder may be a mixture of different types of surfactants but the total concentration of anionic surfactant in the granulate laundry detergent is in the range from 10 to 50 wt %.
- the surfactant that comes from the base powder is preferably greater than 70% anionic surfactant.
- the shading dye granule is visually distinct (VD) from a granular background powder in order to provide a visual cue.
- the shading dye granule is for adding to a base powder (main detergent powder).
- the shading dye granule does not contain an anionic surfactant.
- the shading dye granule is admixed with the base powder, which must contain an anionic surfactant, there may be some migration of anionic surfactant to the shading dye granule.
- the ratio of the dye transfer polymer:the charged surfactant prevents spotting whilst permitting dye deposition of substantive dyes from the wash liquors.
- the shading dye is blue or violet. It is preferred that the shading dye(s) have a peak absorption wavelength of from 550nm to 650nm, preferably from 570nm to 630nm.
- Dyes are coloured organic molecules which are soluble in aqueous media that contain surfactants. Dyes are described in 'Industrial Dyes', Wiley VCH 2002, K.Hunger (edit or).
- Dyes are listed in the Color Index International published by Society of Dyers and Colourists and the American Association of Textile Chemists and Colorists . Dyes are preferably selected from the classes of basic, acid and direct dyes.
- Direct violet and direct blue dyes are preferred.
- the dyes are bis- azo or tris -azo dyes.
- the carcinogenic benzidene based dyes are not preferred.
- Bis-azo copper containing dyes such as direct violet 66 may be used.
- the direct dye is a direct violet of the following structures: or wherein:
- Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99.
- Cotton substantive acid dyes give benefits to cotton containing garments.
- Preferred acid dyes are:
- Preferred azine dyes are: acid violet 50 and acid blue 98.
- acid dyes are acid violet 17, acid black 1, acid red 17 and acid blue 29.
- the acid dye is present at 0.001 wt% to 0.006 wt% of the formulation.
- the composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores.
- Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
- Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
- the hydrophobic dye is present at 0.0005 wt% to 0.004 wt% of the formulation.
- Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International.
- Preferred examples include triarylmethane basic dyes, azo basic dye, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141 and thiazolium dyes.
- Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton.
- the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species.
- Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.
- Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.
- the shading dye granule according to the present invention comprising from 0.1 to 99.999 wt%, preferably from 0.5 to 18 wt%, more preferably from 0.5 to 2 wt% by weight of an anti-dye transfer polymer (ADTP) selected from: polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles.
- ADTP anti-dye transfer polymer
- ADTPs anti-dye transfer polymers
- the preferred anti-dye transfer polymer is PVP.
- the shading dye granule preferably contains a carrier preferred examples of carrier are bentonite, sodium chloride, zeolite, and sodium sulphate.
- a binder is a material used to bind together two or more other materials in mixtures. Its two principal properties are adhesion and cohesion.
- the binder is other than a non-ionic surfactant. Binders are standard in the art of laundry detergent granules, examples of which are: Sokalan® CP45, Sokalan® CP5, ethylene glycol, surfactants, anionic surfactants, polyethylene glycol, polyvinyl pyrrolidone, polyacrylates, citric acid and mixtures thereof.
- the binder has a melting point above 30 °C.
- the binder is selected from the group consisting of a polyacrylate, polyethylene glycol, and polyacrylate/maleate copolymer.
- Suitable polymers for use herein are water-soluble.
- water-soluble it is meant herein that the polymers have a solubility greater than 5 g/l at 20 °C in demineralised water.
- the binder is preferably an acidic polymer.
- an acidic polymer it is meant herein that a 1% solution of said polymers has a pH of less than 7, preferably less than 5.5.
- Suitable polymers for use herein have a molecular weight in the range of from 1000 to 280,000, preferably from 1500 to 150,000.
- Suitable polymers which meet the above criteria and are therefore particularly useful in the present invention include those having the following empirical formula I wherein X is 0 or CH2; Y is a comonomer or comonomer mixture; R1 and R2 are bleach-stable polymer-end groups; R3 is H, OH or C1-4 alkyl; M is H, and mixtures thereof with alkali metal, alkaline earth metal, ammonium or substituted ammonium; p is from 0 to 2; and n is at least 10, and mixtures thereof.
- the proportion of M being H in such polymers is preferably such as to ensure that the polymer is sufficiently acidic to meet the acidity criteria as hereinbefore defined.
- Polymers according to formula I are known in the field of laundry detergents, and are typically used as chelating agents, as for instance in GB-A-1,597,756 .
- Preferred polycarboxylate polymers fall into several categories.
- a first category belongs to the class of copolymeric polycarboxylate polymers which, formally at least, are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid as first monomer, and an unsaturated monocarboxylic acid such as acrylic acid or an alpha -C1-C4 alkyl acrylic acid as second monomer.
- preferred polycarboxylate polymers of this type are those in which X is CHO, R3 is H or C1-4 alkyl, especially methyl, p is from about 0.1 to about 1.9, preferably from about 0.2 to about 1.5, n averages from about 10 to about 1500, preferably from about 50 to about 1000, more preferably from 100 to 800, especially from 120 to 400 and Y comprises monomer units of formula II
- Such polymers are available from BASF under the trade name Sokalan® CP5 (neutralised form) and Sokajan® CP45 (acidic form).
- Binder materials are commercially readily available.
- the water soluble polymers of the Sokalan® type sold by BASF® are preferred.
- the granules are preferably of the size from 50 to 1800 microns.
- the granule size is as determined by passing through a mesh sieve.
- Preferably the size is in the range 100 to 800 microns.
- the dye solvent violet 13 was mixed in non-ionic surfactant (7EO) to form a 0.5 wt% solution. To this was added the [nitrolotris(2,1-ethanediyloxy)] tris[propanol] salt of direct violet 9, DV9, (Ex Ciba Speciality Chemicals). The non-ionic was added to the carrier in a high shear mixer. Following this the binder, Sokalam CP5 (ex BASF) was added. Where appropriate polyvinylpyrrolidone, PVP, was added to the starting non-ionic solution.
- the resultant granules were dried in an oven at 353K finally sieved to give granules in the size range 500 to 1400 microns.
- the granules had the following composition. All percentages refer to dry weight%.
- Granule bentonite 7EO DV9 PVP CP5 1* 69.93 20.56 0.20 0.00 9.41 2 69.71 20.68 0.20 0.21 9.51 3 69.41 20.65 0.08 0.21 9.83 4* 69.38 20.93 0.08 0.00 9.58 * comparative examples
- the granules of example 1 were separately added to a detergent powder (20% linear alkyl benzene sulphonate, 30% sodium carbonate, 40% sodium chloride, remainder minors including fluorescer and moisture), at 2 wt%. 10 g of the powder was sprinkled onto a 25 by 25 cm piece of white cotton sheeting, immersed in 1 cm of demineralised water. The cloth was soaked for 90 minutes, then thoroughly rinsed and dried. Each experiment was repeated four times. Cloths soaked with Granule 1 and 2 were compared, and Granule 3 and 4 were compared, as they had equivalent levels of DV9. The eight clothes from each comparison were ranked in terms of the degree of dye staining/spotting. The cloth with the least staining/spotting received a score of 1, that with the second lowest level of staining a score of 2, and so on, so that the most stained/spotted cloth had a score of 8.
- the granules containing the dye transfer inhibition polymer show reduced levels of spotting/staining.
- the granules of example 1 were added to the base washing powder of example 2, such that when the washing powder was dissolved at 2g/L the wash liquor contained 200ppb of SV13.
- Granule 2 and granule 3 were individually added to exemplary powder formulations A, B, C and D at 1 wt % to generate final formulations for use in washing and shading textiles.
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Description
- The present invention relates to the delivery of shading dyes to fabrics.
-
WO 2005/003274, to Unilever , discloses that shading dyes are added to laundry detergents to increase whiteness. One drawback with these powders is that under certain conditions localised spotting occurs on fabric treated with the detergent powder.WO 2006 /020162 andWO 2006/053598 disclose laundry compositions comprising granules containing a dye. - A shading dye granule present in a laundry detergent formulation is susceptible to providing unwanted spotting of fabrics.
- This problem is ameliorated by having an anti-dye transfer agent present in the shading dye granule.
- In one aspect the present invention provides a shading dye granule comprising:
- (i) from 0.001 to 95 wt% of a shading dye;
- (ii) from 0.1 to 99.999 wt% of a dye transfer polymer selected from: polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles;
- (iii) from 0 to 80 wt% of a non-ionic surfactant;
- (iv) from 0 to 20 wt % of an anionic or cationic surfactant;
- (v) from 0 to 99.5 wt% of a carrier; and,
- (vi) from 0 to 50 wt% of a binder, wherein the weight ratio of the dye transfer polymer:the charged surfactant is from 1:0 to 1:1, wherein the shading dye is blue or violet.
- In another aspect the present invention provides a granular laundry detergent composition comprising:
- 1. (a) from 0.00005 to 10 wt% of visually distinct laundry detergent granule as defined in any one of claims 1 to 3;
- 2. (b) from 99.99995 % to 90 wt % of a granular base powder, wherein the granular laundry detergent composition comprises 10 to 50 wt % of an anionic surfactant.
- The surfactant that comes from the base powder may be a mixture of different types of surfactants but the total concentration of anionic surfactant in the granulate laundry detergent is in the range from 10 to 50 wt %. The surfactant that comes from the base powder is preferably greater than 70% anionic surfactant.
- Preferably, the shading dye granule is visually distinct (VD) from a granular background powder in order to provide a visual cue.
- The shading dye granule is for adding to a base powder (main detergent powder).
- Preferably the shading dye granule does not contain an anionic surfactant. When the shading dye granule is admixed with the base powder, which must contain an anionic surfactant, there may be some migration of anionic surfactant to the shading dye granule.
- The ratio of the dye transfer polymer:the charged surfactant prevents spotting whilst permitting dye deposition of substantive dyes from the wash liquors.
- The shading dye is blue or violet. It is preferred that the shading dye(s) have a peak absorption wavelength of from 550nm to 650nm, preferably from 570nm to 630nm. A combination of dyes which together have the visual effect on the human eye as a single dye having a peak absorption wavelength on polyester of from 550nm to 650nm, preferably from 570nm to 630nm. This may be provided for example by mixing a red and green-blue dye to yield a blue or violet shade.
- Dyes are coloured organic molecules which are soluble in aqueous media that contain surfactants. Dyes are described in 'Industrial Dyes', Wiley VCH 2002, K.Hunger (editor).
- Dyes are listed in the Color Index International published by Society of Dyers and Colourists and the American Association of Textile Chemists and Colorists. Dyes are preferably selected from the classes of basic, acid and direct dyes.
- Direct violet and direct blue dyes are preferred. Preferably the dyes are bis-azo or tris-azo dyes. The carcinogenic benzidene based dyes are not preferred.
- Bis-azo copper containing dyes such as direct violet 66 may be used.
-
- ring D and E may be independently naphthyl or phenyl as shown;
- R1 is selected from: hydrogen and C1-C4-alkyl, preferably hydrogen;
- R2 is selected from: hydrogen, C1-C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;
- R3 and R4 are independently selected from: hydrogen and C1-C4-alkyl, preferably hydrogen or methyl;
- X and Y are independently selected from: hydrogen, C1-C4-alkyl and C1-C4-alkoxy; preferably the dye has X= methyl; and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.
- Preferred dyes are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 31, direct violet 35, direct violet 40, direct violet 41, direct violet 51, and direct violet 99.
- Cotton substantive acid dyes give benefits to cotton containing garments. Preferred acid dyes are:
- (i) azine dyes, wherein the dye is of the following core structure:
the dye is substituted with at least one SO3 - or -COO- group;
the B ring does not carry a negatively charged group or salt thereof;
and the A ring may further substituted to form a naphthyl;
the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, Cl, Br, I, F, and NO2. - Preferred azine dyes are: acid violet 50 and acid blue 98.
- (ii)DANSA dyes of the following core structure:-
Y is selected from: NO2; CN; I; Br; Cl; F; H; OCOR2; NHCOR3; R4; R5O; and, NR6R7, wherein R2, R3, R4, and R5 are independently selected from a branched or linear C1 to C7-alkyl chain and R6 and R7 are independently selected from: H; a branched or linear C1 to C7-alkyl chain that is unsubstituted or is substituted by groups independently selected from: OH; Cl; F; OCOCH3; COOCH3; OCOC2H5; and, COOC2H5; and,
X is selected from: H; SO2N (R8) COCH3; SO2N (R8) -Ar; SO2N (R8) -Ar; and SO2-Ar, wherein Ar is an aromatic group and R8 is H, CH3 or C2H5,
with the proviso that the Y ring does not carry a negatively charged group or salt thereof. - (iii) MAAD dyes the following core structure:
- X is selected from -OH, CH3O-, CH3CH2O-, and -NR1R2, wherein R1 and R2 are independently selected from: H, a branched or linear -C1-C7-alkyl chain, -COR3, wherein R3 is a branched or linear -C1-C7-alkyl chain, and a -SO2Ar group, wherein Ar is a phenyl or methyl substituted phenyl group;
- Y is an aromatic group selected from: phenyl and napthyl, and Y may be substituted by R4O-, R4CONH-, R4-, C1, Br, I, F, NO2, and -NR4R5, wherein R4 and R4 are independently selected from: H, a branched or linear -C1-C7-alkyl chain or a phenyl group.
- Other preferred acid dyes are acid violet 17, acid black 1, acid red 17 and acid blue 29.
- Preferably the acid dye is present at 0.001 wt% to 0.006 wt% of the formulation.
- The composition may comprise one or more hydrophobic dyes selected from benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores. Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.
- Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.
- Preferably the hydrophobic dye is present at 0.0005 wt% to 0.004 wt% of the formulation.
- Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International.
- Preferred examples include triarylmethane basic dyes, azo basic dye, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71, basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141 and thiazolium dyes.
- Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton.
- Preferably the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species such as a polymer, so as to the link the dye to this species. Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International.
- Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.
- The shading dye granule according to the present invention comprising from 0.1 to 99.999 wt%, preferably from 0.5 to 18 wt%, more preferably from 0.5 to 2 wt% by weight of an anti-dye transfer polymer (ADTP) selected from: polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles.
- The anti-dye transfer polymers (ADTPs) discussed above are well known in the art and commercially available, reference in made to
US6833336 and references found therein. - The preferred anti-dye transfer polymer is PVP.
- The shading dye granule preferably contains a carrier preferred examples of carrier are bentonite, sodium chloride, zeolite, and sodium sulphate.
- A binder is a material used to bind together two or more other materials in mixtures. Its two principal properties are adhesion and cohesion. The binder is other than a non-ionic surfactant. Binders are standard in the art of laundry detergent granules, examples of which are: Sokalan® CP45, Sokalan® CP5, ethylene glycol, surfactants, anionic surfactants, polyethylene glycol, polyvinyl pyrrolidone, polyacrylates, citric acid and mixtures thereof.
- Preferably, the binder has a melting point above 30 °C.
- Preferably the binder is selected from the group consisting of a polyacrylate, polyethylene glycol, and polyacrylate/maleate copolymer.
- Suitable polymers for use herein are water-soluble. By water-soluble, it is meant herein that the polymers have a solubility greater than 5 g/l at 20 °C in demineralised water.
- The binder is preferably an acidic polymer. By an acidic polymer, it is meant herein that a 1% solution of said polymers has a pH of less than 7, preferably less than 5.5.
- Suitable polymers for use herein have a molecular weight in the range of from 1000 to 280,000, preferably from 1500 to 150,000.
- Suitable polymers which meet the above criteria and are therefore particularly useful in the present invention, include those having the following empirical formula I
- Polymers according to formula I are known in the field of laundry detergents, and are typically used as chelating agents, as for instance in
GB-A-1,597,756 - Such polymers are available from BASF under the trade name Sokalan® CP5 (neutralised form) and Sokajan® CP45 (acidic form).
- Binder materials are commercially readily available. The water soluble polymers of the Sokalan® type sold by BASF® are preferred. The following is a list of such suitable products: Sokalan CP 10; Sokalan CP 10 S; Sokalan CP 12 S; Sokalan CP 13 S; Sokalan CP 45; Sokalan CP 5; Sokalan CP 7; Sokalan CP 9; Sokalan DCS; Sokalan HP 165; Sokalan HP 22 G; Sokalan HP 25; Sokalan HP 50; Sokalan HP 53; Sokalan HP 53 K; Sokalan HP 56; Sokalan HP 59; Sokalan HP 60; Sokalan HP 66; Sokalan PA 110 S; Sokalan PA 15; Sokalan PA 15 CL; Sokalan PA 20; Sokalan PA 20 PN; Sokalan PA 25 CL; Sokalan PA 30; Sokalan PA 40; Sokalan PM 70; and, Sokalan SR 100.
- The granules are preferably of the size from 50 to 1800 microns. The granule size is as determined by passing through a mesh sieve. Preferably the size is in the range 100 to 800 microns.
- The dye solvent violet 13 was mixed in non-ionic surfactant (7EO) to form a 0.5 wt% solution. To this was added the [nitrolotris(2,1-ethanediyloxy)] tris[propanol] salt of direct violet 9, DV9, (Ex Ciba Speciality Chemicals). The non-ionic was added to the carrier in a high shear mixer. Following this the binder, Sokalam CP5 (ex BASF) was added. Where appropriate polyvinylpyrrolidone, PVP, was added to the starting non-ionic solution.
- The resultant granules were dried in an oven at 353K finally sieved to give granules in the size range 500 to 1400 microns.
- The granules had the following composition. All percentages refer to dry weight%.
Granule bentonite 7EO DV9 PVP CP5 1* 69.93 20.56 0.20 0.00 9.41 2 69.71 20.68 0.20 0.21 9.51 3 69.41 20.65 0.08 0.21 9.83 4* 69.38 20.93 0.08 0.00 9.58 * comparative examples - The granules of example 1 were separately added to a detergent powder (20% linear alkyl benzene sulphonate, 30% sodium carbonate, 40% sodium chloride, remainder minors including fluorescer and moisture), at 2 wt%. 10 g of the powder was sprinkled onto a 25 by 25 cm piece of white cotton sheeting, immersed in 1 cm of demineralised water. The cloth was soaked for 90 minutes, then thoroughly rinsed and dried. Each experiment was repeated four times. Cloths soaked with Granule 1 and 2 were compared, and Granule 3 and 4 were compared, as they had equivalent levels of DV9. The eight clothes from each comparison were ranked in terms of the degree of dye staining/spotting. The cloth with the least staining/spotting received a score of 1, that with the second lowest level of staining a score of 2, and so on, so that the most stained/spotted cloth had a score of 8.
- The total score across the 4 cloths for each granule were then compared:
Granules containing 0.20 wt% DV9Granule 1 (no PVP) total score = 24 Granule 2 (PVP) total score = 12 Granule 3 (PVP) total score = 11 Granule 4 (no PVP) total score = 25 - The granules containing the dye transfer inhibition polymer show reduced levels of spotting/staining.
- The granules of example 1 were added to the base washing powder of example 2, such that when the washing powder was dissolved at 2g/L the wash liquor contained 200ppb of SV13.
- To the wash liquor was added pieces of woven cotton and knitted nylon-elastane fabric such the liquor:cloth was 100:1. The liquor was agitated for 60 minutes at 293K, the clothes rinsed twice and the colour change measured by reflectometry and expressed as CIE L*a*b* values.
- The results are given below expressed as the ΔE values relative to the control washed without dye
- All granules gave good deposition of the dyes to the fabrics evidenced by the ΔE values.
Granule Cotton Nylon-elastane ΔE ΔE 1 4.2 4.0 2 3.3 4.2 3 1.4 4.2 4 1.3 4.2 -
Formulation A B C D NaLAS 15 20 10 14 NI(7EO) - - - 10 Na tripolyphosphate - 15 - - Soap - - - 2 Zeolite A24 7 - - 17 Sodium silicate 5 4 5 1 Sodium carbonate 25 20 30 20 Sodium sulphate 40 33 40 22 Carboxymethylcellulose 0.2 0.3 - 0.5 Sodium chloride - - - 5 Lipase 0.005 0.01 - 0.005 Protease 0.005 0.01 - 0.005 Amylase 0.001 0.003 - - Cellulase - 0.003 - - Fluorescer 0.1 0.15 0.05 0.3 Water/impurities/minors remainder remainder remainder remainder - Granule 2 and granule 3 were individually added to exemplary powder formulations A, B, C and D at 1 wt % to generate final formulations for use in washing and shading textiles.
Claims (4)
- A shading dye granule comprising:(i) from 0.001 to 95 wt% of a shading dye;(ii) from 0.1 to 99.999 wt% of a dye transfer polymer selected from: polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles;(iii) from 0 to 80 wt% of a non-ionic surfactant;(iv) from 0 to 20 wt % of an anionic or cationic surfactant;(v) from 0 to 99.5 wt% of a carrier; and,(vi) from 0 to 50 wt% of a binder, wherein the weight ratio of the dye transfer polymer:the charged surfactant is from 1:0 to 1:1, wherein the shading dye is blue or violet.
- A shading dye granule as defined in claim 1, wherein the charged surfactant is an anionic surfactant.
- A shading dye granule according to any preceding claim, wherein the shading dye is selected from: acid dyes, basic dyes and direct dyes.
- A granular laundry detergent composition comprising:(a) from 0.00005 to 10 wt% of visually distinct laundry detergent granule as defined in any one of claims 1 to 3;(b) from 99.99995 % to 90 wt % of a granular base powder, wherein the granular laundry detergent composition comprises 10 to 50 wt % of an anionic surfactant.
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EP09737914.3A EP2268784B2 (en) | 2008-05-02 | 2009-02-18 | Reduced spotting granules |
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EP08155571 | 2008-05-02 | ||
PCT/EP2009/051893 WO2009132870A1 (en) | 2008-05-02 | 2009-02-18 | Reduced spotting granules |
EP09737914.3A EP2268784B2 (en) | 2008-05-02 | 2009-02-18 | Reduced spotting granules |
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CN (1) | CN102015989B (en) |
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BRPI0910682B1 (en) | 2020-09-24 |
ES2400204T5 (en) | 2015-11-26 |
EP2268784B1 (en) | 2012-11-21 |
MY153627A (en) | 2015-02-27 |
CN102015989A (en) | 2011-04-13 |
AR071603A1 (en) | 2010-06-30 |
WO2009132870A1 (en) | 2009-11-05 |
ZA201007320B (en) | 2012-01-25 |
CN102015989B (en) | 2012-07-04 |
EP2268784A1 (en) | 2011-01-05 |
CL2009001053A1 (en) | 2010-01-15 |
ES2400204T3 (en) | 2013-04-08 |
BRPI0910682A2 (en) | 2015-09-29 |
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